Sie sind auf Seite 1von 273

European Commission

14
KH-40-01-448-EN-N
Pollutants in urban waste
water and sewage sludge

ISBN 92-894-1735-8
OFFICE FOR OFFICIAL PUBLICATIONS
OF THE EUROPEAN COMMUNITIES

L-2985 Luxembourg
9 789289 41 735 8
See our publications catalogue at:
http://europa.eu.int/comm/environment/pubs/home.htm
A great deal of additional information on the European Union is available on the Internet.
It can be accessed through the Europa server (http://europa.eu.int).

Cataloguing data can be found at the end of this publication.

Luxembourg: Office for Official Publications of the European Communities, 2001

ISBN 92-894-1735-8

© European Communities, 2001


Reproduction is authorised provided the source is acknowledged.
P
POOLLLLU
UTTA
ANNTTS
S IIN
NUUR
RBBA
ANNW
WAAS
STTE
EWWA
ATTE
ERR

A
ANND
DSSE
EWWA
AGGE
ESSLLU
UDDG
GEE

FFiinnaall R
Reeppoorrtt

P
Prreeppaarreedd bbyy

IIC
COON
N

II C
CCCoonnssuullttaannttss LLttdd,, LLoonnddoonn

U
Unniitteedd K
Kiinnggddoom
m

FFeebbrruuaarryy 22000011

FFoorr D
Diirreeccttoorraattee--G
Geenneerraall E
Ennvviirroonnm
meenntt

1
Executive Summary

Authors

I C Consultants Ltd London

Professor Iain Thornton

(scientific co-ordinator)

Dr David Butler

Paul Docx

Martin Hession

Christos Makropoulos

Madeleine McMullen

Dr Mark Nieuwenhuijsen

Adrienne Pitman

Dr Radu Rautiu

Richard Sawyer

Dr Steve Smith

Dr David White

Technical University Munich

Professor Peter Wilderer

Stefania Paris

IRSA Rome

Dr Dario Marani

Dr Camilla Braguglia

ECA Barcelona

Dr Juan Palerm

Pollutants in Urban Waste Water and Sewage Sludge 2


Executive Summary

Table of Contents

EXECUTIVE SUMMARY 5

1. INTRODUCTION 9

1.1 INTRODUCTION TO POLLUTANTS IN URBAN WASTEWATER (UWW) AND


SEWAGE SLUDGE (SS)
1.2 OBJECTIVES AND GOALS

2. POTENTIALLY TOXIC ELEMENTS, SOURCES, PATHWAYS, AND FATE THROUGH


URBAN WASTEWATER TREATMENT SYSTEMS 13

2.1.SOURCES AND PATHWAYS OF POTENTIALLY TOXIC ELEMENTS IN UWW AND SS


2.1.1 DOMESTIC SOURCES
2.1.2 COMMERCIAL SOURCES
2.1.3 URBAN RUNOFF
2.2 INFLUENCE OF VARIOUS TREATMENT PROCESSES ON THE FATE OF
POTENTIALLY TOXIC ELEMENTS THROUGH WASTEWATER TREATMENT SYSTEMS
(WWTS) AND SEWAGE SLUDGE TREATMENT (SST)
2.3 QUANTITATIVE ASSESSMENT OF POTENTIALLY TOXIC ELEMENTS IN
UNTREATED UWW, TREATED UWW AND TREATED SS

3. ORGANIC POLLUTANTS: SOURCES, PATHWAYS, AND FATE THROUGH URBAN


WASTEWATER TREATMENT SYSTEMS 64

3.1. SOURCES AND PATHWAYS OF ORGANIC POLLUTANTS IN UWW AND SS


3.1.1 DOMESTIC AND COMMERCIAL
3.1.2 URBAN RUNOFF
3.2 INFLUENCE OF VARIOUS TREATMENT PROCESSES ON THE FATE OF ORGANIC
POLLUTANTS THROUGH WWTS AND SS
3.3 QUANTITATIVE ASSESSMENT OF ORGANIC POLLUTANTS IN UNTREATED UWW,
TREATED UWW AND TREATED SS

4. HEALTH AND ENVIRONMENTAL EFFECTS OF POLLUTANTS IN UWW AND SS 94


4.1 POTENTIALLY TOXIC ELEMENTS
4.2 ORGANIC POLLUTANTS

Pollutants in Urban Waste Water and Sewage Sludge 3


Executive Summary

5. A REVIEW OF EU AND NATIONAL MEASURES TO REDUCE THE POTENTIALLY


TOXIC ELEMENTS AND ORGANIC COMPOUNDS CONTAMINATION OF UWW AND SS
102

6. CASE STUDIES 113


(A) PLATINUM GROUP METALS IN URBAN ENVIRONMENT
(B) SUSTAINABLE URBAN DRAINAGE
(C) POLLUTANT SOURCES AND LOAD FROM ARTISANAL ACTIVITIES IN URBAN
WASTEWATER (THE MUNICIPALITY OF VICENZA, INCL. GOLD JEWELLERY SHOPS)
(D) PHARMACEUTICALS IN THE URBAN ENVIRONMENT
(E) PERFUME COMPOUNDS IN WASTEWATER AND SEWAGE SLUDGE
(F) SURFACTANTS IN URBAN WASTEWATERS AND SEWAGE SLUDGE
(G) USE OF POLYELECTROLYTES; THE ACRYLAMIDE MONOMER IN WATER
TREATMENT
(H) CASE STUDY: LANDFILL LEACHATE
(I) PTE (POTENTIALLY TOXIC ELEMENTS) TRANSFERS TO SEWAGE SLUDGE
(J) EFFECT OF CHEMICAL PHOSPHATE REMOVAL ON POTENTIALLY TOXIC
ELEMENT CONTENT IN SLUDGE

7. REPORT SYNOPSIS, DISCUSSIONS AND CONCLUSIONS 205


7.1 COMMENTS, CHALLENGES AND STRATEGIES FOR THE NEXT FIVE TO TEN
YEARS
7.2 IDENTIFICATION OF GAPS IN THE AVAILABLE INFORMATION,
7.3 RECOMMENDATIONS FOR FURTHER RESEARCH
7.4 SUGGESTIONS

APPENDICES 232
APPENDIX A - URBAN WASTEWATER TREATMENT SYSTEMS (WWTS) AND SEWAGE SLUDGE
TREATMENT (SST) - EU AND REGIONAL ASPECTS
APPENDIX B - PHYSICO-CHEMICAL PROPERTIES OF SELECTED POLLUTANTS

DATABASES, REFERENCES

GLOSSARY AND ABBREVIATIONS

Pollutants in Urban Waste Water and Sewage Sludge 4


Executive Summary

POLLUTANTS IN URBAN WASTE WATER AND SEWAGE SLUDGE

EXECUTIVE SUMMARY

Water policy in the European Union is aiming to promote sustainable water use and a major
objective of the new Water Framework Directive (2000/60/EC) is the long-term progressive
reduction of contaminant discharges to the aquatic environment in urban wastewater
(UWW). Sewage sludge is also a product of wastewater treatment and the Urban Waste
Water Treatment Directive (91/271/EEC) aims to encourage the use of sludge whenever
appropriate. Potentially toxic elements and hydrophobic organic contaminants largely
transfer to the sewage sludge during waste water treatment with potential implications for the
use of sludge although some may be emitted with the effluent water.

Inputs of metals and organic contaminants to the urban wastewater system (WWTS) occur
from three generic sources: domestic, commercial and urban runoff. A review of available
literature has quantified the extent and importance of these various sources and the inputs
from different sectors. In general, urban runoff is not a major contributor of potentially toxic
elements to UWW. Inputs from paved surfaces due to vehicle road abrasion and tyre and
brake-lining wear have been identified and losses from Pb painted surfaces and Pb and Zn
from roofing materials represent localised sources of these elements.

Platinum and Pd are components of vehicle catalytic converters and emissions occur as the
autocatalyst deteriorates. Catalytic converters are the main source of these metals emitted
to the environment and releases have increased with the expansion in use of autocatalysts.
Platinum group metals (PGMs) potentially enter UWW in runoff and transfer to sewage
sludge in a similar way to other potentially toxic elements. The Pt content in sludge is
typically in the range 0.1 – 0.3 mg kg-1 (ds) and the background value for soil is 1 µg kg-1.
PGMs are inactive and immobile in soil.

In contrast to potentially toxic elements, inputs of the main persistent organic pollutants of
concern, including: PAHs, PCBs and PCDD/Fs, to UWW are principally from atmospheric
deposition onto paved surfaces and runoff. Combustion from traffic and commercial sources
accounts for the major PAH release to the environment, although inputs from food
preparation sources also represent an important and often under-estimated contribution of
certain PAH congeners. PCDD/Fs are released during waste incineration and also by coal
combustion. Soil acts as a long-term repository for these contaminant types and
remobilisation by volatilisation from soil is an important mechanism responsible for recycling
and redistributing them in the environment. For example, the industrial use of PCBs was
phased out in Europe during the 1980s-1990s, but 90 % of the contemporary emissions of
PCBs are volatilised from soil. Since emission controls are already in place for the main
point sources and PAHs, PCDD/Fs or PCBs enter UWW principally from diffuse atmospheric
deposition and environmental cycling, there is probably little scope, from source control, to
further reduce inputs and concentrations of these persistent organic substances in UWW or
sewage sludge.

Being strongly hydrophobic these organic pollutants are efficiently removed during urban
wastewater treatment (WWTS) and bind to the sludge solids. However, the increasing body
of scientific evidence has not identified a potential harmful impact of these substances on the
environment in the context of the urban wastewater system. Therefore, on balance, the
importance of these contaminants in UWW and sewage sludge has significantly diminished
and there may be little practical or environmental benefit gained from adopting limits or
controls for PAHs, PCBs or PCDD/Fs in UWW or sewage sludge. This is emphasised further
by the high cost and specialist analytical requirements of quantifying these compounds in
sludge and effluent.

5
Executive Summary

Potentially toxic element contamination of urban wastewater and sewage sludge is usually
attributed to discharges from major commercial premises. However, significant progress has
occurred in eliminating these sources and this is reflected in the significant reductions in
potentially toxic element concentration in sewage sludge and surface waters reported in all
European countries where temporal data on sludge and water quality have been collected.
However, potentially toxic element concentrations remain higher in sludge from large urban
wastewater treatment plant (WWTP) compared with small WWTP and they are also greater
in sludges from industrial catchments compared with rural locations. These patterns in
sludge metal content suggest that commercial sources may still contribute significantly to the
total metal load entering UWW. Indeed, recent regional surveys of metal emissions from
commercial premises confirm that further reductions in most elements could be achieved
from this sector. The primary targets for source control include health establishments, small
manufacturing industries (particularly metal and vehicle related activities) and hotel/catering
enterprises, as 30 % of medical centres and 20 % of the other types of activity could be
discharging significant amounts of potentially toxic elements in UWW. Mercury is a specific
case where compulsory use of dental amalgam separators, and substituting Hg with
alternative thermoreactive materials in thermometers, may be effective in reducing
discharges of this element to the WWTS wastewater treatment system .

Faeces contribute 60 – 70 % of the load of Cd, Zn, Cu and Ni in domestic wastewater and
>20 % of the input of these elements in mixed wastewater from domestic and industrial
premises. Faecal matter typically contains 250 mg Zn kg-1, 70 mg Cu kg-1, 5 mg Ni kg-1, 2 mg
Cd kg-1 and 10 mg Pb kg-1 (ds). The other principal sources of metals in domestic
wastewater are body care products, pharmaceuticals, cleaning products and liquid wastes.
Plumbing is the main source of Cu in hard water areas, contributing >50 % of the Cu load
and Pb inputs equivalent to 25 % of the total load of this element have been reported in
districts with extensive networks of Pb pipework for water conveyance. Adjusting water
hardness in order to reduce metal solubilisation from plumbing is technically feasible, but is
likely to be impractical at the regional scale necessary to significantly reduce metal
concentrations in UWW and sludge and may be unpopular with consumers in hard water
areas. The gradual replacement of Pb water pipes can be achieved during building renewal
and renovation programmes.

Reductions in domestic discharges of metals may be possible through increased public


awareness of appropriate liquid waste disposal practices and the provision of accessible
liquid waste disposal facilities. It may be impractical to eliminate the use of metals in body
care products when they are an important active ingredient, but advice and labelling could
be improved to minimise excessive use. Cadmium may be a contaminant present in
phosphatic minerals and removing phosphate from detergent formulations can reduce
associated potential discharges of Cd from domestic sources.

Detergent residues (e.g.nonyl phenol, NP), surfactants (e.g. linear alkyl benzene
sulphonates, LAS), plasticising agents (e.g. di-(2-ethylhexyl)phthalate, DEHP) and
polyacrylamide compounds, added to sludge to aid dewatering, are quantitatively amongst
the most abundant organic contaminants present in UWW and/or sewage sludge.
Dewatering agents based on polyacrylamide may contain traces of the potentially toxic
acrylamide monomer, but this is rapidly degraded and polyacrylamide itself is biologically
inactive. Detergent residues and DEHP are primarily of domestic origin and they are
effectively degraded during aerobic wastewater treatment and are not considered to
represent a potential environmental problem from the discharge of treated effluents to
surface waters. Anaerobic digestion is the principal method employed for stabilising sewage
sludge, but NP accumulates during anaerobic digestion, DEHP is not removed by this
conventional process and, although a significant amount of LAS is biodegraded, residues of
this substance remain because of the large concentrations initially present in raw sludge.
The inability to degrade detergent residues anaerobically and the large concentrations
present in sludge and UWW have prompted ecolabelling initiatives in a number of European
countries to influence consumer choice away from detergents containing these surfactants to

Pollutants in Urban Waste Water and Sewage Sludge 6


Executive Summary

alternative products. This has been successful when supported by extensive public
awareness campaigning. For example, the market share for ecolabelled detergents in
Sweden increased to 95 % and the consumption of LAS has decreased to a similar extent.
Surfactant residues and plasticisers degrade quickly when added to aerobic soils. The
oestrogenic activity of NP is however, a principal concern and measures are proposed to
eliminate the discharge of this substance to UWW.

Natural and synthetic oestrogens are degraded in WWT, but trace amounts remain and
represent the main source of oestrogenic activity in treated effluents. Further work is
necessary to link these substances to oestrogenic responses in aquatic life, but it may be
necessary in future to consider the requirement for tertiary treatment processes (e.g.
ozonation) to eliminate these substances from treated effluents.

A number of other groups of organic compound are identified as being potentially resistant to
wastewater and sewage sludge treatment and the most significant of these are brominated
diphenyl ethers (PBDEs) and chlorinated paraffins. Further research is warranted, in
particular to assess the persistence and potential environmental significance of these
compounds. Synthetic nitro musks are used in perfumed products and traces may be
present in UWW and sludge. Little is known about the environmental fate of these
compounds, but effects on human health from this route seem unlikely given that the main
exposure route is through direct contact.

The degree of removal and biodegradation of pharmaceutical compounds during WWT


varies considerably, although many common analgesic drugs rapidly biodegrade. They are
soluble and transfer to sludge is only of minor concern. Significant amounts of prescribed
drugs are excreted from the body and controlling these inputs from the general population
would be impractical. However, the disposal of unused drugs into UWW should be reviewed
and alternative methods of disposal should be encouraged. The potential significance of
pharmaceuticals in the environment should be assessed in context of the major inputs and
presence arising from widespread veterinary administration of drugs to livestock and farm
waste disposal to land.

A general recommendation to protect the water and soil environment is that a hazard,
biodegradability and fate assessment should be required for all new synthetic chemicals,
irrespective of their purpose or end-use, to determine the potential from them to transfer to
UWW or sewage sludge and the subsequent implications for the environment. Specified
criteria regarding toxicity and biodegradation could be set for compounds that exhibit a
propensity to enter the WWTS and restrictions could be enforced regarding production and
use if these were not met. These decisions would need to balanced against the potential
benefits to health derived from the administration of pharmaceutical drugs.

Strategies aimed at controlling pollutant discharges can only focus on those sources that can
be identified and quantified. Published mass balance calculations indicate there is a high
degree of uncertainty regarding inputs of potentially toxic elements entering the WWTS.
Indeed, unidentified sources may contribute as much as 30 - 60 % of the total metal load
entering the WWTS, although more than 80 % of the Cd discharged is from identified inputs.
This apparent discrepancy could be related to difficulties in measuring the highly variable
inputs of metals in urban runoff and the underestimation of discharges from commercial
premises that have not been subjected to trade effluent control.

The European Commission has proposed a list of 32 priority and 11 hazardous substances
(COM/2001/17) with the aim of progressively reducing emissions and discharges of these
chemicals to the environment. Current developments also suggest that Zn, Cu and LAS may
be the most limiting constituents in sludge if the proposed maximum permissible
concentrations for these substances in soil (Zn and Cu) and sludge (LAS) are carried
through in the revised of Directive 86/278/EEC, but they are not listed as priority substances.
Consideration should be given to designating Zn, Cu and LAS as priority substances to

Pollutants in Urban Waste Water and Sewage Sludge 7


Executive Summary

minimise their to UWW as far as is practicable and to ensure there is a consistent link and
approach to defining the environmental quality standards for sludge with those for
sustainable water use and contaminant discharge reduction.

The main identified priorities for future research relating to contaminant sources, fate and
behaviour in the WWTS are:

• To reduce the uncertainty in quantifying contaminant discharges to UWW by identifying


and surveying specific sources to determine the potential for controlling inputs
particularly from small commercial sources and medical establishments;

• To establish the extent and variability of contaminant entry into UWW by catchment
investigations in relation to precipitation frequency and changes in sludge quality;

• To critically and independently review the fate, behaviour, degradability, toxicity and
environmental consequences of alternative surfactant and plasticing compounds, in
collaboration with the related chemical manufacturing industries, to inform decisions of
the benefits and disadvantages of product substitution in detergent formulations and
plastics manufacture;

• To determine the extent of volatilisation-deposition cycling of persistent organic


pollutants in the environment, identifying the processes controlling the extent and
magnitude of diffuse inputs of these substances to UWW and to provide long-term
predictions of changes in release patterns and the consequences for UWW and sludge;

• To develop a consistent statistical and reporting protocol for national chemical


composition data presented in surveys of sewage sludge quality.

Pollutants in Urban Waste Water and Sewage Sludge 8


1. Introduction

1. INTRODUCTION

The primary objective of this study is to determine the sources of pollution in urban
wastewater (UWW) treated in wastewater treatment systems (WWTS). This includes the
pollutants introduced into the UWW collecting system with run-off rainwater, from domestic
and small commercial sources. The pollutant contents in urban wastewater and sewage
sludge has been evaluated by review of the existing literature, in order that measures may
be proposed to reduce pollution at source.

1.1 Introduction to pollutants in urban wastewater

The pollutants of interest can be divided into two main groups;

• potentially toxic elements (PTEs) including cadmium (Cd), chromium (Cr III and Cr
VI), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn),

• organic pollutants including PAHs, PCBs, DEHP, LAS, NPE, dioxins (PCDD) and
furans (PCDF). Over 6,000 organic compounds have been detected in raw water
sources most of which are due to human activities. While some of these are highly
persistent, others are easily biodegradable in WWTS.

Other pollutants of interest are the metalloids, arsenic and selenium and the metal silver.
Platinum group metals (PGMs), and pharmaceuticals are covered in detail in case studies.

The sources of metal pollution in the wastewater system can be classified into three main
categories:
• Domestic,
• Light industrial (connected to the WWTS) and commercial,
• Urban runoff (which also encompass lithospheric and atmospheric sources).

Pollutants in Urban Waste Water and Sewage Sludge 9


1. Introduction

Atmosphere wet & dry


deposition
deposition

Lithosphere

INDUSTRY

products

DOMESTIC Wastes Product wastes RUNOFF

UWW COLLECTING COMBINED UWW STORM UWW


Wastes
SYSTEMS COLLECTING SYSTEMS COLLECTING SYSTEMS

WASTEWATER
TREATMENT WORKS

Receiving
Water

Figure 1.1: Sources of pollutants in wastewater [after Lester, 1987]

A summary of the various inputs, outputs and pathways followed by water and associated
contaminants from both natural and anthropogenic sources encountered in urban
environments is shown in Figure 1.1. It depicts the drainage area as an open system [Ellis,
1986]. A more detailed urban catchment figure is included in Appendix A.

Wastewater contains many constituents and impurities arising from diffuse and point
sources. Large point sources are easily quantifiable and result from specific activities in the
area that are connected to UWW collecting systems. The contribution from small point
sources, such as households and small businesses, is much more difficult to identify and
quantify, compared to point sources which are usually regulated. UWW is also vulnerable to
illegal discharges of pollutants.

Diffuse sources, such as atmospheric deposition and road runoff have also been
characterised and this study will attempt to present an overview of the available information
in this area. Different methods have been used to estimate point sources and diffuse (non-
point) sources contributions to the pollution load [Vink, 1999]. Inventories of point and diffuse
sources, can link observed water quality trends to changes in socio-economic activities.

Pollutants in Urban Waste Water and Sewage Sludge 10


1. Introduction

The type of pollutants and the magnitude of the outfall loadings are a complex function of:

• size and type of conurbation (commercial, residential, mixed)


• plumbing and heating infrastructure
• atmospheric quality, for example long range transport of pollutants
• factors affecting deposition of pollutants such as precipitation
• activity and intensity surface composition and condition
• urban land use
• traffic type and density
• urban street cleaning
• maintenance practices and stormwater controls
• specific characteristics of storm events
• accidental releases

A review of the sources and pathways of potentially toxic element pollutants in urban
wastewater is presented in Section 2.1 and for organic pollutants in Section 3.1

1.2 Objectives and Goals

The main goals of the study were:

• To determine the sources of potentially toxic elements and organic pollutants in


domestic, commercial, and urban run-off wastewater, which end up in the UWW
collecting system.
• To make a qualitative and quantitative assessment of the pollutants in urban
wastewater and runoff rainwater on the basis of the available data in the literature.
• To evaluate the percentage of inorganic and organic pollutants concentrated in
sewage sludge and the percentage of pollutants released in the environment with the
treated effluents.
• To review wastewater and sewage sludge treatment processes and possible
measures to prevent pollution at source. The most important practices to treat
wastewater and sewage sludge in Europe will be closely examined.
• Based on an overall assessment of the existing data from various sources, to identify
further research directions in those areas with insufficient data.

This report presents a thorough literature review and is primarily based on the analysis and
presentation of case studies from a wide variety of sources and test catchments across
Europe, covering a time range from 1975 to date. Databases used during this project are
listed in the reference section. As theoretical approaches, such as modelling of pollutant
sources and predicted concentrations, are scarce the report attempts to summarise the
monitoring, sampling and measurement of numerous studies, thus providing a concise
overview of pollution source types and concentration ranges. The reader must keep in mind
that there are significant differences between the experiments (in duration, location,
measurement methods, measurement targets and initial conditions), and thus conclusions
on mean or extreme values of pollutants will have to be drawn carefully.

Pollutants in Urban Waste Water and Sewage Sludge 11


2. Potentially Toxic Elements

2. POTENTIALLY TOXIC ELEMENTS: SOURCES, PATHWAYS, AND FATE


THROUGH URBAN WASTEWATER TREATMENT SYSTEMS

The aim is to reduce inputs of pollutants entering the wastewater system to background
levels because this represents the minimum potential extent of contamination that can be
achieved. Potentially toxic elements are of concern because of their potential for long-term
accumulation in soils and sediments.

The majority of metals transfer to sewage sludge (see Fig 2.1). However, 20% may be lost in
the treated effluent, depending on the solubility and this may be as high as 40% - 60% for
the most soluble metal, Ni. Although the use of sludge on agricultural land is largely dictated
by nutrient content (nitrogen and phosphorus), the accumulation of potentially toxic elements
in sewage sludge is an important aspect of sludge quality, which should be considered in
terms of the long-term sustainable use sludge on land. Application of sludge to agricultural
land is the largest outlet for its beneficial use and this is consistent with EC policy of waste
recycling, recovery and use. This is a critical issue due to the increasing amount of sludge
produced, the increasingly stringent controls on landfilling, the public opposition to
incineration (a potential source of further atmospheric pollution), and the ban on disposal at
sea. Consequently sludge quality must be protected and improved in order to secure the
agricultural outlet as the most cost effective and sustainable option.

Figure 2.1: Origin and fate of metals during treatment of wastewater [from ADEME,
1995]

Pollutants in Urban Waste Water and Sewage Sludge 12


2. Potentially Toxic Elements

2.1. Sources and pathways of potentially toxic elements in UWW

The average concentrations of potentially toxic elements in domestic and commercial


wastewater are given in Table 2.1. The maximum concentrations of potentially toxic
elements found in commercial wastewater are generally greater than those in domestic
wastewater. This is supported by Scandinavian studies [SFT-1997a, 1997b, 1999]
considering all urban sectors together, which judged that commercial and light industrial
sectors contributed larger loads of potentially toxic elements to urban wastewater than
household sources.

Table 2.1 Concentrations of metals in domestic and commercial wastewater


[Wilderer and Kolb, 1997 in Munich, Germany]

Element Domestic Commercial


Wastewater [mg.l-1] Wastewater [mg.l-1]

Pb 0.1 ≤ 13
Cu 0.2 0.04-26
Zn 0.1-1.0 0.03-133
Cd <0.03 0.003-1.3
Cr 0.03 ≤20
Ni 0.04 ≤7.3

Table 2.2 Potentially toxic elements in UWW from various sources


(% of the total measured in the UWW)

Pollutant Country Domestic Commercial Urban Not Reference


Wastewater Wastewater Runoff Identified
Cd France 20 61 3 16 ADEME, 1995
Norway 40 SFT report 97/28
UK 30 29 41 WRc, 1994
Cu France 62 3 6 29 ADEME, 1995
Norway 30 SFT report 97/28
UK 75 21 4 WRc, 1994
Cr France 2 35 2 61 ADEME, 1995
Norway 20 SFT report 97/28
UK 18 60 22 WRc, 1994
Hg France 4 58 1 37 ADEME, 1995
Pb France 26 2 29 43 ADEME, 1995
Norway 80 SFT report 97/28
UK 43 24 33 WRc, 1994
Ni France 17 27 9 47 ADEME, 1995
Norway 10 SFT report 97/28
UK 50 34 16 WRc, 1994
Zn France 28 5 10 57 ADEME, 1995
Norway 50 SFT report 97/28
UK 49 35 16 WRc, 1994

Pollutants in Urban Waste Water and Sewage Sludge 13


2. Potentially Toxic Elements

Cd distribution Cu distribution

Domestic Domestic
Storm events Storm events
Commercial Commercial
Non Identified
Non Identified

Cr distribution Hg distribution

Domestic Domestic
Storm events Storm events
Commercial Commercial
Non Identified
Non Identified

Pb distribution Ni distribution

Domestic Domestic
Storm events Storm events
Commercial Commercial
Non Identified
Non Identified

Zn distribution

Domestic
Storm events
Commercial
Non Identified

Figure 2.2 Pie charts showing the breakdown of potentially toxic elements entering
UWW from different sources in France (ADEME 1995) This uses the French data in Table
2.2 but is included to give a clearer visual representation of the source breakdown for the
different metals.

Pollutants in Urban Waste Water and Sewage Sludge 14


2. Potentially Toxic Elements

The data in Table 2.2 and Figure 2.2 show that for some elements over 50% of the
potentially toxic elements in wastewater are unaccounted for. This is in line with findings by
Critchley & Agy [1994] Better source inventory data is essential in order to effectively target
reductions in emissions from all the different sources. It may be that identification of some of
the industrial sources will require increased trade effluent discharge controls if
concentrations of pollutants are to be reduced. Domestic and urban run-off sources may
require different types of action, such as changes in products used.

Emissions of potentially toxic elements from industrial point sources were the major sources
of pollution to urban wastewater. However, stringent and more widespread limits applied to
industrial users has reduced the levels of potentially toxic elements emitted by industry into
urban wastewater considerably. This continues a general decline of potentially toxic
elements from industrial sources since the 1960s, due to factors such as cleaner industrial
processes, trade effluent controls and heavy industry recession. For example, the liquids
used in metal finishing typically contain 3-5 mg.l-1 of copper, 5-10 mg.l-1 of chromium, 3-5
mg.l-1 of zinc, 5-10 mg.l-1 of zinc, 1-5 mg.l-1 of cyanide, and 10-50 mg.l-1 of suspended solids
[Barnes, 1987]. However, metal finishing industries are now required to pre-treat these
liquids before disposal, reducing toxic discharges by 80-90%.

In the Netherlands, a survey of potentially toxic element load in UWW influent [SPEED,
1993], also made estimations for 1995 and forecasts up to 2010. The overall prevalence of
potentially toxic elements in the UWW system is expected to decrease, mainly due to a
decrease in runoff and industrial sources, while the potentially toxic elements share in
WWTS loads from households was expected to increase. As industrial sources of potentially
toxic elements in UWW decline, the relevant importance of diffuse sources will increase.

Wiart and Reveillere [1995] carried out studies at the Achères WWTS in France. Their
studies showed a significant decrease (50-90%) in the potentially toxic element content of
sewage sludge since 1978, following the application of the "at-source discharge reduction"
policy [Bebin, 1997]. However, the main concern is now with organic pollutants, and current
regulations require monitoring of the influent, in order to set up a baseline database from
which limits may then be devised.

Pollutants in Urban Waste Water and Sewage Sludge 15


2. Potentially Toxic Elements

2.1.1 Domestic sources

Domestic sources of potentially toxic elements in wastewater are rarely quantified due to the
difficulty in isolating them. Domestic sources include the potentially toxic elements
discharged from the household to UWW collecting systems and, in addition, corrosion from
materials used in distribution and plumbing networks, tap water and detergents.

A study by RIVM (Dutch Institute of Public Health and the Environment) in the Netherlands
[SPEED, 1993], quantified the waterborne emissions of potentially toxic elements from
household sources, dentistry and utility buildings in the urban environment. Table 2.3 shows
the data of waterborne potentially toxic elements emissions in tonnes per annum.

Table 2.3 Emissions by Dutch households of potentially toxic elements


[adapted from SPEED, 1993].

Potentially Gross waterborne emissions* tonnes.y-1 to surface


toxic element water (1993)
Household Dentistry Utility buildings
sources
Copper 94 0.6 27
Zinc 118 - 26
Lead 13 - 3.1
Cadmium 0.7 - 0.2
Nickel 7.3 - 0.9
Chromium 2.9 - 0.3
Mercury 0.3 2.3 0.01
* 96 % of the waterborne emissions are expected to go to the UWW collecting systems, with 4% going
directly to surface waters.

Domestic products containing potentially toxic elements used on a regular basis at home
and/or at work, are also reviewed by Lewis [1999]. The following lists the principal PTEs and
products containing them that may enter urban wastewater;

Cadmium: is predominantly found in rechargeable batteries for domestic use (Ni-Cd


batteries), in paints and photography. The main sources in urban wastewater are from
diffuse sources such as food products, detergents and bodycare products, storm water
[Ulmgren, 2000a and Ulmgren, 2000b].

Copper: comes mainly from corrosion and leaching of plumbing, fungicides (cuprous
chloride), pigments, wood preservatives, larvicides (copper acetoarsenite) and antifouling
paints.

Mercury: most mercury compounds and uses are now banned or about to be banned,
however, mercury is still used in thermometers (in some EU countries) and dental
amalgams. Also, mercury can still be found as an additive in old paints for water proofing
and marine antifouling (mercuric arsenate), in old pesticides (mercuric chloride in fungicides,
insecticides), in wood preservatives (mercuric chloride), in embalming fluids (mercuric
chloride), in germicidal soaps and antibacterial products (mercuric chloride and mercuric
cyanide), as mercury-silver-tin alloys and for "silver mirrors".

Nickel: can be found in alloys used in food processing and sanitary installations; in
rechargeable batteries (Ni-Cd), and protective coatings.

Lead: The main source of lead is from old lead piping in the water distribution system. It can
be found in old paint pigments (as oxides, carbonates), solder, pool cue chalk (as
carbonate), in certain cosmetics, glazes on ceramic dishes and porcelain (it is banned now

Pollutants in Urban Waste Water and Sewage Sludge 16


2. Potentially Toxic Elements

for uses in glazes), also in "crystal glass". Lead has also been found in wines, possibly from
the lead-tin capsules used on bottles and from old wine processing installations.

Zinc: comes from corrosion and leaching of plumbing, water-proofing products (zinc
formate, zinc oxide), anti-pest products (zinc arsenate - in insecticides, zinc dithioamine as
fungicide, rat poison, rabbit and deer repellents, zinc fluorosilicate as anti-moth agent), wood
preservatives (as zinc arsenate), deodorants and cosmetics (as zinc chloride and zinc
oxide), medicines and ointments (zinc chloride and oxide as astringent and antiseptic, zinc
formate as antiseptic), paints and pigments (zinc oxide, zinc carbonate, zinc sulphide),
printing inks and artists paints (zinc oxide and carbonate), colouring agent in various
formulations (zinc oxide), a UV absorbent agent in various formulations (zinc oxide), "health
supplements" (as zinc ascorbate or zinc oxide).

Silver: originates mainly from small scale photography, household products such as
polishes, domestic water treatment devices, etc. [Shafer, et.al, 1998, Adams and Kramer,
1999]

Arsenic and Selenium: are among the potentially toxic metalloids found in urban
wastewaters. These are of importance due to their potential effects on human/animal health.
Only a limited number of studies have taken these into account. Arsenic inputs come from
natural background sources and from household products such as washing products,
medicines, garden products, wood preservatives, old paints and pigments. Selenium comes
from food products and food supplements, shampoos and other cosmetics, old paints and
pigments. Arsenic is present mainly as DMAA (dimethylarsinic acid) and as As (III) (arsenite)
in urban effluents and sewage sludge [Carbonell-Barrachina et.al., 2000].

Pollutants in Urban Waste Water and Sewage Sludge 17


2. Potentially Toxic Elements

Household products

Household products were investigated as potential sources of PTE pollution entering the
WWTS. Table 2.4 shows metal concentrations in various household products in UK
Table 2.4 Metal concentrations in household products
[Comber and Gunn, 1996, WRc report, 1994].

Product Zinc Copper Cadmium Nickel


(µg g-1) (µg g-1) (µg g-1) (µg g-1)
Washing Powders a 37.9 1.4 74.3 <0.5
‘Big Box’ b 35.9 <0.5 136.0 <0.5
c 3.3 <0.5 6.6 <0.5
Washing Powders ‘Ultra’ a <0.1 <0.5 24.0 <0.5
b 2.3 1.40 10.6 <0.5
c 1.0 1.38 11.8 <0.5
Fabric Conditioners a 0.1 <0.5 9.4 0.6
b <0.1 <0.5 9.0 <0.5
c 0.1 <0.5 10.7 <0.5
Hair Conditioners a <0.1 <0.5 16.8 <0.5
b 1.0 1.4 17.2 <0.5
c 1.7 <0.5 8.6 <0.5
d 0.5 1.4 68.0 1.0
Cleaners a 0.3 2.8 26.0 <0.5
b <0.1 <0.5 17.8 <0.5
Shampoo (medicated) a 4900 1.4 17.4 <0.5
Washing Up Liquid a 0.2 1.1 11.0 0.8
Bubble bath a 0.2 <0.5 13.6 <0.5
b <0.1 1.4 10.4

As can be seen from Table 2.4 there is a great deal of variability between products and also
between types of the same products in terms of potentially toxic element content.

The high variability of cadmium concentrations found in the big box washing powders can be
explained by the differences in the composition of phosphate ores used in their production.
Cadmium impurities in these phosphate ores have been shown to vary greatly depending on
mining source [Hutton et al reported in WRc report 1994]. Reducing the amount of
phosphate in washing powders, or choosing phosphate ores with low Cd concentration could
lead to a reduction in Cd in wastewater from diffuse sources. In Sweden the amount of
cadmium in sewage sludge was reduced from 2 mg kg-1 ds to 0.75 mg kg-1 ds [Ulmgren,
1999], and cadmium discharges from households in the Netherlands have been substantially
reduced due to the switch to phosphate-free detergents [SPEED, 1993]. The 'Ultra' washing
powders, usually phosphate-free, have smaller potentially toxic element contents than the
traditional powders, and are designed to be used in smaller quantities. A shift to these newer
products will reduce the overall metal load from this source.

The products with the highest metal contents are shown in bold in Table 2.4. The medicated
(anti-dandruff) shampoos contain zinc pyrithione and the high zinc concentrations will thus
raise the zinc inputs to the UWW collecting system. In 1991 these shampoos were estimated
to represent 26% of the market [*BLA Group 1991- reported in Comber and Gunn 1996 and
WRc 1994]. Cosmetics are not included here but they may also contain high levels of zinc
and several of these products are likely, at least in part, to enter in the waste water system.
One study in France [ADEME, 1995a] identified that the main sources of potentially toxic
elements in domestic wastewater came from cosmetic products, medicines, cleaning
products and liquid wastes (including paint), which were directly discharged from the
household sink.

Pollutants in Urban Waste Water and Sewage Sludge 18


2. Potentially Toxic Elements

Table 2.5 provides a general picture of some of the potentially toxic elements in various
domestic products including food products [after Lester, 1987 and WRc report 1994].
Sources for each metal are marked with a tick. In addition to the main metals considered in
this study, cadmium, chromium (III and VI), copper, mercury, nickel, lead and zinc, silver,
arsenic, selenium and cobalt are also included. Other metals and metalloids for which more
information is necessary include manganese, molybdenum, vanadium, antimony and tin.

TABLE 2.5 Domestic sources of potentially toxic elements in urban wastewater


[modified from Lester, 1987, and WRc, 1994]
Product type Ag As Cd Co Cr Cu Hg Ni Pb Se Zn
Amalgam fillings √
and thermometers
Cleaning products √ √
Cosmetics, √ √ √ √ √ √ √
shampoos
Disinfectants √
Fire extinguishers √
Fuels √ √ √ √
Inks √ √
Lubricants √ √ √
Medicines and √ √ √ √ √
Ointments
Health supplements √ √ √ √ √
Food products √ √ √ √ √
Oils and lubricants √ √ √ √
Paints and √ √ √ √ √ √ √ √ √ √
pigments
Photographic √ √ √
(hobby)
Polish √ √ √
Pesticides and √ √ √ √ √
gardening products

Washing powders √ √ √
Wood- √ √ √
preservatives
Other sources
Faeces and Urine √ √ √ √ √ √ √ √ √
Tap Water √ √ √ √ √
Water treatment √ √ √ √ √
and heating
systems

Domestic activities

The main domestic sources of potentially toxic elements in wastewater were estimated by
WRc [1994] to be (in order of importance):
cadmium: faeces > bath water > laundry > tap water > kitchen
chromium: laundry > kitchen > faeces > bath water > tap water
copper: faeces > plumbing >tap water > laundry > kitchen
lead: plumbing > bath water > tap water > laundry > faeces > kitchen
nickel: faeces > bath water > laundry > tap water > kitchen
zinc: faeces > plumbing > tap water > laundry > kitchen.

Pollutants in Urban Waste Water and Sewage Sludge 19


2. Potentially Toxic Elements

Estimates of the mean potentially toxic element inputs to UWW collecting systems from
domestic activities are presented in Table 2.6. The results show that for the particular UK
(hard water) catchment studied in 1994, the domestic inputs of copper and zinc are major
contributors to the overall level of potentially toxic elements reaching the WWTS. Most of the
zinc is derived from faeces and household activities such as washing and cleaning.
Chromium, lead and cadmium were also found to be mainly from domestic activities rather
than from plumbing.

Table 2.6 Potentially toxic element loads to the UWW collecting systems from
domestic activities [adapted from Comber and Gunn, 1996]

Activity (study in a hard Load (µg.person-1.day-1)


water catchment area) Zn Cu Pb Cd Ni Cr
Washing Machine Input Water 662 6859 36.0 0.6 27 4
Washing 4452 977 515 11 52 238
Dishwashing Input Water 39 69 2.9 0.03 2 0.3
(machine) Washing 42 8 6 1.3 2 10
Dishwashing Input Water 591 6125 32 0.5 24 3.7
(hand) Washing 1010 <20 46 7.8 138 136.7
Bathing Input Water 1140 10651 46 1.0 40 5.9
Bathing 1095 67 45 13.1 9 7.4
Toilet Input Water 2531 8082 63 2.0 77 8.5
Faeces 11400 2104 121 48.0 284 51.5
Miscellaneous Input Water 1453 6951 62.7 1.2 54 7.0

Predicted Total 24416 41894 978 86 710 464.2


Measured mean from Catchment 15314 46772 1237 71 925 686
housing estates Population
50 000
Predicted load to UWW 1.2 2.1 0.05 0.01 0.04 0.02
collecting systems from
domestic sources (kg/day)
Measured mean total load to 2.6 3.3 0.3 N/A 0.1 0.15
the WWTS kg per day
% of potentially toxic 46.0 64.2 16.9 N/A 25.7 15.3
elements from domestic
sources in the UK

Based on the above results, changes in population behaviour, such as a shift to dishwasher
use rather than washing up by hand, would reduce potentially toxic element input into the
WWTS.

It is noted that, while the quantities of potentially toxic elements dissolved in water from
plumbing will vary across the Europe they will make up a significant proportion of the
potentially toxic element loading going to any WWTS.

Table 2.7 summarises the percentages of the domestic inputs at the Shrewsbury WWTS, in
the UK. As can be seen over a fifth of the copper, zinc, cadmium and nickel entering the
wastewater treatment plant from domestic sources are from faeces. This emphasises the
fact that faeces are an important source of potentially toxic elements pollution. This source is
also very difficult to reduce. The percentage inputs of chromium and lead from this source
are much lower.

Pollutants in Urban Waste Water and Sewage Sludge 20


2. Potentially Toxic Elements

Table 2.7 Potentially toxic elements entering wastewater, breakdown by source [WRc,
1994]
Cu Zn Cd Ni Pb Cr
Percentages of total load
Break down of domestic sources as percentage of total metal entering WWTS
Plumbing Input Bathing 12.4 1.2 0.3 1.6 4.4 0.1
(% of total entering WWTS) Toilet 8.9 2.1 0.5 4.3 8.1 0.2
Washing 8.0 0.7 0.2 0.9 3.2 0.1
Machine
Miscellaneous 8.0 1.2 0.3 2.4 6.1 0.2
Dishwashing 7.1 0.6 0.2 0.8 2.7 0.1
Activities Faeces 20.6 28.0 20.0 23.6 3.1 2.1
(% of total metal entering Washing 9.53 10.8 4.6 4.4 18.6 9.3
WWTS) Machine
Bathing 0.2 2.6 0.9 0.8 1.1 0.3
Dishwashing 2.6 4.6 11.2 1.1 5.1

Human faeces contain high concentrations of potentially toxic elements from normal dietary
sources and this represents a principal input of metals to domestic wastewater and sludge of
domestic origin. The normal dietary contribution of metals represents the background metal
concentration represents the background metal concentration and is the minimum
achievable in waste water and sludge.

Concentrations are expected to vary with the intake of metals in the diet, drinking water and
medication and may also be influenced by the increasing prevalence of mineral
supplementation of food, for example with zinc, iron, selenium, and manganese. One study
in France (ADEME 1997) found the following concentrations of potentially toxic elements in
faeces (as dry matter): Zn: 250mg kg-1, Cu: 68mg kg-1, Pb: 11mg kg-1, Ni: 4.7mg kg-1, and
Cd: 2mg kg-1. Differences can also occur due to geographical variations in the dietary habits.
For some elements, such as Cd, the weighted average concentration in sludge (e.g. 3.3 mg
kg-1 in the UK) is typical of the amount originating naturally in faeces from the normal trace
amounts of this element ingested in food (typically 18.8 µg d-1). Other differences in reported
concentrations of Cd in different EU member states is discussed in section 2.3.

Domestic water and heating systems

Studies in the USA [Isaac et.al, 1997], and Europe [WRc 1994] show that corrosion of the
distribution-plumbing-heating networks contribute major inputs of Pb, Cu and Zn. Lead
concentration for instance can vary between 14 µg.l-1 at the household input and 150 µg.l-1 at
the output.

It has been found that concentrations of copper in sewage sludge are directly proportional to
water hardness [Comber et al 1996]. Hard water (high pH) is potentially more aggressive to
copper and zinc plumbing, increasing leaching. However, the opposite is true for lead in that
it dissolves more readily in than soft, acidic water. The high lead levels in drinking water in
Scotland due to its soft waters are a major concern.

Reductions in the amounts of copper and lead in wastewater have been reported by pH
adjustment of tap water and addition of sodium silicate. The addition of alkali agents to water
at the treatment stage and the replacement of much lead piping has led to reductions in lead
concentration [Comber et al., 1996]. Adjusting the pH of tap water may be limited by
practical and economic factors.

Zinc in domestic plumbing comes from galvanised iron used in hot water tanks but is less
problematic than lead and copper because the amount decreases with the ageing of the
installations. Copper corrosion and dissolution is also greater in hot water than in cold water

Pollutants in Urban Waste Water and Sewage Sludge 21


2. Potentially Toxic Elements

supplies [Comber et al 1996]. The 'first draw' (initial flow of water in the morning) has higher
amounts of copper and lead compared to subsequent draws [Isaac et.al., 1997]. The Cu
content was found to be between 73.7 and 1430 µg l-1, and Pb content between 8.3 and
22.3 µg l-1, much greater than in the average effluent from households. Water treatment
would be recommended for certain water domestic uses, such as boilers and heating
systems, in order to reduce the metal corrosion.

The type of housing was also found to be important by the WRc report [1994]. Table 2.8
gives an average concentration of effluent from two types of estates, "1960s residential" and
"1990s residential" from daily bulk- and flow-weighted samples. The larger copper levels
from the "modern estate" can be explained by the newer plumbing system. In many
countries copper is the major element used in plumbing. In the UK it has been estimated that
leaching from copper plumbing accounts for over 80% of the copper entering domestic
wastewater [Comber et al 1996]. The higher lead level found in the newer housing did not
correlate with similar studies comparing old and new housing and could not be explained
satisfactorily; as in general older houses in the UK contain more lead plumbing. Lead from
solders in the piping system may also be an important source. In other regions of the EU
steel and zinc galvanised iron are used widely. This may explain why zinc in sludge is
proportionally greater than Cu in other member states compared with the UK.

Table 2.8 Mean concentration of potentially toxic elements in the effluent from
households in two types of residential areas [WRc Report, 1994]

Potentially toxic Zn Cu Ni Cd Pb Cr Hg
element concentration µg.l-1
" 1960s residential" 74.3 219.4 5.2 0.71 9.02 5.65 0.114
" 1990s residential" 147.0 458.3 7.56 0.34 90.61 3.3 0.088

In summary, potentially toxic elements entering UWW collecting systems from domestic
sources are related to:

• household water consumption


• the plumbing and heating system in the household
• the concentrations of potentially toxic elements in the products used in the household
and quantities of the products used
• any grey water recycling schemes
• how much of the products are discharged into wastewater.

Pollutants in Urban Waste Water and Sewage Sludge 22


2. Potentially Toxic Elements

2.1.2 COMMERCIAL SOURCES

Limited data is available for the potentially toxic element contribution from commercial
sources and health care inputs (such as hospital and clinical wastes). Inputs from artisanal
sources are looked at in more detail in a separate Case Study in Section 6.

Cadmium could originate from laundrettes, small electroplating and coating shops, plastic
manufacture, and also used in alloys, solders, pigments, enamels, paints, photography,
batteries, glazes, artisanal shops, engraving, and car repair shops. Data from ADEME
[1995], estimated that worldwide, 16000 tonnes of cadmium were consumed each year; 50-
60% of this in the manufacture of batteries and 20-25% in the production of coloured
pigments.

Chromium is present in alloys and is discharged from diffuse sources and products such as
preservatives, dying, and tanning activities. Chromium III is widely used as a tanning agent
in leather processing. Chromium VI uses are now restricted and there are few commercial
sources.

Copper is used in electronics, plating, paper, textile, rubber, fungicides, printing, plastic, and
brass and other alloy industries and it can also be emitted from various small commercial
activities and warehouses, as well as buildings with commercial heating systems.

Lead, as well as being used as a fuel additive (now greatly reduced or banned in the EU) it
is also used in batteries, pigments, solder, roofing, cable covering, lead jointed waste pipes
and PVC pipes (as an impurity), ammunition, chimney cases, fishing weights (in some
countries), yacht keels and other sources.

Mercury is used in the production of electrical equipment and is also used as a catalyst in
chlor-alkali processes for chlorine and caustic soda production. The main sources in effluent
are from dental practices, clinical thermometers, glass mirrors, electrical equipment and
traces in disinfectant products (bleach) and caustic soda solutions.

Nickel is used in the production of alloys, electroplating, catalysts and nickel-cadmium


batteries. The main emission of nickels are from corrosion of equipment from launderettes,
small electroplating shops and jewellery shops, from old pigments and paints. It also occurs
in used waters from hydrogenation of vegetable oils (catalysts).

Zinc is used in galvanisation processes, brass and bronze alloy production, tyres, batteries,
paints, plastics, rubber, fungicides, paper, textiles, taxidermy (zinc chloride), embalming fluid
(zinc chloride), building materials and special cements (zinc oxide, zinc fluorosilicate),
dentistry (zinc oxide), and also in cosmetics and pharmaceuticals. The current trend towards
electrolytic production of zinc which, in contrast to thermally produced zinc, has virtually no
cadmium contamination. This means that cadmium pollution to UWW due to the corrosion of
galvanised steel will in time become negligible. [SPEED 1993].

Platinum and platinum group metals (PGMs) such as palladium and osmium can enter
UWW from medical and clinical uses, mainly as anti-neoplastic drugs. The amount in
hospital/clinical effluent has been estimated to be between 115 and 125 ng l-1 [Kümmerer
and Helmers, 1997, Kümmerer et.al., 1999] giving a total emission of 84-99 kg per annum
from hospitals in Germany. Other sources of platinum metals in the environment related to
commercial activities come from catalysts used in petroleum/ammonia processing and
wastewaters, from the small electronic shops, jewellery shops, laboratories and glass
manufacturing. Section 6 contains a detailed Case Study (a) on PGMs in urban waste water
and sewage sludge.

Pollutants in Urban Waste Water and Sewage Sludge 23


2. Potentially Toxic Elements

Silver could potentially be emitted from photographic and printing shops, from jewellery
manufacturers and repairers, plating and craft shops, glass mirror producers and small-
scale water filters.

Studies in Spain showed the presence of elevated concentrations of Cd, Cu, Hg, Pb and Zn
in urban wastewater and in the coastal environment [Castro, et.al., 1996], with large
concentrations of copper and zinc possibly due to the use of fungicides in glass-houses.

A summary of concentrations of metals found in effluent from commercial sources in


different regions in Europe is given in Table 2.9.

Table 2.9 Summary of potentially toxic elements in UWW from commercial sources
( g l-1)
Element Country Industry Industrial Effluent Reference
-1
(µg l )
Cd Germany All sectors 3-1,250 Wilderer et al 1997
Greece Petroleum industries 300-400 NTUA, 1985
Cu Germany All sectors 37-26,000 Wilderer et al 1997
Greece Metal and electrical industries 5,000-10,000 NTUA, 1985
Italy Artisanal galvanic shops 20,500 EBAV, 1996
Goldsmiths and jewellery 700-1,900
shops (max.13,300)
Cr Germany All sectors <10-20,100 Wilderer et al 1997
Greece Metal and electrical industries 500-13,000 NTUA, 1985
Tanneries 100-7,000,000
Italy Artisanal galvanic shops 16,000 EBAV, 1996
Pb Germany All sectors <50-13,400 Wilderer et al 1997
Greece Metal and electrical industries 500 NTUA, 1985
Italy Ceramics and photoceramics 6,000 EBAV, 1996
shops
Ni Germany All sectors <10-7,300 Wilderer et al 1997
Greece Metal and electrical industries 500-14,500 NTUA, 1985
Italy Artisanal galvanic shops 19,700 EBAV, 1996
Zn Germany All sectors 30-133,000 Wilderer et al 1997
Greece Metal and electrical industries 60-2,830 NTUA, 1985
Italy Goldsmiths and jewellery 1,000 (max. 7,000) EBAV, 1996
shops
As Spain Paper mills 3.4 Navarro, et.al
1993

In 1999, a project carried out by Anjou Recherche [LIFE, 1999], attempted to classify all
commercial sources of wastewater pollution based on a matrix of 73 main pollutants
including many potentially toxic elements and certain organic pollutants. The UWW
collecting system of Louviers, for example, had listed 1054 establishments of which 39%
were capable of emitting at least one of these pollutants. Ten classes of activities were
recorded, of which health and social action (33.5%), manufacturing industry (20%), hotels
and restaurants (17.8%), and collection services (10%) appeared most often as potential
polluters. It was found on average, that between a third and a half of the activities emitted
pollutants. In the Louviers area, it was found that 53 urban businesses and institutions could
potentially emit cadmium, 168 chromium, 147 copper, 35 nickel, 167 mercury, 50 lead, and
63 zinc. This suggests that more can be done to reduce trade effluent discharges.

Between 1990 and 1992, Stockholm Water Company investigated measures to reduce
discharges of potentially toxic elements into the UWW collecting system. This programme
involved the following groups: the city council, neighbouring municipalities, small businesses
and industry, professional associations and NGOs as well as local households. Efforts to
reduce pollution entering the wastewater system were divided among all the major sources
i.e., small businesses and industry, wastewater from urban runoff, household wastewater
and storm water.

Pollutants in Urban Waste Water and Sewage Sludge 24


2. Potentially Toxic Elements

Collaborative projects were developed both for research, product development and
educational programmes. Local commercial organisations (particularly the Swedish Dental
Federation) co-operated in the project; new technologies were developed and an evaluation
of alternative products was carried out. Pollution limits were imposed that were determined
to be appropriate to encourage the purchase of the endorsed environmental products. This
programme of research, and earlier work during the 1980s led to a reduction of between 50
and 80% of potentially toxic elements in sewage sludge [Ulmgren 2000a].

The results of some more specific investigations into sources of potentially toxic elements in
UWW are outlined below.

Motor industry - vehicle washing

Scandinavian studies [SFT-1997a, 1997b, 1999] showed that the motor industry, followed by
vehicle workshops contribute most to the potentially toxic element load in UWW. Vehicle
washing, particularly heavy goods vehicles (HGVs), was found to be an important source of
potentially toxic element contamination.

In Sweden, oil separators are commonly used in vehicle washing and motor industries
before discharging effluent to UWW collecting systems. Most facilities in Sweden are
reported to be equipped with combined oil separators and sludge traps where the dispersed
oil and sludge should be retained. However, tests at one of the light vehicle (LV) washing
facilities showed that this equipment was ineffective with practically no difference between
the influent (before the separator) and the effluent (after the separator). This was due to the
formation of stable emulsions in the wastewater caused by the detergents in the
microemulsion formulations used for vehicle washing [Paxéus, 1996b].

A study by the Norwegian Pollution Control Authority [SFT, 1999] examining potentially toxic
element pollutants in Norway found that out of six petrol stations investigated, only one had
an oil separator/sand trap that worked effectively. Although designed to reduce the
contamination of urban wastewater, oil separating devices are generally ineffective at
reducing pollutant emissions from vehicle washing and motor industry facilities.

Dental practices and healthcare (mercury)

In the late 1980s, the high concentration of mercury in sewage sludge (SS) at Henrikdal
WWTS, Stockholm, prompted an investigation to identify potential sources (Table 2.10). It
was concluded that the high mercury content of sludge was attributable to dental practices
and the use of mercury in dental amalgams. Amalgam separators were ineffective at
retaining mercury and new legislation was introduced to combat this [Ulmgren, 2000a].
Recent reduction or bans on the use of mercury in various products, such as batteries and
thermometers, has led to a reduction of mercury input into UWW [Ulmgren, 2000a and
Ulmgren, 2000b]. Mercury recycling schemes have also proved to be successful, and could
be extended to other countries and activities.

Other discharges from dental technicians shops are covered in detail in Section 6, Case
Studies.

Pollutants in Urban Waste Water and Sewage Sludge 25


2. Potentially Toxic Elements

Table 2.10 Sources of mercury in urban wastewater in Sweden


[Table adapted from text, Ulmgren 2000a]

Source Comments
Heavy Industry no Ruled out as a source of mercury to UWW and SS as these were
not connected to the UWW collecting system
Small and no Ruled out as they were operated in such a way that no
Medium contamination of the wastewater was likely
Enterprises
(18 Companies)
Storm Drains yes 20% of the total mercury load came from storm drains. This was
largely traced to the deposition of particulates emitted from
crematoria which are estimated to be about 50 kg of mercury a year
Household yes About 15% of the mercury entered the waste water system through
Wastewater the use of mercury thermometers in the home, and also from small
amounts of mercury in food and amalgam fillings in teeth
Dentists and yes High mercury content of sludge was largely attributable to dental
Dental practices and the use of mercury in dental amalgams
Technicians
Hospitals yes Samples indicated that hospitals emit 10% of the mercury loading
Old Sewage yes Investigations in the last few years have found many sources of
Pipes mercury in old pipes

Similar findings have been reported in other countries. A WRc report [1994] established that
in the UK mercury emissions are much higher from commercial, rather than domestic
sources, mainly due to dental practices. In France, it is estimated [Agence de l'Eau, 1992]
that between 73 and 80 % of the mercury in UWW is from dental practices and amalgam
fillings corrosion. In the Louviers area of France, the analysis of wastewater and sewage
sludge showed that out of the total load of mercury, 50% was lost from medical practices,
13% from dentistry practices, 28% from medical auxiliaries (nurses etc.), 4% from hospital
activities, 4% from veterinary activities, and 1% from ambulance activities. Thus, in this
instance, targeting medical/dental practices may help reduce pollution from mercury [LIFE,
1999].

Other sources of mercury


In 1993, the amount of mercury entering France was 209 tonnes, the amount leaving France
was 87 tonnes, and hence 122 tonnes were entering the environment in the form of waste
[AGHTM, 1999-2000] (see Table 2.11).

Table 2.11: Mercury contained in waste


[from Dossier sur les dechets mercuriels en France: AGHTM, 1999].
Activity Amount (tonnes) % Treated and recycled
Zinc and lead metallurgy 18 4.8
Thermometers 9 5.6
Dentistry amalgams 9 11.4
Batteries 6.8 7.4
Laboratories 0.9 0.0
Fluorescent tubes 0.8 12.5
Barometers 0.4 10.0
High intensity lamps 0.2 10.0
Chlorine production 77 ?

Table 2.11 highlights the amount of mercury waste produced by zinc/lead metallurgy and
chlorine production. In Galicia, north-western Spain, high mercury levels in UWW and
sewage sludge are attributed to chlor-alkali production in the Pontevedra area [Cela et.al.
1992]. In Portugal too, the presence of mercury in treated wastewater, sewage sludge and
the lagoons of Aveira is linked with chlor-alkali production [Lucas et.al, 1986 and Pereira

Pollutants in Urban Waste Water and Sewage Sludge 26


2. Potentially Toxic Elements

et.al, 1998]. There appears to be potential for improved control and recycling of mercury
waste associated with these activities.

Sources of chromium

Mine production of chromium in Finland has increased from 348 thousand tonnes to just
over a million tonnes in 1990 [Mukherjee 1998], representing just under 10% of world
production. The main sources of chromium in wastewater are from the metal, chemical and
leather industries (Table 2.12). As can be seen, the chemical industry contributes over half
of the total emissions to UWW and surface waters in this region.

Table 2.12 Chromium emissions to water in Finland [adapted from Mukherjee, 1998]
Source Category Emissions to water (not exclusively UWW)
tonnes per annum % of total contribution
Chemical Industry 14.3 58.1
Paint Manufacture 0.01 <0.1
Electroplating 0.1 0.4
Ferro-chrome and Stainless Steel 4.6 18.7
Plants
Leather Processing 5.5 22.5
Total 24.6 100.0

Mukherjee [1998] reports that in Scandinavia, chromium compounds are also used in wood
preservatives, along with arsenic compounds (As2O5) and an oily mixture of organic
chemicals (phenol and creosol).

All wet-textile processing in Finland discharges its wastewater, containing chromium and
other metals, to the WWTS. The textile companies studied [Kalliala, 2000] produced
between 50 and 500 litres of wastewater per kg of textile produced. Wastewater analyses
were carried out at six major Finnish textile companies (two of these include analysis for
potentially toxic elements (Table 2.13)):

Table 2.13 Potentially toxic elements in wastewater from textile processing in Finland
[Kalliala, 2000]
Wastewater analysis (µg l-1)
Company 2 Company 4
Lead 0.11 -
Chromium 0.03 60
Copper 0.4 80
Zinc - 20

There is a very high variation in the process emissions between these two plants. Company
2 was noted to use cellulose blends while company 4 was noted to have mainly polyester
and polyester blends.

Pollutants in Urban Waste Water and Sewage Sludge 27


2. Potentially Toxic Elements

Sources of lead

Data from ADEME [1995] showed that worldwide consumption of lead is around 5.4 million
tonnes per year. In a Swedish study [Palm, Östlund, 1996] in the Stockholm area the total
amount of lead used in products such as those listed previously, was estimated at between
44,000 and 47,000 tonnes per annum. Clearly the potential for lead entering UWW from
these sources will vary greatly. The largest amount of lead that finds its way to the WWTS is
likely to be contributed by piping. Estimates for the amount of lead used are 8,000 tonnes in
lead jointed water pipes used inside buildings, followed by 2,000 tonnes used in lead jointed
water pipes used outdoors (higher replacing rate), and 120 tonnes used in PVC piping.

In the case of Finland, the Ministry of the Environment report that the drinking water
pipelines are predominantly plastic (85% PVC and PEH), with 11% cast iron; no lead is used
for pipes conveying water. The wastewater pipes for the UWW collecting system are 57%
concrete and 41% plastic.

Pollutants in Urban Waste Water and Sewage Sludge 28


2. Potentially Toxic Elements

2.1.3 URBAN RUNOFF

Runoff to UWW collecting systems and waterways has been intensely studied due to its
potentially high loading of potentially toxic elements [WRc, 1994]. Atmospheric inputs to the
urban runoff depend on the nature of surrounding industries, on the proximity of major
emission sources such as smelters and coal fired power stations and the direction of the
prevailing wind. Potentially toxic element loads can be five fold greater in runoff near
commercial activities, than in residential areas far from industrial emitters. Roof runoff and
building runoff also contribute to the total runoff loading and may be a source of considerable
amounts of potentially toxic elements such as zinc, lead, copper and cadmium. Road and
roof runoff sources are particularly important during storm events, which will allow flushing of
potentially toxic elements and other pollutants from surfaces. Furthermore, it is important to
note that the metal species released are usually in a freely dissolved, bioavailable form.
Nevertheless, these sources are very variable, as every event is different and depends on
traffic, material and age of roofs and other surfaces, and meteorological and environmental
conditions.

Although a number of studies had focused on the effects of urban land use in the
quantification of precipitation runoff, it was not until the 1950s that the first qualitative1
studies were undertaken [Palmer, 1950 and 1963; Wilkinson, 1956]. Table 2.14 provides
concentrations for a number of potentially toxic elements in urban runoff, as a summary of
various investigations from 1975 to 1978. It is important to note that the measured
concentrations differ considerably. The main sources of pollution in urban precipitation runoff
can be summarised as follows [based on Mitchell, 1985]:

• Road and vehicle related pollution


• Degradation of roofing materials
• Construction
• Litter, vegetation and associated human activities
• Erosion of soil

Table 2.14 Maximum and mean concentrations of potentially toxic elements (mg l-1)
in urban precipitation runoff pollutants [after Mitchell, 1985]

Droste and Hartt, Mance and Harman, Mattraw and


Pollutant 1975 1978 Sherwood, 1977
Mean Max Mean Max Mean Max
Lead 0.205 3.7 0.21
Iron 0.317 4.2 5.3
Copper 0.028 0.35
Manganese 0.11 1.7
Zinc 0.271 1.63

A comparative analysis between the different sources of pollution in urban precipitation


runoff is subject to variation, dependent on catchment characteristics, time of year and
measurement procedures. Urban precipitation runoff pollution has received far less attention
than other forms of urban pollution (i.e. atmospheric). Table 2.15, gives an indication of the
geographic and temporal variability involved.

1
Focusing on pollutant loads in rainfall runoff

Pollutants in Urban Waste Water and Sewage Sludge 29


2. Potentially Toxic Elements

Table 2.15 Mean concentrations in rainwater runoff (in µg/l)

Site Cd Cu Pb Zn Reference
Urban (Netherlands) 0.9 8 20 31 Van Daalen, 1991
Central Paris 2.4 60 140 Granier, 1991
Central Paris 0.11 6 13.7 38.8 Garnaud et al., 1996-1997

Garnaud et.al., [1999] attempted a comparative study between the main sources of pollution
in urban precipitation in Paris. In this recent study of individual rain events, bulk samples
were collected within four gutter pipes (roof runoff), three yard-drainage pipes (yard runoff),
six gullies (street runoff) and one combined UWW collecting system, at the catchment outlet.
The results can be seen in Figure 2.3. The values are median values.

Figure 2.3 Comparison between main elements contributing to precipitation runoff in


respect to potentially toxic elements pollution load [after Garnaud et al., 1999]

A comparison of samples from consecutive phases of precipitation runoff (precipitation to


roof runoff to urban runoff to catchment outlet) indicated that the potentially toxic element
concentration increased by a factor of 12, 30, 30 and 60 for cadmium, copper, lead and zinc,
respectively. Corrosion of roof and urban surfaces as well as human activities contributes to
this contamination, including corrosion or emission from vehicles and commercial activities.
Bulk metal concentrations were similar within all urban runoff samples except for zinc and
lead, which were particularly concentrated in roof runoff samples, due to their contamination
by corrosion of roof materials. At all sites it appeared that bulk metal concentrations could be
ranked as: Cd << Cu < Pb << Zn.

Differences in potentially toxic elements concentration in precipitation water and runoff from
roofs and streets have also been found in a German study (Table 2.16). In this case it can
be seen that runoff from streets has the highest potentially toxic element content.

Pollutants in Urban Waste Water and Sewage Sludge 30


2. Potentially Toxic Elements

Table 2.16 Concentration changes of certain contaminants in precipitation water and


runoff from different outflow paths, Germany.
[Xanthopoulos and Hahn, 1993] LOD Limit of detection

Pollutant Precipitation Run-off from Run-off from


[µg/l] roofs [µg l-1] streets [µg l-1]
Pb 5 104 311
Cd 1 1 6.4
Zn 5 24 603
Cu 1.5 35 108
Ni 5 <LOD 57

A study carried out by Rougemaille (1994) analysed the wastewaters of the treatment plant
in Achères in the Paris region and found that lead concentrations varied between 0.05 and
0.5mg l -1 and that the average concentration was 0.1mg l-1. These wastewaters come from
four different urban areas. The study showed that lead concentrations were 3 times larger
during wet weather than during dry weather, hence proving the importance of the runoff
sources.

A study carried out around the region of Nantes in France in 1999, analysed road runoff from
a major highway for a year showing that lead and zinc are the main pollutants present in
runoff waters (Table 2.17).

Table 2.17: Analysis of raw runoff waters [Legret, 1999]

PAH Pb Cu Cd Zn
(ng l-1) ( g l-1) ( g l-1) ( g l-1) ( g l-1)
Mean <96 58 45 1 356
Median <74 43 33 0.74 254
Range <11-474 14-188 11-146 0.2-4.2 104-1544
SD 76 44 27 0.86 288

The Swedish study mentioned in previous sections [Palm, Östlund, 1996], estimated the
total amount of zinc passing into wastewater at 6,300 tonnes per annum. Most of the zinc
present in the urban environment was generated by urban runoff and rain; from roofs and
building surfaces (1,600 tonnes), from cars excluding tyres (1,500 tonnes), from tyres (200
tonnes), and from lampposts and street furniture (an estimated 1,142 tonnes). Zinc was also
attributed to water pipe couplings (1,000 tonnes).

Pollutants in Urban Waste Water and Sewage Sludge 31


2. Potentially Toxic Elements

A Road and vehicle contribution

Roads are a major source of pollution in urban environments and contribute to wastewater
pollution both directly and indirectly (airborne pollutants generation). Sartor and Boyd
[USEPA, 1972] determined the major constituents of road related runoff to be inorganic
matter, but the total mass of inorganic matter present seemed to increase as the antecedent
dry period (ADP) increased. Sources of the organic and inorganic fraction of road-produced
pollutants are summarised as follows:

• Vehicle lubrication systems losses


• Vehicle exhaust emissions
• Degradation of automobile tyres and brakes
• Road maintenance
• Road surface degradation
• Load losses from vehicles (accidental spillages)
• Precipitation (wet deposition)
• Atmospheric deposition (dry deposition)

Potentially toxic elements in runoff occur from motor fuel combustion, brake linings, tyre
wear and road surface wear. Motor fuel combustion was the largest source of lead to runoff
but it is on the decrease due to the gradual phasing out of leaded fuel in the EU. Other
metals emitted from exhausts are zinc, chromium and more recently tin from the
replacement anti-knock compounds in petrol. The presence of Zn and Cd in road surface
sediments can also be explained by the addition of Zn dithiophosphate in the manufacturing
of lubricating oil, Cd being present as an impurity of the original Zn. Brake lining wear
contributes copper, nickel, chromium and lead to runoff. Tyre abrasion contributes to the
load of zinc, lead, chromium and nickel due to the soot and metal oxides constituents.
Cadmium in car tyres is attributed to zinc-diethylcarbonate, which is used during the
vulcanisation process. Road surface wear contributes to emissions of nickel, chromium,
lead, zinc and copper.

Legret and Pagotto (1999) produced estimates of potentially toxic element content from
vehicle related pollution sources (Table 2.18), and contributions to road runoff (Table 2.19).

Table 2.18 Potentially toxic element contents in vehicle and road materials (mg kg-1)
[after Legret and Pagotto, 1999]

Sources Pb Cu Cd Zn
Leaded petrol 200 - - -
Unleaded petrol 17 - - -
Brake linings 3900 142000 2.7 21800
Tyre rubber 6.3 1.8 2.6 10250
De-icing agent 3.3 0.5 0.2 0.5

Pollutants in Urban Waste Water and Sewage Sludge 32


2. Potentially Toxic Elements

Table 2.19 Emissions fluxes in precipitation runoff (kg km-1 annum) and percentage
removed in drainage waters [after Legret and Pagotto, 1999]

Sources Solids Pb Cu Cd Zn
Vehicles Tyre wear 314 0.002 0.0006 0.0008 3.22
Brake 100 0.390 14.2 0.0003 2.17
linings
Petrol - 13.0 - - -
Road Safety - 0.002 0.0002 0.0002 0.95
fence
De-icing 130 0.015 0.002 0.0007 0.002
agent
Air deposition 86 0.014 0.015 0.0009 0.21
Drainage water %2 235 5 2 313 37

The percentages of these potentially toxic elements entering the drainage systems show that
a large proportion of the pollutants released do not end up in the runoff waters but are
probably emitted into the atmosphere. The Zn content in urban runoff remains highly variable
depending on the use of safety barriers made from galvanized steel or from an alternative
material. All parameters are affected by traffic and by variables connected to the
meteorological and environmental conditions of the sites concerned, which make the
comparison highly uncertain (Montrejaud-Vignoles et al., 1996).

The following mechanisms summarise the way the pollutants are transported (pathways)
from the catchment over the roads and finally in the drainage network:

- Soluble contaminants dissolved in the runoff water


- Insoluble particles acting as sorbents for potentially toxic elements and organic
contaminants which are transported by the runoff water [Ellis, 1976; Sylvester
and DeWalle, 1972]
- Removal by air-dispersal involving transfer of the surface contaminants to the
atmosphere either as dry particles or dissolved in surface water.

Note that the first two mechanisms above result in pollutants being transferred ultimately into
receiving waters or sewage sludge, while the last mechanism removes pollutants prior to
their ultimate disposal. The general conclusion, however, is that the majority of road surface
runoff contamination is sediment associated. In particular, the prime transport mechanisms
and pathways with respect to road-runoff sediment transport are [Sartor and Boyd, 1972]:

- Particle entrapment
- Cross surface transport by overland sheet-like flow to the gutter as turbulent
heavy fluid transport process
- Linear transport of the particle material parallel to the kerb line into the road gully.

The transportation of surface particulates is sporadic in nature [Mitchell, 1985]. Metal levels
tend to fall after periods of rain, whilst elevated concentrations have been recorded after
prolonged dry periods. Also introduced in the movement patterns are local storage and
residence effects due to the intrinsic configurations and micro-topography of the road
surface [Harrop, 1983]. The fact that contaminants move through this sequence is well
known, however, the relationship between the contaminants and the various mechanisms
involved are poorly understood. Comparison of metal distribution during particle transport,

2
For value >100% the research identified larger concentrations in the samples than expected from the sources that were
taken into account. This is particularly true for Cd concentrations. Additional sources of Cd (such as lubricating oils, as
discussed earlier) may account for this underestimation.

Pollutants in Urban Waste Water and Sewage Sludge 33


2. Potentially Toxic Elements

from atmosphere to receiving water body, clearly demonstrates a metal mobility evolution
(Garnaud et al., 1999). Extremely labile (i.e. hydrosoluble or exchangeable), within dry
atmospheric deposits Cd, Pb and Zn, become bio-available within street runoff and stable
within UWW collecting system or river sediment. In conclusion particulate metal mobility may
be classified as: Cu<<Cd<Pb<Zn<Fe.

Potentially toxic elements are predominantly associated with inorganic particles and
research indicates that potentially toxic element concentrations increase as particle size
decreases (Sansalone and Buchberger, 1997; Lloyd and Wong, 1999). In particular
Colandini and Legret (1997), found a bimodal distribution with the highest concentrations of
Cd, Cu, Pb and Zn being associated with particles of less than 40 µm in size. Table 2.18
indicates the potentially toxic elements distribution across the particle size distribution for a
number of potentially toxic elements.

Table 2.20 Approximate concentration of potentially toxic elements associated with


particles [after Colandini and Legret, 1997]

Inorganic Approximate concentration of potentially toxic elements


particle size associated with particles (mg kg-1)
fraction (µm) Zinc Lead Copper Cadmium
<40 900 920 240 24000
40-63 275 100 100 5000
63-80 300 100 125 5000
80-125 350 150 175 5000
125-250 400 200 200 5000
250-500 450 175 300 3000
500-1000 240 225 30 3000

Table 2.21 summarises measurements from 1975 to 1982 on concentrations of potentially


toxic element pollutants in road runoff in three German towns:

Table 2.21 Summary of pollutant loads in urban runoff caused by road related sources
from 1975 to 1982 [after Klein, 1982]

Pollutant mean Test catchments


concentrations Pleidelsheim Obereisesheim Ulm / West
(mg/l)
Cd 0.0059 0.0059 0.0028
Cr 0.0096 0.02 0.0052
Cu 0.097 0.117 0.058
Fe 3.42 5.16 2.18
Pb 0.202 0.245 0.163
Zn 0.36 0.62 0.32

Pollutants in Urban Waste Water and Sewage Sludge 34


2. Potentially Toxic Elements

Vehicle emissions:
Prior to the lead ban in fuel3, research had identified exhaust lead emissions to account for
more than 90% of atmospheric lead pollution. Although the main source of lead in the
average urban atmosphere is lead from fuel additives, it appears that only 5% of the lead
can be traced in runoff water. The greatest part may, therefore, disperse in the atmosphere
or settle on the soil by the roadside (Hewitt and Rashed, 1990). The actual rate and form of
lead emission is crucially dependent on driving conditions. High engines speeds and rapid
acceleration can increase emission levels due to reactivation of particles deposited on the
exhaust system. Total lead emissions can double if the engine and/or weather is cold. The
deposition from petrol to the road surface was estimated to be 0.049g Pb.vehicle-1. km -1. In
the case of lead-containing fuel, approximately 75% of lead is discharged to the atmosphere
(Hewitt and Rashed, 1990) and a further 20% is retained in engine sump oil (Wilson, 1982).

Concentration of lead added to petrol has rapidly declined in the EU during the 1980s due to
legislation. In Austria for example, the lead emissions between 1985 and 1995 have been
reduced by approximately 88 % [UBA, 1999]. Figure 2.4 is indicative of this period of policy
change (between 1972 and 1992). Note the high correlation between lead in petrol and lead
air pollution despite the large rise in traffic flow experienced in the same period.

Figure 2.4 Reduction in lead concentrations in air and petrol between 1972-1992
in the EU [after Montague and Luker, 1994]

Platinum group metals4 (PGMs) are increasingly used in vehicle exhaust catalysts (VECs)
and can be traced in the urban environment [Farago et al., 1995]. These are covered in
detail in Section 6, case studies.

3
Amid mounting concern that the lead dispersed in the environment was causing damage to humans and the
environment, a series of regulations and directives have been adopted in Europe since the 1980s, in order to phase out
the use of leaded petrol. Lead content of petrol has been reduced from 0.4g l-1 to 0.15gl -1, following the Lead In Petrol
Directive 85/210/EEC. Further regulations on air quality have now come into force limiting the levels of lead in air, with an
attainment date of 2005. Some countries, namely: Austria, Denmark, Finland, Germany, the Netherlands, Norway,
Sweden, and the UK have already phased out its use.
However, in some countries in Eastern Europe, higher levels of lead are permitted, up to 0.4g l-1. In most of the newly
independent states and the Russian Federation, permitted lead levels are 0.15-0.37 g l -1. Various strategies for reduction
of lead in petrol have been made in these countries, though it is expected that some will have difficulty in achieving these
targets.
4
Platinum, palladium in vehicle exhaust catalysts and rhodium in three-way catalysts

Pollutants in Urban Waste Water and Sewage Sludge 35


2. Potentially Toxic Elements

Vehicle degradation:

Tyre wear releases lead, zinc and hydrocarbons, either in particulate form or in larger pieces
as a result of tyre failure. The deposition of Zn on the road surface from tyres has been
determined to be 0.03g vehicle km-1 (Mitchell, 1985). Metal particles, especially copper and
nickel, are released by wear of clutch and brake linings. Additionally, the presence of Ni and
Cr in storm runoff can result from the degradation of car bumpers and window sealings
where both metals are used in the manufacture of chrome plating. Copper is a common
constituent of piping and other components of the engine and chassis work. The contribution
to road surface material of vehicle tyres and brake linings from different road types has been
summarised in Table 2.22.

Table 2.22 Input from tyre wear and brake lining degradation for each road category
[after Muschack, 1990]
Type Total Individual elements
of street Abrasion (g ha of road-1 annum-1)
(kg ha of
road-1) Pb Cr Cu Ni Zn
Tyre Brake Tyre Brake Tyre Brake Tyre Brake Tyre Brake Tyre Brake
wear lining wear lining wear lining wear lining wear lining wear lining
Residential
way 137 6.8 60 7.3 10 13.7 12 210 10 51 35 0.9

Residential
street 62 8.5 76 9.0 13 17.0 17 260 12 63 43 1.7

Distributor
72 12.4 112 16.6 19 24.9 26 381 18 93 63 2.4
road
Main
distributor 109 19.1 172 20.4 29 38.3 39 586 27 143 96 2.6
road
Main road 127 30.3 266 32.2 44 60.5 60 926 42 226 149 2.1
Dual
carriageway
120 43.4 382 46.3 64 86.9 72 1329 61 324 214 5.8
Motorway 328 82.1 572 87.6 120 164 164 2513 115 613 405 11.0

These findings are also supported by evidence in non-EU countries. Drapper et al. (2000) in
an experimental site in Australia concluded that brake pad and tyre wear, caused by rapid
vehicle deceleration, contributes to the concentrations of copper and zinc in road runoff.
Laser particle sizing indicated that the median size (by volume) of the sediment found was
100 µm, but have settling times of around 24 hours under laboratory conditions. The
explanation offered to this unexpected behaviour is the presence of potentially toxic
elements. One of the most important findings of this study (which took into account both
Australian and US research), was that traffic volume cannot account for more than 20-30%
of the variability of pollutant load variations and therefore a traffic volume criterion on
whether or not the precipitation runoff should be treated may not be acceptable. Drapper et
al. (2000) also stated that precipitation intensity and preceding dry days could be a
significant factor influencing actual pollutant concentrations. It can be argued that a more
suitable criterion for treatment need assessment would be the environmental significance of
the receiving waters.

Road related sources:


Pollution in precipitation runoff from road-related sources stems mainly from maintenance
practices including de-icing, road surface degradation and re-surfacing operations.

De-icing agents include large amounts of sodium chloride, and may also contain smaller
concentrations of iron, nickel, lead, zinc chromium and cyanide as contaminants. Their use
can greatly increase corrosion rates in vehicles and metal structures leading to increased
metal deposition. Salt in solution can also create conditions that allow the release of toxic
metals such as mercury from silts and sludge [WRc, 1993]. It is likely that de-icing is a major
source (at least in the winter) of bromide, nickel and chromium [Hedley and Lockley, 1975]

Pollutants in Urban Waste Water and Sewage Sludge 36


2. Potentially Toxic Elements

and it is suggested it may affect the solubility and mobility of other metals, notably of lead,
which may precipitate more readily in the presence of sodium [Laxen and Harrison, 1977].

The use of NaCl as a de-icing agent may change the behaviour of the accumulated
contaminants in roadside soils. In soils exposed to high Na concentrations with a
subsequent supply of lower salinity water, as in snowmelt periods and storm flow events,
there is a risk of colloid dispersion and mobilization [Norrstrom and Jacks, 1998]. Soil
column leaching experiments with NaCl and low-electrolyte water have provided evidence
for the mobilisation of organic colloids and Fe-oxides, suggesting that potentially toxic
elements may reach the groundwater via colloid-assisted transport [Amrhein et al., 1992,
1993]. Moreover, the use of road-salt may result in the increased mobilisation of potentially
toxic elements due to complexation with chloride ions [Doner, 1978; Lumsdon et al., 1995].

Complexed cyanide ion (in the form of sodium ferrocyanide) is added as anti-caking
agent to de-icing agents, and compounds containing phosphorus may also be added as
rust inhibitors. Novotny et al. (1998) argue that although ferrocyanide is non-toxic in its
original form, its instability under predominant natural surface waters conditions, results in
decomposition to free cyanide which is toxic (free cyanide↔HCN(aq)+CN-(aq)). The initial
cyanide form is only stable within the pH range 8 to 14 and zero to –600mV redox potential
(Eh). The rate of decomposition is estimated around 10.2µg l-1 h -1 in salt water. Meeusen et
al. (1992) estimated similar rates of decomposition.

Road surface degradation is likely to release various substances: bitumen and aromatic
hydrocarbons, tar and emulsifiers, carbonate and metals depending on the road construction
techniques and materials used. The following table provides some indication of the
concentrations of potentially toxic elements released from road surface abrasion, classified
by type of road encountered in urban areas.

Pollutants in Urban Waste Water and Sewage Sludge 37


2. Potentially Toxic Elements

Table 2.23 Emissions from abrasion of urban streets surface material


[after Muschack, 1990]
Type Total abrasion Individual elements
of street (kg ha of road-1 (g ha of road-1annum-1)
annum-1) Pb Cr Cu Ni Zn
Residential way 1734 177 619 88 2030 285
Residential street 2148 219 767 110 2513 352
Distributor road 3152 322 1125 161 3688 517
Main distributor
4850 495 1731 247 5674 795
road
Main road 7665 782 2736 391 8965 1257
Dual carriageway 11000 1124 3927 561 12870 1804
Motorway 10000 1020 3570 510 11700 1640

Accidental discharges:
Although spillages can be considered a minor add-in in terms of total pollutant loading, they
can be one of the most serious sources of contaminants in urban areas. They can range
from minor losses of fuel to major losses from fractured tanker vehicles. The resulting impact
on wastewater treatment plants or directly to water receptors is hard to estimate due to the
random nature and the unpredictability to both the extent of the spill and its position relative
to the precipitation runoff system.

In the case of chemical accidents, water or foam medium are used for road cleaning
purposes or for fire fighting. The compositions of a typical and unusual load of the surface
run-off are compared in Table 2.24.

Table 2.24 Example of a typical and unusual load in run-off water from a German
motorway [Ascherl, 1997, Krauth and Klein, 1982]

Parameter Run-off rain water- mean value Water for firefighting- [mg l-1]
[mg l-1]
Cd 0.0059 0.057
Cr 0.0096 0.053
Cu 0.097 0.203
Fe 3.42 4.0
Pb 0.202 0.439
Zn 0.36 4.7

Information relating to the frequency of accidental spillages is presented in Table 2.25,


based on data extracted from NRA (Thames Region, UK), indicating pollution incidents
registered from 1988 to 1993 (July):

Table 2.25 Accidental spillages in Thames Region (UK)

Year 1988 1989 1990 1991 1992 1993(July)


Number of incidents reported 2811 3613 3444 3417 3598 1979
Road incidents reported 125 177 175 136 212 104
Road incidents where pollution 88 63 64 42 58 36
substantiated

Pollutants in Urban Waste Water and Sewage Sludge 38


2. Potentially Toxic Elements

B Roof runoff

Runoff from roof surfaces constitutes a significant fraction of the total sealed surface runoff
and is often regarded as unpolluted. Assessment of roof runoff quality found in literature
gives rather contradictory results. Some authors conclude that rain runoff from roof surfaces
is polluted (e.g. Zillich 1991; Good 1993); others found that there is a low pollution potential
associated with roof runoff (Shinoda 1990). For the specific case of potentially toxic
elements pollution however, the literature seems to agree that roof runoff can be at least as
polluted as road runoff (Herrmann et al., 1994; Förster, 1999). The pollution effect is much
greater when the source of pollutants is the roof material itself. Förster (1999) found that zinc
concentrations in runoff from zinc sheet roof were actually two or three orders of magnitude
above those measured in runoff from roofs without any metal components (i.e. fibrous
cement roof).

However, even in the case of normal rooftops (non-metal dominated) there is a


concentration of potentially toxic elements to be expected due to various metal components
(gutters, downspouts, fittings etc.). The main pollutants in this case are zinc and copper. The
runoff rate of zinc was proven to be considerably lower than its corrosion rate, varying
between 50±90% for zinc and 20±50% for copper during exposures up to five and two years,
respectively (Wallinder et al., 2000). Similar to its corrosion rate, runoff rates of zinc are
strongly related to the atmospheric SO2 concentration and are, as such, different for a rural,
compared to an urban or an industrial, environment. Observed lead pollution from roof runoff
(which can be considered significant in many cases compared to other sources) can be
explained by the use of lead in window frames and rooftops (the case of slate roofs in Figure
2.5) and the use of lead sheeting, particularly in the UK. The lead emission factor from lead
flashing and roofing in Denmark is estimated at 5.10-4 kg kg-1year-1 (Jøergensen and
Willems, 1987]. The presence of cadmium can be explained by the fact that cadmium is a
minor contaminant of zinc products.

A study in Calais, France, and its surrounding area found that concentrations of cadmium,
mercury, and lead in roof sludge were: 34.5 mg kg-1, 4.4 mg kg-1, and 4mg kg-1 respectively
in the urban areas [ADEME, 1997]. A study carried out in Nancy in 1996 analysed wet
weather runoff and determined the main metal-contributing sources. For zinc, roof runoff was
the largest source as it contributed 72%, and road runoff only contributed 12%. For lead, the
main source was again roof runoff with 33% contribution and then road runoff with 32%
[Autugelle et al., AGHTM, 1996]. However, these data may not be typical, as they represent
one storm event.

Relationships between rooftop material and runoff pollutant load can be observed in Figure
2.5 and Table 2.27

Pollutants in Urban Waste Water and Sewage Sludge 39


2. Potentially Toxic Elements

Figure 2.5 and Table 2.27 Rooftop material and runoff pollutant load [after Gromaire-
Mertz et al., 1999]
Roof Name Covering Gutter
Material Material

Tile 1 Interlocking Zinc


Clay Tiles

Tile 2 Flat clay tiles Copper


(70%)
+ zinc
sheets
Zinc Zinc Sheets Zinc

Slate Slate Zinc

Table 2.28 provides some indicative ranges of potentially toxic element pollution
concentrations from roof runoff. For comparison purposes the ranges of concentrations of
the same pollutants from other sources in the same study, are also included. The median
value is used, instead of the mean, to filter out the effect of isolated extreme events.

Table 2.28 Potentially toxic element pollution concentrations from roof runoff
[after Gromaire – Mertz et al., 1999]

Roof runoff Yard runoff Street runoff


Min. Max. Median Min. Max. Median Min. Max. Median
-1
Cd (µg l ) 0.1 32 1.3 0.2 1.3 0.8 0.3 1.8 0.6
Cu (µg l-1) 3 247 37 13 50 23 27 191 61
Pb (µg l-1) 16 2764 493 49 225 107 71 523 133
Zn (µg l-1) 802 38061 3422 57 1359 563 246 3839 550

Lead pollution from roof degradation is strongly particle-bound (measurements indicated


median values of 87%), whereas the distribution between particle and dissolved pollution
fluctuates for the rest of the potentially toxic elements. Although solids are the main vector of
pollution in street and yard runoff, literature agrees that in the case of roof runoff the
dissolved phase is of primary importance [Gromaire – Mertz et al., 1999; Förster, 1996;
Förster, 1999; Wallinder et al., 2000]. The very high concentrations of dissolved potentially
toxic elements in roof runoff make its infiltration hazardous and highly dependent on roof
materials. Low settling velocities for roof runoff particles in conjunction with high percentage
of dissolved pollutants make settling alone an insufficient technique for treatment.
Uncontrolled local infiltration practices (infiltration trenches etc) may lead to serious local soil
contamination and present a threat to groundwater quality.

In conclusion it can be said that roof runoff pollution is influenced by roof material, air
pollution, the precipitation event (intensity, antecedent dry period), the meteorology (season,
wind speed and direction) and the pollutants’ physico-chemical properties. It can under
certain conditions by far exceed threshold toxicity values. The following suggestions
(Förster, 1999) summarise a number of research areas that should be considered to
minimise roof runoff pollution.

Pollutants in Urban Waste Water and Sewage Sludge 40


2. Potentially Toxic Elements

• First flush diversion valves and their automated control


• Sorbents for potentially toxic elements
• Durable coating for potentially toxic element surfaces
• Alternative materials for gutters and downpipes (eg plastics or carbon fibre based
materials, not metals or PVC)
• Roof runoff quality database sufficient for predictive modelling.

C Construction and building maintenance

Contaminants from paints:


While lead concentrations in consumer products (i.e. petrol) continue to decrease, there
seems to be enough residual material from historic lead use to cause high lead
concentrations in the environment. In a recent study by Davis and Burns (1998) in the US,
lead runoff from painted structures in an urban setting was assessed. Although construction
practices in the US can be considered different from those in EU, the conclusions of the
Davis and Burns (1998) study should be taken into account due to the variability of the
structures investigated. In many cases, high lead concentrations were found. Lead
concentrations (100 ml over 1600 cm) from washes of 169 different structures followed the
order (geometric mean, median, Q10±Q90): wood (40, 49, 2.6±380 mg.l-1)>brick (22, 16,
3.3±240 mg.l-1)>block (9.7, 8.0, <2±110 mg.l-1). Lead concentration depended strongly on
paint age and condition. Lead levels from washes of older paints were much higher than
from freshly painted surfaces, which were demonstrated quantitatively as: paint age [>10 y]
(77, 88, 6.9±590 mg.l-1)>>[5±10 y] (22, 16, <2±240 mg.l-1)>[0±5 y] (8.4, 8.1, <2±64 mg.l-1).
Lead from surface washes was found to be 70% or greater in particulate lead form,
suggesting the release of lead pigments from weathered paints. High intensity washes were
found to liberate more particulate lead than lower intensities. It can be concluded that old
surface paints can contribute high masses of lead into a watershed, targeting these
structures for source preventive actions to curtail future lead input into the environment.

Contaminants from concrete leaching:


Concrete is one of the main materials used in building and road construction and is
systematically in contact with precipitation, much of which ends up in the UWW collection
systems. Recent work (PCA, 1992) identified As, Be, Cd, Cr, Hg, Ni, Pb, Sb, Se and Th in
concrete in detectable concentrations. Hillier et al. (1999) discuss the importance of the
concentrations of these pollutants in leachate from Portland cement. They concluded that
leaching of well-cured Portland cement produces undetectable concentrations of toxic
metals (such as the ones outlined in 80/778/EEC for water fit for human consumption). In
poorly cured (1 day) Portland cement there were detectable concentrations of vanadium
(reaching concentrations of 61.7 ppb). However, even this cannot be considered very
significant, as the leaching was restricted to the surface of the samples. Furthermore, the
water-to-cement ratio has no significant impact on the leaching potential of the cement. This
study suggests that concrete leaching is not a major source of metals to UWW.

D Wet and dry deposition

Rainwater can add its own absorbed and dissolved pollutants to the loads generated from
other sources. This was shown in Figure 2.3, which shows the initial potentially toxic element
loading of precipitation and the subsequent additional loading from roof, pavement and road
surfaces. Both traffic density and location of industry have a strong influence on the
deposition of potentially toxic elements in precipitation.

The composition of atmospheric loaded precipitation water in urban regions in Germany,


contaminated with atmospheric wash-out, is represented in Table 2.29.

Pollutants in Urban Waste Water and Sewage Sludge 41


2. Potentially Toxic Elements

Table 2.29 Composition of atmospheric loaded run-off water in German urban regions
[Freitag et al. 1987, Göttle 1988, Hahn 1995].

PTE Values Munich


(Pullach/ Harlaching)
Mean value Extreme values 1988
[mg l-1] [mg l-1] [mg l-1]
Zn 0.05-0.15 0.02-1.9 0.0945
Cu 0.007-0.2 <0.06 0.0355
Pb 0.03-0.11 <0.24 0.0121
Cd 0.001-0.003 <0.13 0.0014
Mn 0.05 <0.1 -
Cr 0.002 <0.08 -

Currently, vehicle traffic, steel and glass production, and combustion processes represent
the main sources of lead in the atmosphere. Data by ADEME studies have shown that
atmospheric fallout contributes 87-536 g ha-1year-1 of lead, and is particularly high in urban
areas. These studies determined that 70-80% of lead present in UWW comes from runoff,
15-20% from commercial sources and 5% from domestic sources. The main cadmium
sources are from combustion processes (vehicle traffic, waste combustion in incineration
plants). Combustion processes and chlorine and steel production represent the main
sources of the atmospheric mercury emissions in the Central Region. Table 2.30 shows the
reduction in Cd, Hg and Pb emissions in Austria between 1985 and 1995 as a result of
legislative controls.

Table 2.30 Emissions and predicted yearly emissions of potentially toxic elements in
Austria, 1985-2010 [UBA, 1999].
PTEs 1985 1990 1995 Prediction Prediction
[t y-1] [t y-1] [t y-1] 2005 2010
[t y-1] [t y-1]
Cadmium 4.80 3.10 1.80 1.20 1.30
Mercury 4.30 2.70 1.50 1.20 1.10
Lead 320.00 202.00 39.00 24.00 21.00

The presence of impermeable surfaces in urban areas prevents natural filtration processes
in the soil zone from removing the pollution. The actual quality of the rain can vary
dependent on pollution sources other than urban traffic. In coastal areas the increased
concentrations of sodium and chloride in precipitation will increase the susceptibility of
vehicles to corrosion. A road drainage study in Sweden noted precipitation pH of between
3.8 and 4.9 [Morrison et al. 1988].

Atmospheric sources contribute significantly to the mass of contaminant available on an


impervious urban surface for transport by surface runoff. This deposition may occur during a
storm event or as dust fall during dry periods. Cattell and White (1989) [as reported in Ball et
al. 2000] in their study in Sydney reported that the geometric mean of the total phosphorous
concentration is 29 µg l-1. If the mean annual precipitation for Sydney of approximately 1600
mm is considered, then the likely annual phosphorus load is approximately 0.5kg ha-1y-1,
which is more than half the likely annual phosphorus load from an urban catchment of 0.7kg
ha-1y-1 [Lawrence and Goyen, 1987] to 1.1kg ha-1y-1 [Cullen, 1995].

The second of the two atmospheric sources of contamination is dry deposition in the period
between storm events. For dry deposition, removal by stormwater runoff is not the sole
mechanism responsible for depletion of the contaminant store, which is developed on the
catchment surface. As well as removal by storm events, removal also can occur through
street sweeping, through the local turbulence arising from the motion of vehicles on roads,
and through wind events where the wind has sufficient capacity to entrain the contaminant
and to move it from the surface of the urban catchment [Ball et al., 2000].

Pollutants in Urban Waste Water and Sewage Sludge 42


2. Potentially Toxic Elements

Table 2.31 Dry Weather Build-up of Contaminants on Road Surfaces


[after Ball et al., 1998]

Constituent Load (mg/m of gutter)


Constituent Minimum Maximum Mean
Pb 1.4 7.4 3.7
Zn 0.7 3.9 1.8
Cu 0.3 1.8 0.9
Cr 0.02 0.61 0.14
P 0.23 1.9 0.8

Dry atmospheric fallout can be responsible for large proportions of road dust but estimates
vary according to atmospheric and weather patterns, as well as with different sampling and
estimation methods. Nevertheless, atmospheric deposition can be very significant proportion
of the total particulate/sediment input to a highway and since much of it is inert, inorganic
and often calcareous in nature (depending upon local geology and building stone), it can
prove beneficial in neutralising acid emissions, reducing potentially toxic element solubility
and assisting in the binding of organic and other pollutants [Luker and Montague, 1994].

Snowfall has an increased pollutant scavenging efficiency because of the large snowflake
surface area and the increased ionic strength of the melt water provides enhanced metal
exchange capabilities. Trees in urban settings are also effective scavengers of metals, which
are deposited on surfaces at leaf fall.

Atmospheric contaminants are deposited during the early stages of a precipitation event and
therefore the resulting impermeable surface loading tends to be independent of both
precipitation volume and intensity, with the pollutant load tending to increase with the length
of antecedent dry period and with local traffic density.

E Sewer cleaning
Sewer cleaning is carried out for a number of reasons, but principally to deal with blockages
or to remove sediment in order to restore hydraulic capacity and limit pollutant accumulation.
A number of cleaning techniques and methods is in use, depending particularly on location
and severity, including rodding, winching, jetting, flushing and hand excavation (Lester &
Gale, 1979). A combination of more than one method may well be used in any particular
locality.

The frequency with which sewers are cleaned will depend on the maintenance strategy in
operation. If reactive maintenance is used, problems are dealt with on a corrective basis as
they arise (i.e. after failure). This approach will always be required to a certain extent, as
problems and emergencies occur from time-to-time in every system. However, its frequency
cannot be predicted. In planned maintenance, potential problems are dealt with prior to
failure. Unlike reactive maintenance, planned maintenance is proactive and has the objective
of reducing the frequency or risk of failure (Butler & Davies, 2000). Planned maintenance
differs from routine maintenance (operations at standard intervals, regardless of need), and
involves identifying elements that require maintenance and then determining the optimum
frequency of attention. Frequency of cleaning will thus vary from place to place but is usually
less than once per year even in heavily affected sewers.

Sediment removed from sewers during cleaning is normally classified as a controlled waste,
and is therefore disposed of to licensed landfill sites.

Pollutants in Urban Waste Water and Sewage Sludge 43


2. Potentially Toxic Elements

2.2 Influence of various treatment processes on the fate of potentially toxic elements
through WWTS and SST

PTE transfers to sewage sludge


Sludges from conventional sewage treatment plants are derived from primary, secondary
and tertiary treatment processes. The polluting load in the raw waste water is transferred to
the sludge as settled solids at the primary stage and as settled biological sludge at the
secondary stage. Potentially toxic elements are also removed with the solids during the
primary and secondary sedimentation stages of conventional wastewater treatment. Metal
removal during primary sedimentation is a physical process, dependent on the settlement of
precipitated, insoluble metal or the association of metals with settleable particulate matter.
Minimal removal of dissolved metals occurs at this stage and the proportion of dissolved
metal to total metal in the effluent increases as a result. The efficiency of suspended solids
removal is the main process influencing the extent of metal removal during primary
wastewater treatment. However, the relative solubilities of different elements present in the
wastewater are also important. Thus, nickel shows the poorest removal (24 %) during
primary treatment whereas 40 % of the Cd and Cr in raw influent is transferred to the primary
sludge. Primary treatment typically removes more than 50 % of the Zn, Pb and Cu present in
raw sewage.

The removal of metals during secondary wastewater treatment is dependent upon the
uptake of metals by the microbial biomass and the separation of the biomass during
secondary sedimentation. Several mechanisms control metal removal during biological
secondary treatment including:

• physical trapping of precipitated metals in the sludge floc;


• binding of soluble metal to bacterial extracellular polymers;

In general; the patterns in metal removal from settled sewage by secondary treatment are
similar to those recorded for primary sedimentation. However, the general survey of removal
efficiencies listed in Table 2.32 suggests that secondary treatment (by the activated sludge
process) is more efficient at removing Cr than the primary stage. Operational experience and
metal removals measured by experimental pilot plant systems provide guidance on the
overall likely removal and transfers to sludge of potentially toxic elements from raw sewage
during conventional primary and secondary wastewater treatment. This shows that
approximately 70 – 75 % of the Zn, Cu, Cd, Cr, Hg, Se, As and Mo in raw sewage is
removed and transferred to the sludge (Blake, 1979) and concentrations of these elements
in the final effluent would be expected to decrease by the same amount compared with the
influent to the works. Lead may achieve a removal of 80 %, whereas the smallest overall
reductions are obtained for Ni and approximately 40 % of this metal may be transferred to
the sludge.

The majority of potentially toxic elements in raw sewage are partitioned during wastewater
treatment into the sewage sludge or the treated effluent. However, atmospheric volatilisation
of Hg as methylmercury, formed by aerobic methylation biotransformation processes, is also
suggested as a possible mechanism contributing to the removal of this element during
secondary wastewater treatment by the activated sludge system (Yamada et al., 1959).
Whilst some of the Hg removal observed in activated sludge may be attributed to bacterially
mediated volatilisation, it is unlikely that this is a major route of Hg loss because of the
significant quantities of Hg recovered in surplus activated sludge (Lester, 1981).

Pollutants in Urban Waste Water and Sewage Sludge 44


2. Potentially Toxic Elements

Table 2.32 PTE removals and transfer to sewage sludge during conventional
urban wastewater treatment [Lester, 1981]
PTE Removal (%)
Primary(1) Secondary(2) Primary + Primary +
secondary secondary(3)
Zn 50 56 78 70
Cu 52 57 79 75
Ni 24 26 44 40
Cd 40 40 64 75
Pb 56 60 70 80
Cr 40 64 78 75
Hg 55 55 80 70
Se 70
As 70
Mo 70
(1)
Mean removal (n = 5) from raw sewage and transfer to sludge during primary sedimentation
(2)
Mean removal (n = 9) in activated sludge from settled sewage, (3)Blake (1979)

Predicting the fate of potentially toxic elements during WWT and sludge treatment
Chemical contaminants present in UWW are associated principally with the organic and
mineral fractions in sewage. The microbial biomass in secondary treatment is also effective
at scavenging potentially toxic elements from the settled sewage transferring metals to the
activated sludge. About 60 - 80 % of the wastewater load of potentially toxic elements such
as Cu and Pb is transferred into sludge (Table 2.32) and the sludge contains approximately
1000 times (mg kg-1 ds basis) the concentration of these metals present in the wastewater
(mg l -1). The relationship between metal concentrations in wastewater and in sludge can be
determined empirically as follows (after Blake 1979):

S = P / ((Ws/1x106) x (100/T)) mg kg-1 ds

Where P = Concentration of contaminant in wastewater mg l-1


S = Concentration of contaminant in sludge mg kg-1 ds
Ws = Dry solids content of wastewater mg l-1
T = Transfer efficiency of contaminant from wastewater to sludge during
sewage treatment %
Ds = Dry substance

For example, a wastewater containing 1.3 mg l-1 of Zn (P) and 450 mg l-1 of dry solids (Ws)
would produce sludge with a Zn concentration of 2000 mg kg-1, assuming a transfer factor of
70 % (T):

S = 1.3 / ((450/1x106) x (100/70)) mg kg-1


= 2000 mg kg-1

This relationship can also be used to estimate the concentrations of metals in the raw
sewage effluent, based on analytical data for the metal content in sludge and the dry solids
in the raw wastewater:

P = S x ((Ws/1x106) x (100/T)) mg l-1

The concentration in the final effluent, F mg l-1, can therefore be estimated from:

F = (1-T/100) x (S x ((Ws/1x106) x (100/T))) mg l-1

Based on the above assumptions, the Zn content in the final effluent in this example is
estimated to be:

Pollutants in Urban Waste Water and Sewage Sludge 45


2. Potentially Toxic Elements

F = (1-70/100) x (2000 x ((450/1x106) x (100/70))) mg l-1

= 0.4 mg l-1

A more mechanistic approach to predicting the fate of metals during wastewater treatment is
described by Monteith et al. (1993) using a computer-based mathematical model. The
mechanistic model, TOXCHEM (Bell et al., 1989), includes both steady state and dynamic
models to simulate operation of a conventional activated sludge plant, incorporating grit
removal, primary clarification, aeration and secondary clarification unit processes.
Biodegradation, surface volatilisation, air stripping, precipitation and sorption removal
mechanisms are determined for trace metallic and organic contaminants in the model’s
database. A sensitivity analysis feature allows the user to investigate the impact of design
and operating conditions and the contaminant’s physical/chemical properties on removal by
unit process and by mechanism.

Inputs to the TOXCHEM model include influent wastewater flow rate, influent metals
concentrations, dimensions of individual process units, plant operation conditions (e.g. mixed
liquor suspended solids concentration), and raw wastewater, primary effluent, and
secondary effluent suspended solids concentrations. The model then predicts metal
concentrations in primary sludge, return activated sludge, surplus activated sludge, and
secondary settler effluent, based on mass balance calculations and removals through
precipitation and sorption. The steady-state model accounts for removal by sorption of
soluble metals onto settleable solids and precipitation of the metals into a settleable form.
The following assumptions were used to develop the model equations:

1, The system is at equilibrium with regard to sorption and desorption;


2, Sorption follows a linear isotherm;
3, Precipitation and dissolution are instantaneous;
4, Precipitated metals are integrated into the biomass and are removed at the same
efficiency as the bulk solids during primary and secondary settlement.

In both the primary settlement and aeration tanks, the model calculates the metal
concentrations in the soluble and solid phases:

Ct = C s + Cx
Cx = Cp + KpXCs

Where:

Ct = total metal concentration, mg l-1


Cs = soluble metal concentration, mg l-1
Cx = solid-phase metal concentration, mg l-1
Cp = concentration of precipitated metal, mg l-1
Kp = linear sorption coefficient, l g-1
X = mixed liquor volatile suspended solids (MLVSS) concentration, g l-1

The values of Kp and metal solubilities are experimentally defined. Solubility was determined
from dosing studies in which metal concentrations were measured in filtered and unfiltered
wastewater samples at equilibrium.
The soluble, sorbed and precipitated metal fractions are calculated by the expression:

Ctest = CT,0/(1 + KP.1Xo)


Where
CT,0 = influent total metal concentration
KP.1 = primary clarifier sorption coefficient
Xo = influent volatile suspended solids (VSS) concentration.

Pollutants in Urban Waste Water and Sewage Sludge 46


2. Potentially Toxic Elements

Fractional removal of metals in the primary and secondary settlers is calculated by:
FRm = (FRsolidsCx)/CT,0

Where
FRm = fractional removal of metal in settler, and
FRsolid = fractional removal of solids in settler.

Fractional removal of the solids is input by the user based on site-specific experience. The
output for the primary and secondary settlers is calculated by:

Ct,out = (1-FRm) CT,0


Where Ct,out = total outlet metal concentration.

The TOXCHEM model was validated against operational data on effluent metal contents
collected from a full-scale wastewater treatment plant (Table 2.33). The predictions were
compared to observed values in the final effluent using linear regression analysis and the r2
statistic. Copper exhibited the highest correlation between predicted and observed effluent
concentrations of the elements tested and the r2 value for this metal was 0.96. The model
predicted that 70 % of this element would be transferred to the sewage sludge. Zinc also
gave relatively good agreement between predicted and observed effluent concentrations and
the results showed that 50 – 60 % of Zn in wastewater would be recovered in the sludge.
The poorest correlation of modelled and actual values was obtained for Ni and the r2 was
0.41 in this case. The model underestimated the removal of Ni by the wastewater treatment
plant and the predicted value was 26 % compared with the observed removal of 37 %. Lead
and Cr have low solubilities and in both cases, the TOXCHEM model predicted much larger
removals of approximately 70 % for these metals than was observed in practice at the
sewage treatment works. However, the model predictions for Pb and Cr were comparable
with operational experience at other wastewater treatment plant (Table 2.32). The slopes of
the regressions lines fell within the range 0.58 – 1.96 bracketing the ideal slope of 1.0. The
model provided good representations of the concentrations of Cu, Ni and Zn in the final
effluent, but was less satisfactory for Pb or Cr. Cadmium was not subject to the verification
exercise because concentrations in the effluent were below the analytical limit of detection.
The modelling and experimental studies showed that Cd and Ni were the most soluble
metals, and the most poorly removed, while Pb and Cr were the least soluble. The majority
of metals, with the exception of Ni, were maintained in the mixed liquor, and the mass
collected in effluent was small in comparison to the total influent mass. At low metal
concentrations (0.02 – 0.1 mg l-1), the soluble fraction is controlled by sorption to solids. At
larger influent metal concentrations, precipitation is the main process controlling soluble
metal fractions. In consequence of this differential fate of metals in WWTS, nickel may need
tighter regulation at source to reduce the amount in the effluent.

The mechanistic approach to model development incorporates the main chemical and
physical processes that are recognised as being important in removing metals from
wastewater. However, in some circumstances, there may be specific properties of a
wastewater at a particular treatment works that influence metal behaviour and removal
efficiency that are not accounted for by these basic assumptions. For example, recoveries of
insoluble elements such as Cr or Pb in sewage sludge are usually relatively high and of the
order >75 % (Table 2.33). This contrasts with the recoveries of these elements measured by
Monteith et al. (1993), which were much lower than those normally observed in practice.
Operational and mechanistic models have the capability to predict partitioning and
distribution of potentially toxic elements from raw sewage during conventional wastewater
treatment. They provide insights into the physico-chemical processes controlling metal
removal in terms of solubility, sorption and precipitation mechanisms, and calculate the mass
balance and partitioning of metals into sewage sludge and the final effluent. The metal
concentration in sludge can be calculated using the estimated partitioning coefficients and
the mass of primary and biological sludge produced by primary sedimentation and
secondary wastewater treatment.

Pollutants in Urban Waste Water and Sewage Sludge 47


2. Potentially Toxic Elements

Table 2.33 Predicted metal concentrations in sewage effluents estimated by the


TOXCHEM model relative to observed values at a full-scale sewage treatment plant
(adapted from Monteith et al., 1993)

PTE Mean concentration (mg l-1) r2 for Removal (%)


Influent Observed Predicted predicted Observed Predicted
effluent effluent vs.
observed
Zn 0.120 0.051 0.057 0.61 58 53
Cu 0.120 0.041 0.034 0.96 66 72
Ni 0.027 0.017 0.020 0.41 37 26
Pb 0.069 0.051 0.022 0.66 26 68
Cr 0.026 0.016 0.007 0.63 39 73

Effect of stabilization processes on metal concentrations in sewage sludge


Potentially toxic element concentrations in sewage sludge are influenced significantly by the
type of stabilization process operated at a WWTS. For example, the destruction of volatile
solids by microbial decomposition of putrescible organic matter in sludge by mesophilic
anaerobic digestion or aerobic composting processes increase the metal content in direct
relation to the extent of volatile solids removal by microbial decomposition.

Unstabilised, co-settled primary + activated sludge typically contains 75 % of volatile matter


on a dry solids basis. During anaerobic digestion, 40 % of the volatile matter is destroyed
reducing the volatile solids concentration in digested sludge by about 50 % compared to the
undigested product. Potentially toxic elements are conserved and are retained in the sludge
during the digestion process. As a consequence of the microbial decomposition of organic
matter, metal concentrations increase in direct proportion to the loss of solids and are
typically raised by approximately 40 % compared with undigested sludge.

Volatile matter is also lost during aerobic composting of sewage sludge (Figure 2.6).
Composting dewatered sewage sludge cake requires a bulking agent, such as straw or
woodchips, to increase porosity and reduce moisture content to values that will support
aerobic microbial decomposition processes. Straw is often used for this purpose and may be
mixed with sludge cake at 25 % ds at a rate of 5 – 10 % on a fresh weight basis (Smith and
Hall, 1991). The addition of bulking agent to sludge reduces the initial metal concentration.
However, metal concentrations in the composting material increase proportionally in linear
relation to the extent of volatile matter destruction by microbial activity. In windrow
composting trials (Smith and Hall, 1991), for example, the volatile solids concentration of
composting sewage sludge and straw decreased by 21 % during a period of 100 days
(Figure 2.6). During that period, the metal concentration in the composted product was
increased above the value in the original sludge (Figure 2.7).

Pollutants in Urban Waste Water and Sewage Sludge 48


2. Potentially Toxic Elements

Figure 2.6 Volatile solids content of sludge-straw compost at different rates of straw
addition (fresh weight) to sludge cake (25 % ds) over time (Smith and Hall, 1991)

75

70
Volatile
Solids
65 5.0%
Content (%)
7.0%
60 8.5%

55

50
0 20 40 60 80 100 120
Time (days)

Sludge stabilisation processes reduce the fermentability of the sludge and the potential
odour nuisance and health hazards associated with its use on agricultural land. However,
the loss of volatile matter during microbial decomposition also significantly increases its
metal content by as much as 40 % compared with material that has not been subject to a
biological stabilisation process. More than 75 % of the sludge produced in the EU is treated
by anaerobic or aerobic digestion. Despite the wide adoption of biological stabilisation
processes for sludge throughout the EU, which generally increase the metal content of
sludge, reported potentially toxic element concentrations in sewage sludge continue to
decline (e.g. Figure 2.7).

This further emphasizes the major and significant improvements in sludge quality, in terms of
potentially toxic element content, that have been achieved in the past 20 years through
improved industrial practices and the successful and effective implementation of trade
effluent controls.

Pollutants in Urban Waste Water and Sewage Sludge 49


2. Potentially Toxic Elements

1300
1200

Cu (mg kg-1 ds)


1100
1000
900
800
700
600
500
50 55 60 65 70 75

1600
Zn (mg kg-1 ds)

1400
1200
1000
800
600
400
200
0
50 55 60 65 70 75

Volatile Solids Content (%)


Figure 2.7 (a) Cu and (b) Zn concentrations in sewage sludge-straw compost in
relation to volatile solids content (Smith and Hall, 1991)

Pollutants in Urban Waste Water and Sewage Sludge 50


2. Potentially Toxic Elements

(a) Zinc (b) Cadmium


2000 2
1.8

Total Cd (Log mg kg-1 ds)


1800
Total Zn (mg kg-1 ds)

1.6
1600
1.4
1400 1.2
1200 1
0.8
1000
0.6
800
0.4
600 0.2
400 0
1978 1983 1988 1993 1998 1978 1983 1988 1993 1998

Year Year

Figure 2.8 Reduction in (a) zinc and (b) cadmium concentrations (untransformed and
log10 transformed data, respectively) in sewage sludge from Nottingham STW, UK
during the period 1978 – 1999

Pollutants in Urban Waste Water and Sewage Sludge 51


2. Potentially Toxic Elements

2.3 Quantitative assessment of potentially toxic elements in untreated UWW, treated


UWW and treated SS

There is limited information available on pollutant concentrations in influent and effluent from
WWTS. Concentrations may also be less than the detection limit of the analytical techniques
used. It must be noted that the variability of influent concentrations within a WWTS can be
very high due to season, precipitation, and levels of industrial and domestic activities. This
means that comparisons based on small numbers of samples must be made with caution.

Table 2.34 Concentrations of potentially toxic elements found in influents and


effluents of WWTS

PTE Country Domestic Urban WWTS Reference


Wastewater Runoff
( g l-1) ( g l-1) Influent Effluent
( g l-1) ( g l-1)
Cd Austria 30 (<20-60) 70 (<20- Hohenblum et al.,
170) 2000
France 6-85 ADEME, 1995
0.2-4.2 Legret,1999
Germany 0.5 80* 0.4 0.1 Raach et al., 1999
<5 Wilderer et al 1997
Greece <1 <1 Greek report, 2000
Italy: <5 Braguglia, et.al., 2000
Central n.a
Northern
Sweden* 200-800 100 Adamsson et al 1998
(domestic)
Cu Austria 120 (90- 120 (<70- Hohenblum et al.,
130) 190) 2000
Germany 150 Wilderer et al 1997
Greece <100 <100 Greek report, 2000
Sweden* 350000- 50000 Adamsson et al 1998
800000 (domestic)
Italy: 20-900 Braguglia, et.al., 2000
Central 2-25
Northern
France 0.011- Legret,1999
0.146
Cr Austria 7100 3900 Hohenblum et al.,
(6200-7900) (<900- 2000
5600)
Germany 30 Wilderer et al 1997
Italy: < 20 Braguglia, et.al., 2000
Central 0.5-32
Northern
Sweden* 4000-14000 3000 Adamsson et al 1998
(domestic)

(Table 2.34 continued)


Hg Austria <10 <10 Hohenblum et al., 2000
France 1-8 ADEME, 1995
Germany 0.4 1* 0.6 0.1 Raach et al., 1999
Greece <1-3 <1-9 Greek report, 2000
Italy: <1 Braguglia, et.al., 2000
Central n.a
Northern
Pb Austria 30 (<20-60) 70 (<20- Hohenblum et al., 2000
160)

Pollutants in Urban Waste Water and Sewage Sludge 52


2. Potentially Toxic Elements

France 14-188 51-630 ADEME, 1995


Legret,1999
Germany 100 110* 81 31 Raach et al., 1999
100 Wilderer et al 1997
Greece <1-5000 <1-17 Greek report, 2000
Italy: < 20 Braguglia, et.al., 2000
Central 0.3-9
Northern
Spain 10-64 Cabrera, et.al,1995
Sweden* 4000-23000 2000 Adamsson et al 1998
(domesti
c)
Ni Austria <40-170 240 Hohenblum et al., 2000
(<40-
620)
Germany 40 Wilderer et al 1997
Italy: < 50 Braguglia, et.al., 2000
Central 0.5-95
Northern
Sweden* 3000-10000 3000- Adamsson* et al 1998
5000
(domesti
c)
Zn Austria 1000 2500 Hohenblum et al., 2000
(<20-3700) (20-
5000)
France 104-1544 Legret,1999
Germany 100-1000 Wilderer et al 1997
Greece 450-3200 <20-900 Greek report, 2000
Italy: 100-900 Braguglia, et.al., 2000
Central 12-185
Northern
*Sweden 150000- 50000 Adamsson et al 1998
1300000 (domesti
c)
As Spain 2.2 Navarro, et.al. 1993
Se Spain: Diaz, et.al., 1996
Se (IV) 0.4
Se (VI) 0.3
Fe France 60-999000 ADEME, 1995
*The data from Sweden are from a very small aquaculture wastewater plant, which only serves a few
houses and may not be typical of other WWTS.

Organotin compounds were the subject of monitoring in Switzerland by Fent and Müller
[1991], and Fent [1996]. Monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were
monitored in raw wastewater (influent), effluent and sewage sludge (Table 2.35). Phenyltin
compounds were also investigated.

Table 2.35 Organotin compounds in Zürich WWTS

Unit MBT DBT TBT


Raw wastewater ng l-1 140 to 560 130 to 1,030 60 to 220
Digested sludge mg kg-1 ds 0.3 to 0.8 0.5 to 1.0 0.3 to 1.0

The potentially toxic element loading per inhabitant, per year has been determined in two
German studies (Table 2.36). There is a good correlation between these studies for zinc,
copper, lead and cadmium concentrations in the influent and effluent of WWTS.

Pollutants in Urban Waste Water and Sewage Sludge 53


2. Potentially Toxic Elements

Table 2.36 Potentially toxic element loading per member of population in two German
towns [Raach et al.,1999; DAF, 1995]

Flow Element Raach et al.,1999 DAF, 1995


[g inhabitant-1 a-1)] [g inhabitant-1 a-1)]
Influent Zn 69 75
Cu 19 28
Pb 14 32
Cd 0.1 0.5
Effluent Zn 26 39
Cu 6.3 6.9
Pb 5.1 5.0
Cd 0.03 0.07

In Norway and Sweden; emissions of potentially toxic elements from WWTS serving more
than 20,000 persons account for almost 80 percent of the wastewater. The discharges of
metals from these WWTS in Sweden and Norway are summarised in Table 2.37. This shows
that, for Sweden, the amount of potentially toxic elements discharged with urban wastewater
decreased over the period 1992 to 1998 for all metals, except for copper. The statistical data
do not take into account the WWTS size and also the potentially toxic elements reported are
for the treated sewage sludge. There is only limited data available on potentially toxic
element content in the treated wastewater (effluent), due to the low concentration, often
below detection limits.

Table 2.37 Emissions of potentially toxic elements from WWTS in Sweden and Norway
1998

Element Sweden Sweden Norway


1992 1998 1998
(kg.annum-1)
Cadmium 325 137 150
Chromium 5420 3308 3000
Copper 14060 15377 15000
Mercury 530* 304 300
Nickel 8165 7603 8000
Lead 2960 1464 1500
Zinc 37420 32346 32000
* data for 1995 [Statistika centralbyrån Sweden, 1998; SFT-1999]

Power et al. [1999] monitored water in the Thames, UK and found statistically significant
reductions in the concentrations of Cd, Cu, Hg, Ni and Zn over the period 1980 to 1997. For
lead, the initial improvements were reversed by drought in the period 1990-1997 resulting in
a slight, though statistically significant rise in Pb concentrations. However; Pb had fallen prior
to this and was still found to have a statistically significant decrease overall in the period
1980-1996 (Table 2.38).

Pollutants in Urban Waste Water and Sewage Sludge 54


2. Potentially Toxic Elements

Table 2.38 Achieved concentration reductions of potentially toxic elements in waters


in the Thames estuary, compared with other European estuaries

PTE Thames Thames % Elbe Rhine Humber Severn


1986/7 1995 reduction 1983 1984 1984 1988
µg.l-1 µg.l-1 µg.l-1 µg.l-1 µg.l-1 µg.l-1
Cd 0.43 0.32 24.1 0.10 0.30 0.31 0.25
Cu 31.30 10.70 65.8 2.00 5.50 2.17 5.00
Hg 0.24 0.09 63.0 - - - -
Ni 17.30 6.30 63.4 3.25 3.20 - 4.50
Pb 16.30 9.90 39.4 1.90 - 1.24 <0.03
Zn 92.00 29.10 68.4 - 21.80 - 17.50
[from Power et al 1999, data included from *Mart 1985, *Nolting 1986, *Balls 1985, *Apte 1990]

The overall reductions in most metal concentrations in the Thames was greater than 50
percent over the years 1986-1995, with lower reductions being experienced for lead and
cadmium. This complements evidence for sludge quality that overall PTE emissions have
markedly improved.

In spite of the reductions achieved by 1995 in the River Thames, potentially toxic element
concentrations are still high compared to the levels found in the 1980s in the other rivers in
the study. It is concluded that while much progress has been made in reducing the
anthropogenic sources of potentially toxic element pollution discharged into the Thames,
improvements are still needed if water is to approximate to background levels. For cadmium
and mercury; the year 2000 levels are forecast to be about twice estimated background
levels [Power et al 1999].

A study carried out in the Rhine region in France [Commission Internationale pour la
Protection du Rhin, 1999] examined all pollutant sources entering the river over a period of
10 years. The study showed that the decrease in certain pollutants was due to pre-
treatment, cleaner technologies and more care in the handling of the priority substances.
Nevertheless, in 1996, the study showed that diffuse and domestic (communal) sources are
important contributors, particularly storm runoff for mercury, lead, and copper.

The study further divided the sources for each metal and other pollutants into greater detail
for each of the riverine countries in the region (France, Switzerland, Belgium, Luxembourg,
Netherlands, Germany). An estimate into the source breakdown of metal pollution into the
Rhine is included in Figure 2.9.

Pollutants in Urban Waste Water and Sewage Sludge 55


2. Potentially Toxic Elements

Percentage contribution of heavy metals for the different sources in the Rhine
100%

90%

80% Diffuse
70%

60%

50% Communal

40%

30%
Industrial
20%

10%

0%
Hg Cd Cu Zn Pb Cr Ni

Figure 2.9 The percentage of potentially toxic elements in the Rhine from different
sources (France, 1999)

The communal sources of wastewater into the river Rhine (in France), include wastewater
from the UWW collecting system, hence showing the widespread presence of these
pollutants (Table 2.39). For mercury, lead, and copper more than half is due to storm runoff.
Erosion and drainage are also important sources, contributing 18% of the mercury and 55%
of the chromium. Atmospheric deposition generally tends to contribute around 8% of the total
diffuse metal contribution, particularly for cadmium and zinc.

Table 2.39: Potentially toxic element pollution contribution by different sources in kg


a-1. [from Commission Internationale pour la Protection du Rhin, 1999]

Diffuse sources Hg Cd Cr Cu Zn Pb Ni
kg.annum-1
Erosion 18 53 5144 3547 10642 4789 5853
Surface runoff 1 10 474 229 1013 67 62
Drainage 7 286 429 2145 28600 2145 1430
Atmospheric deposition 8 75 189 1131 9425 1508 566
Separating system 8 57 475 1900 7600 1520 855
Storm discharge 32 126 630 3780 17640 3780 1890
Untreated wastewater 16 62 310 1860 8680 1860 930
Houses not connected to 2 7 36 216 1008 216 108
UWW collecting systems
Point sources
Industry 74 242 5548 11190 41100 3120 14300
Communal sources 40 200 1400 12470 30000 2700 3500

Pollutants in Urban Waste Water and Sewage Sludge 56


2. Potentially Toxic Elements

A comparison of potentially toxic element concentrations in sewage sludge applied to


farmland in different countries within the EU (Table 2.40) indicates there is some variation
apparent in the metal contents of sludges used in agriculture. For example the reported
average concentrations of Cd in German and UK sludges in 1996 were 1.5 and 3.5 mg kg-1,
respectively (CEC, 2000a). This could indicate differences in the amount of Cd discharged to
sewer in these countries from industrial, domestic and diffuse inputs or the adoption of
different sludge treatment practices and regulatory procedures influencing metal content.
However, these issues are difficult to reconcile given the policies on preventing industrial
discharges of Cd followed in both countries and that both states practice extensive sludge
stabilisation treatment. A possible explanation may be related to the statistical characteristics
of metal concentration data and how data on metal contents in sludge are reported. For
example, CEC (2000a) does not state whether arithmetic averages or weighted averages
are given for metal contents. The UK figures are weighted according to works size and
provide a conservative estimate of sludge metal content because sludge from large
treatment works usually have larger metal concentrations compared with smaller works (EA,
1999). For example, the median Cd concentration in sludge used on to farmland from large
works (2.9 mg Cd kg-1, pe>150000) in the UK was more than twice that from small works
(1.3 mg Cd kg -1, pe<10000) in 1996/97. This trend could be interpreted as being the result of
higher industrial inputs of metals to the large works, although it may also be explained by the
greater interception of atmospheric deposition of metals by paved areas in urban centres
that are served by the largest sewage treatment works. The majority of sludge recycled to
land in the UK is produced by 55 large works (160,000 t ds y-1) whereas approximately 840
small works generate sludge (45,000 t ds y-1) for agricultural use. Therefore, an arithmetic
mean would indicate a significantly lower concentration was apparent for sludge because all
works would have equal weighting. Indeed, the median concentrations recorded for UK
sludge are comparable to the values reported for Germany.

Table 2.40 Comparison of potentially toxic element concentrations (mg kg-1) in


sewage sludge applied to agricultural land in Germany and the United Kingdom in
1996 (CEC, 2000)

Potentially toxic Germany United Kingdom United Kingdom


element (average) (weighted average) (median)
Zn 776 792 559
Cu 305 568 373
Ni 24 57 20
Cd 1.45 3.3 1.6
Pb 57 221 99
Cr 40 157 24
Hg 1.35 2.4 1.5

Pollutants in Urban Waste Water and Sewage Sludge 57


2. Potentially Toxic Elements

Table 2.41 Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Cadmium

CADMIUM Country Mean Median Min. Max. Survey Year/s


Austria 1.5 1.2 0.4 3.4 1994/95 (11)
Germany 1.5 1995-97 (4)
Denmark 1.4 1995-97 (4)
France 4.1 1995/97 (4)
Finland 1.0 1995-97 (4)
Greece (a) 1.6 1996 (6)
(b) 1.4 1997 (1)
Italy 0.8 23 1998/99 (10)
Ireland 2.8 1997 (4)
Luxembourg 3.8 1997 (4)
Netherlands 3 1990 (16)
Sweden 1.5 1995/96 (4)
UK 3.5 1995/96 (4)
Norway 0.97 1998 (12)
Poland 9.93 13.5 0.8 15.3 1999 (3)
EU 4.0 1992 (9)
2.2 1994-98
USA 38.1 8.95 1988 (13)
25 1992 (2)

Limits Agricultural Sewage Sludge


Soils
EU 1-3 10 1* (4)
WHO 7 (5)
USEPA 39 (14)

Table 2.41b Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Chromium
CHROMIUM Country Mean Median Min. Max. Survey Year/s
Austria 62 54 25 130 1994/95 (11)
Germany 50 52 46 52 1995-97 (4)
Denmark 33 34 24.8 40.3 1995-97 (4)
France 69.4 58.8 80 1995/97 (4)
Finland 85.7 84 82 91 1995-97 (4)
Greece (a) 885.8 1996 (6)
(b) 43.8 1997 (1)
Italy 14.8 1400 1998/99 (10)
Ireland 165 1997 (4)
Luxembourg 51 1997 (4)
Netherlands 64 1990 (16)
Sweden 38.4 37.7 39 1995/96 (4)
UK 159.5 157 162 1995/96 (4)
Norway 28.5 1998 (12)
Poland 144.2 136.5 6.8 289.0 1999 (3)
EU 145 1992 (9)
74 1994-98
USA 589 150 1988 (13)
178 1992 (2)

Limits Agricultural Sewage Sludge


Soils
EU 30 –100 1000 600* (8)
(proposed)
USEPA 1200 (14)

Pollutants in Urban Waste Water and Sewage Sludge 58


2. Potentially Toxic Elements

Table 2.41c Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Copper
COPPER Country Mean Median Min. Max. Survey Year/s
Austria 264 240 170 540 1994/95 (11)
Germany 275 1995-97 (4)
Denmark 284 1995-97 (4)
France 322 1995/97 (4)
Finland 288 1995-97 (4)
Greece (a) 302 1996 (6)
(b) 103 1997 (1)
Italy 160 373 1998/99 (10)
Ireland 641 1997 (4)
Luxembourg 206 1997 (4)
Netherlands 190 1990 (16)
Sweden 522 1995/96 (4)
UK 562 1995/96 (4)
Norway 287.1 1998 (12)
Poland 237.5 183.4 24.1 592.0 1999 (3)
EU 380 1992 (9)
365 1994-98
USA 639 444 1988 (13)
616 1992 (2)

Limits Agricultural Sewage


Soils Sludge
EU 50-140 1000-50* (4)
USEPA 1500 (14)

Table 2.41d Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Mercury

MERCURY Country Mean Median Min. Max. Year/s of Survey


Austria 5.1 2.1 1.0 48.0 1994/95 (11)
Germany 1.2 1995-97 (4)
Denmark 1.29 1995-97 (4)
France 2.85 1995/97 (4)
Finland 1.4 1995-97 (4)
Greece 4.1 1996 (6)
Italy 0.46 5 1998/99 (10)
Ireland 0.6 1997 (4)
Luxembourg 1.9 1997 (4)
Netherlands 1.8 1990 (16)
Sweden 1.85 1995/96 (4)
UK 2.50 1995/96 (4)
Norway 1.34 1998 (12)

EU 2.7 1992 (9)


2.0 1994-98
USA 3.24 2.3 1988 (13)
2.3 1992 (2)

Limits Agricultural Sewage


Soils Sludge
EU 1-1.5 10 0.5* (4)
WHO 5 (15)
USEPA 17 (14)

Pollutants in Urban Waste Water and Sewage Sludge 59


2. Potentially Toxic Elements

Table 2.41e Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Nickel

NICKEL Country Mean Median Min. Max. Year/s of Survey


Austria 39 35 14 94 1994/95 (11)
Germany 23.3 1995-97 (4)
Denmark 22.8 1995-97 (4)
France 35.5 1995/97 (4)
Finland 41 1995-97 (4)
Greece (a) 67 1996 (6)
(b) 23.6 1997 (1)
Italy 25 182.5 1998/99 (10)
Ireland 54 1997 (4)
Luxembourg 24 1997 (4)
Netherlands 37 1990 (16)
Sweden 19.3 1995/96 (4)
UK 58.5 1995/96 (4)
Norway 15.4 1998 (12)
Poland 41.1 36.7 8.4 78.8 1999 (3)
EU 44 1992 (9)
33 1994-98
USA 90.6 46.5 1988 (13)
71 1992 (2)

Limits Agricultural Sewage Sludge


Soils
EU 30-75 300 50* (4)
WHO 850 (5)
USEPA 420 (14)

Table 2.41f Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Lead

LEAD Country Mean Median Min. Max. Year/s of Survey


Austria 109 100 40 290 1994/95 (11)
Germany 67.7 1995-97 (4)
Denmark 59.9 1995-97 (4)
France 119.9 1995/97 (4)
Finland 43 1995-97 (4)
Greece (a) 283 1996 (6)
(b) 140.6 1997 (1)
Italy 41 560 1998/99 (10)
Ireland 150 1997 (4)
Luxembourg 128 1997 (4)
Netherlands 145 1990 (16)
Sweden 48.2 1995/96 (4)
UK 221.5 1995/96 (4)
Norway 21.7 1998 (12)
Poland 211.8 190.6 27.7 456.5 1999 (3)
EU 97 1994-98

USA 204 152 1988 (13)


170 1992 (2)

Limits Agricultural Sewage Sludge


Soils
EU 50-300 750-70* (4)
WHO 150 (5)
USEPA 300 (14)

Pollutants in Urban Waste Water and Sewage Sludge 60


2. Potentially Toxic Elements

Table 2.41g Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Zinc

ZINC Country Mean Median Min. Max. Year/s of Survey


Austria 1188 1250 700 1700 1994/95 (11)
Germany 834 1995-97 (4)
Denmark 777.2 1995-97 (4)
France 837.6 1995/97 (4)
Finland 606 1995-97 (4)
Greece (a) 2752 1996 (6)
(b) 1236 1997 (1)
Italy 391 4213 1998/99 (10)
Ireland 562 1997 (4)
Luxembourg 1628 1997 (4)
Netherlands 1320 1990 (16)
Sweden 620.5 1995/96 (4)
UK 778 1995/96 (4)
Norway 340 1998 (12)
Poland 3641 2948 546 7961 1999 (3)
EU 1000 1992 (9)
817 1994-98
USA 1490 970 1988 (13)
1285 1992 (2)

Limits Agricultural Sewage Sludge


Soils
EU 150-300 2500-150* (4)
USEPA 2800 (14)

Table 2.41h Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Arsenic

ARSENIC Country Mean Median Min. Max. Year/s of Survey


Italy 1.1 1.8 1998/99 (10)
UK 2.5 1996/97 (7)
USA 11.0 6.7 1988 (13)
4.9 1992 (2)

Limits Agricultural Sewage Sludge


Soils
WHO 9 (5)
USEPA 41 (14)

Table 2.41i Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Selenium

SELENIUM Country Mean Median Min. Max. Year/s of Survey


UK 1.6 1996/97 (7)
USA 6.14 4.5 1988 (13)
6.0 1992 (2)

Limits Agricultural Sewage


Soils Sludge
WHO 140 (5)
USEPA 36 (14)

Pollutants in Urban Waste Water and Sewage Sludge 61


2. Potentially Toxic Elements

Table 2.41j Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Silver

SILVER Country Mean Median Min. Max. Year/s of Survey


USA 48.2 852 1988 (15)

Limits Agricultural Sewage Sludge


Soils
WHO 3 (5)
Notes: *For sludge applied to soil lower and higher limits are allowed for soil with pH in the range 5-6 and >7
respectively (Commission of the European Communities (2000) working document on Sludge: 3rd draft.
ENV.E.3.LM, 27 April, Brussels
EU 1992 is for B, DK, F, D, EL, IRL, I, L, NL, P, ESP, UK
EU 1994-98 is derived from table values for AT, D, DK, F, FI, IRL, L, SE, UK and NO.
UK and EU is sludge used in agriculture
USA is for all sludge: detection limit set at minimum level
Greece: (a) values are specific to Athens WWTS;
(b) values are average of two rural WWTS.

References

Agelidis M.O. et al, 1997


Bastian, R.K. 1997
Bodzek, B. et al, 1999.
CEC, 1999.
Chang, A.G et al,
Cristoulas, D.G et al, 1997.
Environment Agency of England and Wales, 1999
European Union, 2000
Hall, J.E. et al, 1994
Braguglia et al 2000
Scharf, S et al, 1997
SFT, 2000
USEPA 1992
USEPA 1993
USEPA 1999
Wiart, J. et al, 1995.

Pollutants in Urban Waste Water and Sewage Sludge 62


2. Potentially Toxic Elements

In the particular case of Greece, Voutsa et al. [1996] have compared the potentially toxic
element content of municipal and industrial sludge for Thessaloniki. The results are
illustrated in Figure 2.10. Sludge A is municipal sludge from Thessaloniki’s main WWTS and
sludge B is from a WWTS treating partially treated industrial wastes from the greater
Thessaloniki region.

Figure 2.10. Potentially toxic element concentrations in sewage sludge from biological
treatment of municipal and industrial wastewater (Municipal sludge: Dark, Industrial
sludge: Light Grey)

As shown concentrations of most metals are 2-9 fold higher in municipal sludge than in
industrial (except for Cd and Cu where the contents are similar). This interesting fact, due
possibly to pre-treatment of the most toxic industrial wastewater on site, is not adequately
explained by the authors.

63
3. Organic Pollutants

3. Organic Pollutants: sources, pathways, and fate through urban


wastewater treatment systems

3.1 Sources and pathways of organic pollutants in UWW

There are a large number of organic pollutants from a wide range of sources which may
enter UWW. Paxéus (1996a) identified over 137 organic compounds in the influent of the
municipal wastewater plants in Stockholm. The physical and chemical properties of some of
these organic pollutants are outlined in Appendix B. The main categories of organic
pollutants detailed in this report are:

Polycyclic Aromatic Hydrocarbons: Polycyclic aromatic hydrocarbons (PAHs) arise from


incomplete combustion or pyrolysis of organic substances such as wood, carbon or mineral
oil. Such combustion processes include food preparation in households and food shops;
discharge of certain petroleum products (from garages, vehicle washing and maintenance,
fuel stations); discharge of storm runoff with PAHs from car exhaust particles and road
runoff; and also from incomplete combustion processes in urban landfills.

The most frequent anthropogenic sources of PAHs are: house fires, heat and energy power
stations, vehicle traffic, waste incineration and industrial plants (cement works, metal
smelting, aluminium production). Forest fires represent natural sources. PAHs concentrate in
sewage sludge due to their low biodegradability.

Polychlorinated Biphenyls (PCBs): There are two main sources of PCBs:


• Directly manufactured PCBs (by chlorination of biphenyls), used as hydraulic liquids
(hydraulic oils), emollients for synthetic materials, lubricants, impregnating agents for
wood and paper, flame protective substances, carrier substances for insecticides and
in transformers and condensers. The EU1996 PCB Disposal Directive 96/59/EC
requires the phasing out of all PCBs by 2010 or by 1999 under international
agreement by the North Sea States. Existing transformers and other electrical
equipment which contain 50-500 mg.kg-1 PCB may be retained in service until the
end of their useful life.
• The other main source of PCBs in the environment are combustion processes, from
waste incineration plants, fossil fuel burning and to other incomplete combustion
processes.
PCBs are adsorbed by solids and therefore they accumulate in sewage sludge. The highly
substituted (high chlorine content) PCBs are the main representatives potentially present in
sewage sludge, while they amount to just 35% of the total technical PCBs. Recycling of
PCBs in the environment is very important and remediating historical pollution would be
necessary if the background levels found are to be reduced.

Di-(2-ethyhexyl)phthalate (DEHP):
DEHP is used as emollient in synthetic materials. In Germany, 90 % of DEHP is used in
PVC and about 10% in laquers and paints. It is common to use DEHP as antifoaming agent
in paper production, as an emulsifier for cosmetics, in perfumes and pesticides, they aid in
the production of different synthetic materials such as dielectric in condensers, and
substitute for substances such as PCBs and pump oil. DEHP specific emissions from
various human activities have been identified by Bürgermann [1988] as follows:

• cellulose/paper production
• DEHP production
• plastisol-coating process
• PVC production and processing, leaching from PVC products
• leaching from waste in landfills
• waste incineration and uncontrolled combustion

64
3. Organic Pollutants

DEHP is found regularly in municipal wastewater and, because of its lipophilic properties, it
concentrates in sewage sludge.

Anionic and Non-ionic Surfactants:

Surfactants are contained as the main active agents in all washing and cleaning agents.
These compounds are covered in detail in Case Study (f).

Polychlorinated Dibenzo-p-dioxins and Dibenzofurans (PCDD/PCDF):

The generic term "dioxins" represents a mixture of 219 different polychlorinated dibenzo-p-
dioxins and furans. The most well known and hazardous dioxin, is the tetrachlorodibenzo-p-
dioxin (TCDD). Dioxin concentrations are calculated as sum of the toxicity equivalents (TEQ)
relevative to the most toxic dioxin [TCDD].

The three main sources of polychlorinated dibenzo-p-dioxins and dibenzofurans are as


follows [Mahnke, 1997, Horstmann, 1995]:
• Chemical reactions or chemical reaction processes: Dioxins arise as unwanted
by-products from the production or use of many organo-chlorine compounds, such as
chlorine bleaching of cellulose in paper production and chlorine alkali electrolysis. In
these cases the formation mechanism can be explained by substitution,
condensation or cyclisation reactions.
• Combustion processes or thermal processes: Dioxins arise by thermal processes
and are released into the atmosphere. The dioxin formation results from a de-novo
synthesis. Important thermal sources are:
o waste incineration plants and incomplete combustion processes in landfills;
o combustion plants;
o iron smelting;
o sinter plants, non-ferrous smelting and recycling plants;
o petrol and diesel engines.
• Dioxins can also arise from all incomplete combustion processes involving
chlorine. This explains the ubiquitous dioxins occurrence in the environment.
Anthropic production of dioxins has predominated since the introduction of
organochlorine compounds in industrial applications (1920). With the improvement of
the catalysts in waste incineration plants and other measures for reducing the dioxins
emission, the fraction of anthropic dioxins has been declining since 1970. Dioxins
can be formed and released into the atmosphere also by natural events, e.g. forest
fires. Dioxins can also be generated by the biochemical transformation of precursor
compounds (for example during degradation of chlorophenols).

Dioxins speciation in household wastewater and laundry wastewater is similar to those in the
sediments of UWW collecting systems and sewage sludge. A mass balance indicates that 2-
7 times more dioxins in sewage sludge originates from households than from urban runoff.
Washing machine effluent is a major source of dioxins in household wastewater. Dioxins
were also detected in shower water, and in urban run-off from various human activities
[Horstmann 1993, 1995]. These results suggest that the importance of household
wastewater as a dioxin source has been underestimated [Horstmann et.al., 1993,
Horstmann, 1995].

Sources of other potential organic pollutants are listed below:

Organic pollutants can originate from food and household related products, such as long
chain fatty acids and their methyl and ethyl esters, originating from faeces, soaps and food
oils. Being relatively hydrophobic these compounds are attached to particles, the
concentration of fatty acids and esters in the unfiltered influent is more than 500 µg/l. Other
organic pollutants from domestic origin are the sterols from animal foods and faeces and
indol from faeces. Caffeine is also found from discharges from coffee processing.

65
3. Organic Pollutants

Plasticisers and flame retardants are still used in many products for household and
industrial applications. Among the organic pollutants present are benzenesulphonamides,
adipates (esthers of hexandioic acid), phthalates (esters of phthalic acid, among which
DEHP is the most common), and several phosphate esters. (2-chloroethanol phosphate) and
TBP (tri-n-butyl phosphate) are used in flame-retardant compositions in textiles, plastics as
well as in other products.

Preservatives and antioxidants are constituents of household and industrial products, and
among the organic pollutants linked with these compounds are parabens (esters of
hydroxybenzoic acid), and also substituted phenols and quinones are among the
constituents.

Solvents both chlorinated and non-chlorinated (alcohols, ethers, ketones) are present in a
large range of products such as car shampoos and degreasing products, household
cleaners and degreasing agents from vehicle maintenance and production. Chlorinated
solvents, such as trichloroethylene and trichloroethane, are in increasingly wide use: the
amounts consumed in France per year are 24,000 and 28,000 tonnes, respectively. The
principal sources of diffuse pollution from chlorinated solvents are due to artisanal activities
such as metal finishing activities and dry cleaners. Nevertheless, domestic sources from
aerosols and other agents are not negligible. Pollution by metal cleaning activities is usually
considered as diffuse discharges as they are usually from small firms with only few
employees. Garages consumed around 15,000 tonnes of solvents in 1988, about 60% of
which is lost to the atmosphere and the rest as waste. Of the 6,000 tonnes, of waste solvent
some will be discharged into the UWW collecting system [Agences de l'Eau, 1993]. Metal
finishing used 50,000 tonnes of solvents in 1991 and their aqueous wastes are discharged
into UWW collecting systems, although these are usually in low levels. Dry cleaning
consumed around 19,500 tonnes of solvents in 1988 and it has been determined that
0.3x10-3 kg of solvent/100 kg of clothes cleaned ended up in wastewater.

Fragrances from households, beauticians and hairdressers, generate mixtures of terpenes


and synthetic musks (galaxolides), and are also found in industrial detergents. These are
covered in more detail in Case Study E, Section 6.

Pesticides and herbicides are also a common component of the urban wastewaters and
they result from road and rail weed treatment, and from gardens, parks and urban woodland
areas. They include the triazine group, the phenyl urea group (e.g. chlorotoluron, isoproturon
and diuron), the phenoxy acid group (eg. Mecoprop and 2,4-D) and glyphosate [Revitt et al.,
1999].

An enormous quantitiy of pharmaceutical products are prescribed every year: 100 tonnes
of human drugs were prescribed in 1995 in Germany [Ternes, 1998]. Pharmaceuticals in the
Urban Environment are discussed in Case Study (d), Section 6.

Triclosan (2,4,4’trichloro-2’hydroxydiphenyl ester) has been used in soaps, shampoo and


fabrics, as an antimicrobial agent. While these compunds are regarded as low toxicity their
2-hydroxy isomers have been shown to undergo thermal and photochemical ring closure to
form polychlorinated dibenzo-p-dioxins which are highly toxic. (Okumura et al 1995).

66
3. Organic Pollutants

3.1.1 Domestic and Commercial Sources

A study carried out in France in 1995 by ADEME, showed the sources of the main organic
micropollutants in sludge from WWTS were mainly domestic and commercially related (see
Table 3.1). Another study, by SFT (in collaboration with the wider Norwegian government
environmental study programme and the A/S Sentralrenseanlegget RA-2 WWTS),
investigated sources of PAH, PCB, phthalates, LAS and NPE. This study found that sewage
from domestic sources, in this instance from an isolated housing estate with a separate
sewage and stormwater drainage system, does make a significant contribution of the above
organic pollutants to urban wastewater [SFT report 98/43].

Table 3.1 Principal sources of organic micropollutants in urban wastewater treatment


works [ADEME, 1995] +++ very likely, ++ likely, + less likely present
POLLUTANT ORIGIN Domestic Storm Commercial
usage runoff effluent

Aliphatic Fuel ++ ++ ++
hydrocarbons
Monocyclic aromatic Solvents, phenols + + ++
hydrocarbons
PAHs By-products of petrol + + +
transformation and
insecticides
Halogens Solvents, plastics, ++ + ++
chlorination
Chlorophenols and Solvents, pesticides + + ++
Chlorobenzenes
Chlorinated PAHs PCB, hydraulic fluids (+) + ++
Pesticides + + ++
Phthalate esters Plastifier + + ++
Detergents ++ + ++
Nitrosamines Industrial by-products 0 + ++
(rubber)

Soil is also a major repository of organic matter and the soluble fractions can leach/run-off in
to water courses, especially in upland areas where measures to remove colour and
formation of trihalomethanes during drinking water treament is important.

A. PAHs and PCBs

Table 3.2 shows that the PAH concentration profiles for three Swedish WWTS varies. This
may in part be due to differences in the catchment areas, with the sources of the pollutants
coming from different local industries. Most of these PAHs are expected to derive from
diffuse commercial activities and traffic but PAHs such as pyrene, which is believed to be
derived from at least 50% domestic sources, is present in all the samples at more consistent
concentrations than some of the other compounds.

Mattson et al (1991) referenced in Paxéus (1996a) found that PAHs from food, an often
overlooked source of this pollutant, from households can reach 50-60 % of the total UWW
collecting system load for pyrene and phenanthrene. This is an important observation as
household sources of PAHs are likely to be more difficult to control than commercial
sources.

Another source of PAHs from domestic and commercial activities is the use of phenol and
creosol in products such as wood preservatives. In Finland, 430 tonnes of wood
preservatives were used in 1995 [Finnish Environmental Institute, 1997]. PAHs may enter
UWW as a result of spillages or as surface runoff from rainwater.

67
3. Organic Pollutants

Table 3.2 PAHs concentrations in urban waste waters in Sweden [Paxéus 1996a]

PAHs WWTS
HST GRYAAB SSW
µg/l µg/l µg/l
Naphthalene, dimethyl 1 0.5 <LOD
Naphthalene, methylpropyl 3 <LOD <LOD
1,1’- Biphenyl, dimethyl 2 0.5 <LOD
1,1’- Biphenyl, ethyl 1 <LOD <LOD
Anthracene/Phenanthrene 1 <LOD 0.5
Methyldibenzothiophene <LOD <LOD 0.5
2,8-Dimethyldibenzothioprene 5 <LOD <LOD
Anthracene/Phenanthrene methyl (different 2 <LOD 3
isomers)
Anthracene/Phenanthrene dimethyl (different 1 <LOD 1
isomers)
Retene <LOD <LOD 0.5
Pyrene 3 <0.5 2.5
Pyrene, methyl (different isomers) 2 <LOD 1
Pyrene, methyl, methylethyl or tetramethyl 1 <LOD 1
1,1-Diphenylethane <LOD 0.5 <LOD
1, (H)- Indene, 1-phenylmethylene 0.5 <LOD <LOD
9H-Flouren-9-one 0.5 <LOD <LOD
2-Anthracenaemine <LOD <LOD 9
Acridine, 9-methyl-Dibenz(b,f) azepine <LOD <LOD 0.5
Octahydrophenanthrene, dimethyl-, isopropyl 0.5 <LOD <LOD
Total PAH 23.5 <2 19.5
HST = Henriksdal Sewage Treatment Plant, GRYAAB = Gothenburg Regional Sewage
Works, SSW = Sjölunda Sewage Works (<LOD = below limit of detection)

A study carried out in the Rhine region of France, [Commission Internationale pour la
Protection du Rhin, 1999], showed that control of organic pollutants from point sources has
been effective at reducing levels of contamination in the Rhine. Between 1985 and 1996, the
pollution from PAHs and PCBs had decreased by over 90%. In 1985, 1,075 kg of PCBs were
discharged, which was reduced to 250 kg in 1992, and to 3 kg in 1996, all of which were
from industrial sources. For trichloromethane, 9,000 kg were discharged in 1985, 2,300 kg in
1992, and 2,210 kg in 1996; of these 600 kg were from industry and 1,610 kg from
communal sources.

68
3. Organic Pollutants

B. DEHP

The Danish Ministry of the Environment and Energy [Danish Report, 1999] have estimated
the annual consumption of phthalates in Denmark to be approximately

o 10,000 tonnes in 1992 (about 90% of this used in soft PVC)


o 11,000 tonnes in 1995

In Germany, the total production of DEHP in 1988 was 234,000 tonnes. Of this, 1% was
discharged to surface and groundwater [Brüggermann, 1988].

The vast majority of phthalate emissions to the environment occur, not during the
manufacture, but during the use of the finished products. While in some cases this is a
commercial setting (such as vehicle washing, which will be examined subsequently), there
are also major sources in the domestic environment. Mattson et al. (1991) mentioned
previously regarding domestic sources of PAHs, estimated the household contribution of
phthalates and adipates to the Gothenburg sewage works as 70% of the total load (this
figure emphasises the ubiquity of compounds and difficulty of control). Two major sources of
domestic releases to wastewater (shown in bold in Table 3.3) are floor and wall coverings
and textiles with PVC prints.

Table 3.3 DEHP emissions in Denmark


[adapted from Appendix 1 Danish Ministry of Environment and Energy Report, 1999]

Product Phthalate use (t y-1) Emission to air Emission to air Release to


during production during use wastewater
(t y-1) (t y-1) during use
(t y-1)
Cars 1000 - 0.1-1 2-10
Floor and Wall 2000 - 0.2 1-5
Coverings
Textiles with 5-15 - - 2-13
PVC prints

C Dioxins and furans (PCDD/Fs)

The Environment Agency of England and Wales [1998] estimates dioxin emissions from
industrial Part A processes to UWW collecting systems in the UK as 4.5 µg (TEQ), whereas
emissions to air from these processes was estimated to be 1.1kg. Routes of these pollutants
into wastewater via deposition or industrial process (i.e. washing of air pollution cleaning
equipment), are not discussed. Actions taken to reduce dioxin emissions continue to ensure
IPC authorisations are met.

Recent research at the University of California, Berkeley, reports that deposition of dioxins to
soil is 6 to 70 times greater than estimated emissions [Eduljee 1999]. This suggests that
either not all sources of dioxin are known and/or the contributions from these sources may
not be accurately characterised.

Table 3.4 shows the dioxin emissions for the years 1994-1998 in Austria. There was little or
no change in the dioxin emissions in Austria over this period, but slight reductions, were
achieved in some sectors. The main reason for the emission reduction in 1998 is due to the
air hold ordinance, which limited dioxin emissions from waste combustion as well as from
steam-boiler plants.

69
3. Organic Pollutants

Table 3.4 Dioxin emissions in the time period 1994-1998, Austria


[Federal Environmental Agency, UNECE/CLRTAP, 1999].

1994 1995 1996 1997 1998


Issuer groups Dioxin emissions (tonnes per annum)
Small consumer
(household, trade, 16,820 18,160 18,400 16,780 16,260
administration)
Industry (burning
3,470 3,730 3,880 3,980 3,910
and processes)
Industry
8,170 8,900 7,990 8,550 8,380
processes
Waste handling
180 180 180 180 180
and landfills
Total 28,640 30,970 30,450 29,500 28,740

In Spain, concentrations of dioxins are reported for recent samples (1999) of sewage sludge
and for archived samples (from 1979 to 1987) [Eljarrat, et.al., 1999]. Results are shown in
Table 3.5. It is estimated that the current concentrations of dioxin in sludge have dropped
since the 1970s-80s. This is expected to be due to the source reduction of pollutants, from
combustion and incineration processes, and from certain pesticides contamination and
emphasises the success that controls on use of compounds and trade effluent discharge in
reducing pollutant levels.

Table 3.5 Concentrations of PCDD/F in sewage sludge in Spain [Eljarrat, et.al., 1999]

Type of sewage Range of Mean value


sludge concentrations (pg.g-1 DW as I-TEQ)
(pg.g-1 DW as I-TEQ)
Fresh [1999] 7 to 160 55
Archived [1979-1987] 29 to 8,300 620

E. Other organic compounds

Adsorbable organo-halogen compounds (AOX) resulting from bleach products and from
chlorine use, were reported in studies done in Portugal, in Ria Formosa lagooned sewage
[Bebianno, 1995] and in Italy in the city of Parma [Schowanek, et.al, 1996]. The average
AOX concentration in sewage was reported as 37 µg.l-1.

Sterols were reported in sewage sludge and around discharge wastewater points in
Portugal, in Faro, Tavira and Olhao [Mudge et al., 1997, 1998 and 1999]. Concentrations
ranged between 0.1 to 27.8 µg.g-1 sterols of dry weight of sludge. Hospital wastewater may
contain high phenol concentrations, up to 20,000 µg.l-1, plus other compounds such as LAS,
NPE, PCBs and pharmaceuticals.

F. Vehicle washing

A specific activity identified as a source of a number of organic pollutants in urban


wastewater is vehicle washing, which consists of two distinct phases:

o Actual cleaning, involving the removal of oily dirt, which, on a quantitative basis
would be expected to be similar to the type of oily dirt (asphalt and vehicle exhaust
particles) which is in road runoff. However, this would also involve the use of
degreasing solvents and surfactants which can enter the wastewater treatment
process.
o Vehicle Treatment, involves the use of protective treatments, often coatings using
different types of wax against corrosion, dust and dirt.

70
3. Organic Pollutants

The effluent is usually discharged to the UWW collecting system. Several studies of the
effluents from vehicle washing facilities have been undertaken [Paxéus 1996a, 1996b,
Paxéus and Schröder, 1996, Ulmgren 2000a]. In Sweden, an environmental standard for car
washing detergents was established in Göteborg in 1992 [EHPA, 1992], based on the
Precautionary Principle and Substitution Principle in the Chemical Products Act. In general
COD values found at the effluents of vehicle washes are in the range of typical untreated
industrial petrochemical wastewaters [Huber, 1988].

In Gothenburg, an important site for vehicle manufacture, vehicle washing was estimated to
correspond to 0.5 % of the total wastewater at the Gothenburg WWTS, which was concluded
to have a very small effect on the total load of organic pollutants at the plant. The major
components of the effluents were aliphatic hydrocarbons and alkylbenzenes, originating from
petroleum base degreasing solvents and the oily dirt on the vehicles themselves (asphalt,
vehicle exhaust particles). Low aromatic products reduce the potential environmental
associated with detergent use in car washing facilities. These are produced by
hydrogenation of petroleum-based solvents where substituted benzenes and naphthalenes
are converted to corresponding naphthenes and decalins. The formation and discharge of
polyaromatic compounds is negligible for detergents that come from low aromatic
microemulsions.

Table 3.6 summarises the results of a study on washing both of light vehicles (LV) and
heavy vehicles (HV) [Paxéus 1996]. As can be seen, HVs tend to contribute larger organic
pollutant loads than LVs.

71
3. Organic Pollutants

Table 3.6 Concentration of organic pollutants in car wash effluents in mg l -1


[after Paxeus, 1996]

Conventional LV HV
parameters
Mean Median Range Mean Median Range
Total oil 291 242 10-1750 550 460 65-1200
COD 1263 1180 120-4200 4600 4500 1700-
7500
Aliphatic hydrocarbons
C8-C16 29 22 1-139 103.86 76.72 41-220
C17-C30 0.6 0.4 <0.001 1.84 1.87 0.9-3.0
Aromatic hydrocarbons
Benzene 0.01 0.01 <0.01-0.2 0.02 0.02 0.02-0.03
Toluene 0.08 0.05 <0.01-0.6 0.10 0.08 0.03-0.2
Naphthalene 0.17 0.13 <0.001- 1.1 0.75 0.3-3
0.7
Biphenyl 0.015 0.005 <0.001- 0.12 0.11 0.04-0.2
0.1
Dibenzofuran 0.001 0.002 <0.001- 0.011 0.011 0.009-
0.03 0.012
Phenathrene 0.005 <LOD <0.001- 0.021 <LOD 0.005-
0.03 0.03
Pyrene 0.003 <LOD <0.001- 0.009 <LOD 0.01-
0.01 0 .02
Fluoranthene 0.003 <LOD <0.001- 0.004 <LOD 0.002-
0.01 0.006
Plasticizers
Diethyl phthalate 0.005 0.01 2E-3-0.06 0.01 0.01 0.01-0.02
Dihexyl phthalate 0.05 0.03 <0.001- 0.3 0.21 <0.001-
0.15 0.7
DEHP 0.52 0.38 0.03 - 4.1 1.50 1.30 0.4 - 3
Washing agents
p-nonylphenol 0.60 0.26 0.01-4 0.43 0.41 0.1-0.8
2-Botoxyethanol 25 15 <0.001- 15 17 <0.001-
270 27

It is not known if this area is representative of the Scandinavian region as a whole in terms of
the car washing input. However, it does seem that car washing is also an important source
of pollutants in Norway [SFT, 1998a, 1998b]. In Norway 41 businesses were reported on as
sources of hazardous organic pollutants, PAHs, phthalates (DBP, BBP, DEHP),
nonylphenols (nonylphenol, nonylphenol mono- and di-ethoxylates). The studies found the
highest pollutant loads in the effluents from motor vehicle workshops to urban wastewater
came from petrol stations with car washes, long haul transport depots with ‘car washes’
commercial laundries, paint spraying workshop and chemical businesses [SFT, 1998a,
1998b].

There are two main types of washing agent available and the choice of these would result in
significant differences in wastewater quality:
• Water-based formulations (microemulsions) containing 10-30% hydrocarbons but
increased surfactants (10-30%);
• Petroleum-based degreasing formulations containing 95-99% of hydrocarbons and
3% surfactants.

Plasticisers found in the effluents from vehicle cleaning included phthalates, although
analysis of the cleaning and washing chemicals showed that they themselves contribute very
little to the discharge of plasticisers.

72
3. Organic Pollutants

3.1.2 Urban runoff

A significant proportion of organic contaminants in wastewater are derived from urban runoff.
These organic compounds include aliphatic and aromatic hydrocarbons, PAHs, fatty acids,
ketones, phthalate esters, plasticisers and other polar compounds. Solvent extractable
organics are dominated by petroleum hydrocarbons, which arise from motor oil and tyres
from road surfaces. Organic pollutant sources have not received the extent of research
attention that potentially toxic element pollution has. For example, in the case of PAHs which
are combustion by-products and enter wastewater principally through atmospheric
deposition and urban runoff, the sources can be stationary (industrial sources, power and
heat generation, residential heating, incineration and open fires) and mobile (petrol and
diesel engine automobile) [Sharma et al.,1994]. Different PAH species are associated with
each one of these sources.

A. Road and vehicle related pollution

The main sources of road and vehicle related metals pollution have been outlined in Section
2.1.3. Table 3.7, shows some of the road and vehicle related sources of organic pollutants.

Table 3.7 Qualitative classification of road related sources of organic pollutants


[after Montague and Luker, 1994].

Traffic Maintenance Accidents


Petrol Tar and bitumen Petrol
(PAHs and MTBE)
Oil Oil Oil
Grease Grease Grease
Antifreeze Solvents Solvents
Hydraulic fluid PAHs
Asphalt
PCBs
Pesticides and
herbicides

Table 3.8 summarises the results from three experimental catchments from 1975 to 1982 on
mean concentrations of PAH.

Table 3.8 Summary of pollutant concentrations in urban runoff caused by road related
sources [after Klein, 1982]

Pollutant mean Test catchments


concentrations (mg.l-1) Pleidelsheim Obereisesheim Ulm / West
PAH 2.61 2.97 2.51

The necessary conditions for PAH formation is the presence of benzene and a high
concentration of radical intermediates, which then form stable compounds. Multiple ring
systems are autocatalytic and promote further ring condensations. Fuel aromatic content has
been shown to influence particle-associated PAH emissions almost linearly [Pedersen et al.,
1980; Nunnermann, 1983; Egeback and Bertilsson, 1983]. However, the relationship
between the aromatic content of petrol and PAH formation is not fully understood.

PAHs are produced by unburned fuel, exhaust gases and vapour, lead compounds (from
petrol additives) and hydrocarbon losses from fuel, lubrication and hydraulic systems.
Volatile solids will be added to the total suspended solids loading of rainfall runoff and can
also act as carriers for both potentially toxic elements and hydrocarbons. Some road dusts
have been found to contain 8.5 µg g-1 of PAHs [Colwill et al., 1984 as reported in Luker and

73
3. Organic Pollutants

Montague, 1994]. The introduction of the catalyst technology for motor vehicles lowered the
emissions of PCDD/F in Germany to about 98% [UBA, 1999].

Tyre wear releases hydrocarbons either in particulate form or in larger pieces as a result of
tyre failure. A tyre loses about 10 to 20 per cent of its weight in a lifetime. Annually it is
estimated an average of 140 g of tyre-derived particles are eroded per metre of road
[Environment Agency of England and Wales, 1999].

Plasticisers (such as diethyl phthalate and dihexyl phthalate) are also considered an
important parameter of organic pollution load in urban runoff. Cary et al. [1989], stated that
plasticisers, especially phthalates, represent the major pollutants found in urban storm water.
The concentrations found for 8 plasticisers were recorded. Of these DEHP was found in the
greater concentrations than the other seven plasticisers combined. The main sources of
plasticisers are traffic grime and dirt, associated with the degradation of plastic components
of the vehicles.

B. Roof Runoff

Regarding roof runoff as an interface between atmospheric boundary layer and the runoff
receiving system, Förster (1993) investigated the role of roofs as source and sink of organic
pollutants. The trace organics analysed included PAH, chlorinated hydrocarbons and nitro
phenols. The research indicated that the insecticide HCH was primarily introduced to the
roof runoff system by wet deposition, while the amount of adsorbed PAHs (pyrene;
benzo[a]pyrene=BaP) in roof runoff exceeded the input by rain with events during colder
times of the year where fossil fuel heating systems constitutes additional source for this
pollutant. The concentration profiles for a number of PAHs are illustrated in Figures 3.1 and
3.2 below.

Figure 3.1 PAH in runoff from zinc sheet roof [after Förster, 1993]

74
3. Organic Pollutants

Figure 3.2 PAH in runoff from tar roof [after Förster, 1993]

As can be seen, the concentrations of PAH in roof runoff from zinc roofs was found to be
about ten-fold higher than for tar roofs. There is a difference in the pattern of distribution for
PAH concentration at different precipitation flow rates. For tar roofs PAH concentration is
highest at the lower and higher precipitation flows and lower at intermediate events, whereas
for zinc roofs it tended to be higher at lower precipitation flows. Therefore, concentrations of
**pollutants in roof runoff can be considered variable depending on the characteristics of the
roof material itself as well as on the characteristics of the precipitation event.

A number of hydrocarbons are present in urban rainfall runoff, particularly those associated
with motor vehicles, such as petrol, fuel oils and lubricants. In an unmodified form these
liquids are insoluble in, and lighter than, water. Typically, 70-75% of hydrocarbon oils show a
strong attachment to suspended solids [Luker and Montague, 1994]. PAHs have an even
greater affinity. In contrast, Methyl-tertiary-butyl-ether (MTBEs) the new additive to unleaded
fuel is significantly more soluble in water than all other hydrocarbons in rainfall runoff.
Hydrocarbons, even in low concentrations, can give rise to surface sheens and thus
adversely affect surface waters. Most hydrocarbons eventually degrade by a combination of
microbial and oxidative processes; degradation though is slow, so the increase in oxygen
demand in watercourses and wastewater is likely to be marginal and not a principal
environmental impact.

C. Urban vegetation control practices

Herbicides and pesticides are used in road maintenance operations to control weeds and
pests on the roadsides and verges. The triazine group of herbicides, including atrazine and
simazine, has been used extensively for roadside weed clearance and is more soluble and
mobile than their organo-chlorine predecessors. Combined levels of atrazine and simazine
above 1µg l-1 are not uncommon in watercourses near highways (Ellis, 1991). Collins and
Ridgeway (1980), report that half of pesticides in urban runoff are associated with particles
<63 µm, although these particles are less than 6% of the total suspended solids load.
In urban areas, pesticides in general, and herbicides in particular, are becoming an integral
part of the control of unwanted vegetation by local and municipal authorities, rail and airport
operators. The main herbicides used in the UK are of the triazine group, the phenyl urea
group (e.g. chlorotoluron, isoproturon and diuron), the phenoxy acid group (e.g. Mecoprop
and 2,4-D) and glyphosate (Revitt et al., 1999). Of the phenyl urea compounds, only diuron

75
3. Organic Pollutants

has been widely used in the urban environment and in 1989 this herbicide accounted for
13% of the total 550 tonnes of active ingredient used in the UK (Department of the
Environment, 1991). The comparable use of triazines was 39% but following the introduction
of restrictions for the non-agricultural use of these herbicides in 1992, many users converted
to the use of diuron and glyphosate for the control of vegetation in urban environments
(White and Pinkstone, 1995). The removal of herbicides by rainfall runoff is influenced by
rainfall characteristics, the time interval between herbicide application, the precipitation event
and the properties of the herbicide. However, the full range of factors that influence herbicide
release from sites of application and the mechanisms governing the transport to, and fate of
herbicides in the aquatic environment are not fully understood [Davies et al., 1995; Heather
and Carter, 1996]. The principal herbicide sources in urban catchments include [Revitt et al.,
1999]:

• Urban parks and private gardens


• Road maintenance (to road kerbstones and backwalls)
• Railway system maintenance.

Concentrations in receiving waters, reported by Revitt et al., (1999) in the UK, were
consistently above the drinking water limit of 0.1 µg l-1 recommended for simazine and
diuron; the mean concentrations of which reached 0.34 and 0.45 µg l-1, respectively. In
France [Farrugia et al., 1999], the average application rates for pesticides on the most
consuming urban land uses are reported as 900 g ha-1 for roads and streets, 4000 g ha-1 for
cemeteries and 500 to 800 g ha-1 for parks and sport yards. Householders may also use
large amounts of herbicides and other pesticides but information on the quantities applied is
not available in published literature. However, there was considerable variation in the extent
of water contamination with herbicides between catchments. Farrugia et al, (1999), reported
the average concentration of diurons in water receiving urban runoff was 5 µg l-1, and
attributed this entirely to use in urban situations.

It is to be noted that the hydrological characteristics of hard urban surfaces provide the ideal
conditions for the efficient transport of herbicides (particularly diuron, see also Farrugia et al.,
1999) into UWW collecting systems. This, combined with the existence of inert physico-
chemical environments involving neutral pH, low nutrient and total organic carbon levels,
absence of absorption sites and low bacterial populations, allow the application of herbicides
in urban areas (although in low use), to be an important potential source of contamination of
waste water.

D. Wet and dry deposition

The main repository of PCBs, PAHs and PCCD/Fs is soil. Volatilisation from soil, then further
atmospheric transport and deposition of PAHs, PCBs and PCDD/Fs is considered to be one
of the main contemporary sources of these contaminants in the environment Wild et al.,.
[1995]. PAHs are difficult to control because they are a combustion product.

The Austrian Federal Environment Agency (UBA) analysed PAHs in several media (surface
and wastewater, sediment, soil, sewage sludge, compost, plants, street dusts and ambient
air) between 1989 and 1998 [Gans, et.al., 1999]. Only 10 % of samples were above the
detection limit for PAHs of between 2.6 and 20.3 ng l -1 and these were all taken during winter
and spring, suggesting that PAH originates from the emissions of heating systems during the
cold period.

Once released (by the sources mentioned in the previous paragraphs), airborne PAHs are
transported by the prevailing meteorology before being removed from the atmosphere
through various scavenging mechanisms. As with other airborne pollutants the major
mechanisms of removal of PAHs from the atmosphere are wet deposition, such as rain,
sleet, snow, hail, and dry deposition to the surface. The wet removal of gaseous compounds
is better understood than particulate PAH removal [Ligocki et al., 1985]. The extent of in-

76
3. Organic Pollutants

cloud or below cloud scavenging, collection efficiency of falling precipitation, solubility and
size particles has been examined in the literature [McVeety, 1986 as reported in Sharma et
al., 1994].

Dry removal is a function of atmospheric conditions and the surface level concentration of
PAHs. PAHs adsorbed to particles greater than 20 µm have higher settling velocities and
thus will settle in the vicinity of the source. However, this mechanism will only account for a
minor percentage of removal, as PAH are mostly adsorbed on particles less than 10 µm in
diameter.

77
3. Organic Pollutants

3.2 INFLUENCE OF VARIOUS TREATMENT PROCESSES ON THE FATE OF ORGANIC


POLLUTANTS THROUGH WASTEWATER TREATMENT AND SEWAGE SLUDGE
TREATMENT

3.2.1 PARTITIONING OF ORGANIC POLLUTANTS IN WASTEWATER TREATMENT


PROCESSES.

The general effect of wastewater treatment processes is to concentrate the organic


pollutants in the sewage sludge and the extent of this removal depends on the properties of
the organic species. The overall result of this process is to discharge a treated wastewater
relatively free of organic and inorganic contaminants and a sewage sludge that contains
most of the organic contamination present in the feed wastewater. The main complication of
this general study arises from the large number of possible organic species that could be
present in the feed stream and the complex chemistry sorbtion mechanisms on the solids.

During the treatment cycle, some organic materials can degrade to a certain extent,
especially in aerobic environments and organic material of biological origin is easy to
degrade. Indeed, some common organic pollutants such as LAS, are specifically added to
detergents because they are aerobically biodegradable. A considerable body of literature
exists on this aspect and a variety of oxidants have been proposed. The main aim of this
type of work has concentrated on reducing the organic pollutant content in sewage sludge
prior to land disposal. Advanced oxidation processes might be used in tertiary treatment
especially if the final effluent is to be used for drinking water. However, use of these
processes; regardless of the power of the oxidant, cannot be expected, a priori, to degrade
all types of organic pollutants within a reasonably short time scale. Indeed, the presence of
organics in final effluents is an obstacle in expanding the recycling of wastewater.

3.2.2 Wastewater Treatment

Traditionally, wastewater treatment is supposed to begin at the head of a WWTS at the inlet
screens used to remove large objects such as wood plastics and paper. However, in reality
wastewater conditioning starts in the sewer, in large conurbations the wastewater can have
quite a significant residence time in a sewer. However, it is suggested that dilution of
sewage with runoff water is likely to have an adverse effect on the efficiencies of the
downstream treatment processes (Dorussen et al., 1997).

Primary treatment is installed to enable sedimentation of the feed wastewater. This process
is used to settle, retain and concentrate most of the particulate material to the bottom of the
tank as primary sludge. The process is affected by temperature and the solids content of the
supernatant or primary overflow is significantly higher if the temperature is low, as it is in
winter. Though simple, primary sedimentation is a widespread process in Europe, although
not practised in all WWTS. In some cases primary sedimentation is not installed and in other
plants flocculation, by addition of flocculants, is carried out in the primary sedimentation tank
(Hahn et al., 1999).

The objective of secondary treatment is to contact the primary overflow (settled sewage) with
air in the presence of aerobic bacteria and other micro-organisms, which convert the organic
matter to carbon dioxide and water to a variable extent. There are two types of plant
commonly used for this process: bio filters and activated sludge. Most WWTS use primary
and secondary processes. However some plants may have tertiary treatment which, can
involve coagulation, flocculation and rapid gravity filtration.

A novel process for secondary treatment is the lagoon (Salter et al., 1999). This is large unit
several meters deep and can be stirred gently and aerated. Aquatic life including fish can
survive in some lagoons. The residence time in the lagoon is long and they can be used to
treat the more contaminated municipal wastes. In addition secondary pre-treatment can be
carried out using magnetic flocs. In this process the organic contaminants present are

78
3. Organic Pollutants

loaded on to the magnetic flocs at a low pH and washed off in a high pH medium (Booker et
al., 1996).

There is some concern about the use of iron coagulants, which is of direct relevance to this
study. Some iron reagents used in wastewater treatment are made as a by-product of
titanium oxide production. The titanium ore contains traces of vanadium and uranium. Two
other tertiary methods often cited are activated carbon and membrane filtration. Both
however are rather expensive. Activated carbon is a very efficient means of removal of
organic pollutants and the technique is widely used in small domestic plants used to polish
drinking water. Membrane filtration is also very effective in removing particulate material
from water. However, the membranes are expensive and fouling can occur.

In order to estimate organic and inorganic pollutant removal in wastewater treatment


processes models are required to simulate them. In such models physical properties of the
pollutants are used to determine the likelihood that they will be removed by the process.
More work is needed on modelling the fate of organic pollutants through WWTS and their
transformation throughout the different treatment methods.

It is clear that the regular screening of priority organic pollutants on a day-to-day basis would
be complex and uneconomical. It has been suggested that determination of adsorbable
organic halogens (AOX) be used as an indicator for these priority substances (Hahn et al.,
1999). AOX determination is a relatively easy technique to use (Korner, 2000). These
substances are sorbed from the water on charcoal, which is subsequently pyrolysed. The
hydroxyhalides produced are sorbed and analysed by titration. Another general test
mentioned in the literature (Ono et al., 1996) is the bacterial umu-test, which measures
damage caused by organic pollutants on DNA.

3.2.3 Properties of Organic Pollutants


Octanol-water partition coefficient and solubility
The octanol- water partition coefficient is the ratio of a compound’s concentration in octanol
to that in water at equilibrium.
Concentration of compound in octanol
Kow =
Concentration of compound in water

Kow is dimensionless and values vary over the range of at least 10-3 to 107 and are usually
expressed logarithmically. Large Kow values are characteristic of large hydrophobic
molecules which tend to be associated with solid organic matter while smaller hydrophilic
molecules have low Kow values. Octanol-water partition coefficients can be measured directly
by using conventional “shake flask” methods (Leo and Hansch, 1971). This experimental
approach is restricted to compounds of low-to-medium hydrophobicity, since for compounds
with high hydrophobicity, the concentration in the aqueous phase is too low to be measured
accurately.

Kow can also be correlated with various environmental parameters, such as solubility. By
definition, the partition coefficient expresses the concentration ratio at equilibrium of an
organic chemical partitioned between an organic liquid and water. This partitioning is, in
essence, equivalent to partitioning the organic chemical between itself and water. One would
expect that a correlation would exist between the partition coefficient and solubility. Lyman et
al. (1990) presented the following correlation between solubility based on 156 compounds:
1
log = 1.339 log K ow 0.978
Sw
where Sw is the solubility expressed in mol l-1. This correlation was obtained empirically and
the correlation coefficient was found to be 0.874.

79
3. Organic Pollutants

Organic carbon-water partition coefficient, KOC


The tendency of a compound to sorb to the organic matter such as humic substances
in soil or sewage sludge particles can be assessed using the organic carbon-water partition
coefficient. It is defined as the ratio between the concentration of the organic compound on
organic carbon (mg.g-1) and its concentration in water (mg.l-1), at equilibrium.

Koc = Concentration of compound on organic carbon


Concentration of compound in water
The likelihood of the leaching of a compound through soil or adsorption onto soil organic
carbon can be assessed from K oc values. Generally, organic compounds with high K oc values
will tend to adsorb onto organic carbon whilst compounds with low values have a greater
tendency to be leached. Koc values can be estimated from the octanol-water coefficient or
water solubility. Karickhoff et al. (1981) found the following correlation:

Log Koc = 0.82 log Kow + 0.14

when he examined sorbtion data for a variety of aromatic hydrocarbons, chlorinated


hydrocarbons, chloro-S-triazines and phenyl ureas. The correlation coefficient was 0.93.

In this study a specific list of organic pollutants has been defined and it can be seen that
their solubilities are very low but the Koc values are very high in the region of 105 indicating
that the sorbtion would be very favourable. From the Koc values and the weight fraction of
organic carbon species present in the feed (f) an estimate of the removal of organic species
can be made. The amount left in the supernatant water as a percentage left (L) is given by:
 1 
L = 100  
 K oc f 
Thus if f = 10-3 and Koc = 10-5, the percentage left would be 1%. There is limited data
available or actual results but figures for L are generally much higher. (Pham et al., 1997)
report that 30% of PCB and only 25% of the PAHs were removed from a specific treatment
plant.

3.2.4 Modelling

Understanding the processes involved in wastewater treatment is likely to provide a basis for
understanding the pathways and partitioning of pollutants in these processes. The way to do
this is to develop models of the processes and to simulate plants using computers. An
example of such a comprehensive model has been published (Gabaldon et al., 1998). The
model does not specifically include large molecular weight organics.

It is of some of interest to note that there is some work on processes that occur in a sewer.
One study aims to model the emissions of volatile organic compounds in cocurrent air flow in
open and closed sewers (Olsen et al., 1998). Another study measures the removal of COD
and proteins within a sewer (Raunkjaer et al., 1995) and found that there were quite
noticeable losses in a sewer. In another study the sewer pipe was considered to consist of a
sediment above which was a bio-film and above that the water phase (Fronteau et al., 1997).

O’Brien et al. [1995] and Mann et al.[1997] present a first order model for a wastewater
plant. In the secondary section aeration for stripping, biodegradation and sorption on to a
PAC (Powdered Activated Carbon) were considered. PCB, PCDD/F or PAH were not
included but the methodology presented in this paper could be applicable to the study of the
fate of these high molecular weight pollutants in secondary treatment. Work has been done
on modelling trickling filter-beds (Shandalor et al., 1997). This predicts the drop of solids
loading in the water as it trickles down the bed. On the more specific case of organic

80
3. Organic Pollutants

pollutant removal, a detailed paper has been published on the removal of volatile organic
contaminants in a wastewater plant (Melcer et al., 1994). However, again no specific
mention of PAH or similar organics was made.

3.2.5 Organic Degradation in Wastewater


Among the organic pollutants being studied in this report, LAS is somewhat unusual as it is
added to water in detergents. Studies in this subject (Holt et al., 1998 and Prats et al., 1997)
report very similar LAS degradation levels of over 90%. Although the removal of LAS in
WWTS is quite effective some 16% of the feed LAS is taken out in the sewage sludge (Field
et al., 1995). In this sorbed form it is more difficult to degrade. Some studies of LAS in river
sediments (Tabor et al., 1996) show that this compound is sorbed on to the solids and only
slowly biodegradable. Thus there would be an amount of non degraded LAS in the solid
residue.

There have been a number of studies on the degradation rate of PCDD, PCDF and PCBs,
which have been reported in a review article (Sinkkonen et al., 2000). The experiments were
conducted in laboratory rigs and the data reported as half-life analogous to radioactive
decay. The mean half-life quoted is given in Table 3.09.

Table 3.9: Half-lives of PCDD, PCDF and PCB in water

Substance Half life in water


(years)
PCDD 2.6
PCDF 5.0
PCB 9.3

This study seems to indicate that these organics will not be degraded in a WWTS. These
half-lives are considerably longer than the residence time in a sewage treatment plant or
sewer. As the authors point out the experiments were conducted near ideal conditions and,
in practice, the half lives are believed to be longer than the figures quoted in the table,
especially if the temperature is low.

PAH compounds are believed to be persistent in the environment. There is some work that
presents evidence that some of these compounds can be degraded in periods of 12-80
hours (McNally et al., 1998). Compared with PCDDs this time period is rapid. However,
these experiments on biological degradation of PAH were carried out under ideal conditions.
There was a constant temperature (20oC), specially adapted bacteria were used and
nutrients were added. In a practical case where low temperature and few nutrients are
present, the actual degradation times would be much longer (in the region of 80-600 hours)
so PAH compounds are unlikely to be degraded in a conventional wastewater treatment
plant. Research in Greece by Samara et.al. [1995] and Manoli et al. [1999], shows that the
lower-molecular mass PAHs are removed effectively in Thessaloniki's WWTS, whereas the
higher molecular mass PAHs are resistant to the biological treatment. The heavy molecular
mass PAHs are partially removed by adsorption, whereas the lower molecular mass PAHs
are removed by volatilisation and/or biodegradation.

Work on oestrogenic compounds, analysing 17β-oestradiol equivalent concentrations, found


that the load of oestrogenic activity in the wastewater was reduced by about 90% in the
sewage plant. Less than 3% of the oestrogenic activities was found in the sludge (Korner et
al 2000).

81
3. Organic Pollutants

3.2.6 Removal of Organics


Coagulants such as aluminium and ferric salts are used in water treatment to remove
particulate matter. However, soluble organics may also be removed by coagulation by
mechanisms such as specific adsorption to floc particles and co-precipitation (Semmens and
Ocanas, 1977). Sridhan and Lee (1972) studied the removal of phenol, citric acid and
glycine from lake waters by co-precipitation with iron. Though these results were reasonable,
excessive concentrations of coagulant (300-1500 mg.l-1) were required. Other workers made
similar findings. Semmens and Ocanas (1977) examined the removal of dihyroxybenzoic
acid (DHBA) and resorcinol from distilled water by coagulation with ferric sulphate. Results
indicated that the extent of organic removal increased as coagulant dosage increased.
Maximum percentage removals were 35% for DHBA and 8% for resorcinol. Semmens and
Ayers (1985) examined the effectiveness of alum and ferric sulphate in removing octanoic
acid, salicylic acid, phenol and benzoic acid from Mississippi river water and water samples
free of organic matter. These compounds were generally poorly removed by coagulation and
in most cases the extent of removal did not depend strongly on coagulant dosage. Removals
ranged between 3-20%. Salicylic acid was most efficiently removed and benzoic acid was
most poorly removed. Generally, better removal of the organic compounds occurred when
natural organics were not present.

The general consensus of the work done to date indicates that the use of coagulants for
removing organics is feasible. However it is impractical as the excessive addition of
coagulants is necessary.

Humic substances account for around 50% of the dissolved organic matter in natural water
(Vik and Eikebrokk, 1989). They are formed easily from waste material and there is evidence
that they will sorb organic matter by binding with them. Activated carbon is widely used as a
means of removing organic compounds from water. The presence of humic acid reduces the
rate of organics uptake (Kilduff et al., 1988). The capacity of activated carbon for
trichloroethylene (Summers et al., 1989, Wilmanki and Breeman, 1990), trichlorophenol
(Najm et al., 1996) and lindane decreased in the presence of humic substances. Other
sorption media such as organoclays (Dentel et al., 1998, Zhoa and Vance, 1998) and an
organic polymer resin (Frimmel et al., 1999) are not so badly affected by the presence of
humic substances. Ying et al., (1988) studied the effects of iron precipitation on the removal
of natural organic compounds like tannic acid and humic acid, and toxic organic compounds
like chlorendic acid (HET), polychlorobiphenyls (PCBs) and organochlorine pesticides.
Freshly formed ferric hydroxide flocs were very effective in removing humic acid and tannic
acid and it was found that the presence of humic acid enhanced significantly the removals of
PCBs and many of the organochlorine pesticides by ferrous and ferric hydroxide
precipitates. Removals were achieved by a combined mechanism of complexation,
adsorption and co-precipitation. This evidence suggests that humic substances are capable
of sorbing organic material.

A process was devised in which organic contaminants were removed by adding humic acid
and a coagulant such as ferric hydroxide (Rebhun et al., 1998). This showed good recovery
for the organics tested. The results of this work suggest that humic acid might be added in a
tertiary cycle. The humic acid could be made by composting grass cuttings, potato peeling
and other waste feeds. Such material could be added to the final effluent of a wastewater
treatment plant followed by contact and flocculation.

3.2.7 Conclusions – removal of organics in wastewater


The practical issue of the removal of organics in wastewater treatment is not well
documented in the literature. Modelling work reviewed here, has shown that the work has
concentrated on the removal and degradation of organic matter of biological origin and that
synthetic organic pollutants have been largely neglected. Clearly modelling work for
pollutants should be promoted.

82
3. Organic Pollutants

This data in turn relies upon analysis of these organic pollutants. Present methods using
GC/MS are extremely complex and not suitable for routine plant use. Lack of easier methods
for their analysis will hinder the development of simple processes to remove these organic
materials. It could be argued that identification of a specific pollutant is not crucial for plant
development and that a generic test would be suitable. One of the most important aspects of
future work is the development or identification of simple tests for WWTP analysis. The
problem is not confined to treatment plants alone but rapid treatment methods could be used
to detect sources of heavy organic chemicals.

One of the results of the difficulty in doing analyses is that there is little data available on
partitioning process. There is a suggestion that around half the organics fed to a wastewater
treatment plant remain in the supernatant stream. This might well be a surprising result given
the measured property values in the region of 105 (dimensionless) would suggest that there
would be a good binding between organic pollutants and the settled sludge. It is possible
that there is some competition for sorbtion sites in the organic matter from the more
concentrated organic compounds.

With more rapid analysis techniques in place, there would be the opportunity to make
process changes to reduce the amounts of organics present in the final effluents. It is felt
that advanced oxidative techniques such as the use of ozone would not be applicable in the
present context as the organics have a very small concentration in solution and have a low
reactivity. One interesting possibility is in situ treatment in sewers such as adding activated
carbon to contaminated streams. As humic substances are efficient scavengers for organic
pollutants, humic acid derived from composting food waste could be added in a tertiary stage
to strip organics from the final effluent. It is a matter of policy, to see if such ideas should be
promoted further but initial work could start before the rapid analysis methods had been
agreed.

Transfer and partitioning of organic contaminants to the sludge matrix


The sorption of organic contaminants onto the sludge solids is determined by physico-
chemical processes and can be predicted for individual compounds by the octanol-water
partition coefficient (Kow). During primary sedimentation, hydrophobic contaminants may
partition onto settled primary sludge solids and compounds can be grouped according to
their sorption behaviour based on the Kow value as follows (Rogers, 1996):

Log Kow < 2.5 low sorption potential


Log Kow > 2.5 and < 4.0 medium sorption potential
Log Kow > 4.0 high sorption potential

Volatilisation and thermal degradation


Many sludge organics are lipophilic compounds that adsorb to the sludge matrix and this
mechanism limits the potential losses in the aqueous phase in the final effluent. A proportion
of the volatile organics in raw sludge including: benzene, toluene and the dichlorobenzenes
may be lost by volatilisation during wastewater and sludge treatment at thickening,
particularly if the sludge is aerated or agitated, and by dewatering. Volatilisation is used to
describe the passive loss of organic compounds to the atmosphere from the surface of open
tanks such as clarifiers. The majority of volatilisation, however, occurs through air stripping in
aerated process vessels. As a general guide, compounds with a Henry’s Law constant >10-3
atm (mol -1 m -3) can be removed by volatilisation (Petrasek et al., 1983). The significance of
volatilisation losses of specific organic compounds during sewage treatment can be
predicted based on Henry’s constant (Hc) and Kow (Rogers, 1996):

Hc > 1 x 10-4 and Hc/Kow > 1 x 10-9 high volatilisation potential


Hc < 1 x 10-4 and Hc/Kow < 1 x 10-9 low volatilisation potential

83
3. Organic Pollutants

However, more recent studies (Melcer et al., 1992) suggest that the stripping of volatiles
may not be as significant as was initially thought and biodegradation during secondary
biological wastewater treatment may be the main mechanism of loss of the potentially
volatile compound types (Table 3.10). For example, Melcer et al. (1992) reported that
biodegradation processes removed ≥90 % of the dichoromethane, 1,1,1-trichoromethane,
trichloroethylene, toluene and xylene from a municipal wastewater. Volatilisation was only a
significant mechanism of removal for 1,4-dichlorobenzene (20 %) and tetrachloroethylene
(60 %). The fate and behaviour of volatile organic compounds in wastewater treatment plant
have been modelled numerically by the TOXCHEM computer-based model that incorporates
four removal mechanisms including: volatilisation, stripping, biodegradation and sorption on
to solids (Melcer et al., 1992).

Table 3.10 Observed and predicted (TOXCHEM) removals of volatile organic


contaminants during wastewater treatment by stripping and biodegradation (Melcer et
al., 1992)
Compound Air stripping (%) Biotransformation (%)
Observed Predicted Observed Predicted
Dichloromethane 2.6 3.2 92.4 91.9
Chloroform 7.4 7.8 73.6 71.9
1,1,1-Trichloroethane 10.5 6.0 79.7 89.1
Trichloroethylene 10.7 3.1 82.7 91.3
Tetrachloroethylene 58.7 64.2 15.8 0.0
1,4-Dichlorobenzene 19.1 17.2 54.7 54.8
Toluene 1.2 0.4 98.6 98.3
p- and m-Xylene 1.3 0.6 98.1 97.9

High temperature treatment of sludge by disinfection processes at 70 oC for 30 minutes can


enhance the loss of volatile compounds. Mono- and two-ringed aromatic compounds
(benzene, toluene, xylene, naphthalene, dichlorobenzene etc) may be partially lost under
these conditions (Wild and Jones, 1989). Other more persistent hydrophobic compounds, eg
lesser chlorinated PCBs, and the three-ringed PAHs, may also be susceptible to
volatilisation. Thermal drying is being introduced as an enhanced treatment process to
produce sanitised biosolids for unrestricted use and for improved handling and bulk
reduction. This process is potentially the most effective at removing volatile substances from
sludge because the solids are exposed to high temperatures (400 oC) and the sludge is
dried to >90 % ds. Thermal degradation may also be an important mechanism for the
removal of organic contaminants from sewage sludge during heat treatment (Wild and
Jones, 1989). Volatile organic compounds in sewage sludge are not regarded as a potential
risk to human health or the environment when sludge is used in agriculture (Wilson et al.,
1994).

Destruction by sludge stabilisation processes


Mesophilic anaerobic digestion is the principal sludge stabilisation process adopted in most
European countries, where approximately 50 % of sludge production is treated by this
methods. Volatile compounds are generally lost to the atmosphere or transferred to the
supernatant during digestion, whereas PAHs and phthalate acid esters are conserved (Bridle
and Webber, 1982).
Many organic contaminants are biodegraded under anaerobic conditions and this is
enhanced by increasing retention time and digestion temperature. Five characteristic
behaviour patterns (Figure 3.3) of decay are observed for organic contaminants in anaerobic
digestion systems based on net gas (total CH4 + CO2) production (Battersby and Wilson,
1989):
• Easily degradable (eg ethylene glycol, diethylene glycol, triethylene glycol, sodium
stearate, ethanol);

84
3. Organic Pollutants

• Degradable after a lag phase (eg phenol, 2-aminophenol, 3- and 4-cresol, catechol,
sodium benzoate, 3 and 4-aminobenzoic acid, 3-chlorobenzoic acid, phthalic acid,
dimethyl phthalate, di-n-butyl phthalate, pyridine and quinoline);
• No degradation or gas production (3- and 4-aminophenol, 2-chlorophenol, 2-cresol,
2-nitrophenol, 2- and 4-chlorobenzoic acid, bis (2-ethylhexyl)phthalate, hexylene
glycol, neopentyl glycol, n-undecane, n-hexadecane, 2,4-D, dieldrin, cis- and trans-
permethrin, tetrahydrofuran, furan, pyrrole, N-methylpyrrole, thiophene, benzene,
pyrimidine, 1-naphthoic acid);
• Inhibitory in the initial phase of incubation (eg 3- and 4-chlorophenol, 2,4- and 2,6-
dichlorophenol, 2,4,6-trichlorophenol, 3- and 4- nitrophenol, 2-phenylphenol, 2-, 3-
and 4-nitrobenzoic acid, CTAB, MCPA, MCPP, lindane, naphthalene,
anthraquinone);
• Inhibitory throughout incubation (eg 3,5-dichlorophenol, pentachlorophenol, 2,4- and
2,5-dinitrophenol, 4-nonylphenol, sodium dodecylbenzene sulfonate, sodium 4-
octylbenzene sulphonate, 2,4,5-T, butyltin trichloride, dibutyltin dichloride, tributyltin
chloride).
Degradation is generally aided by carboxyl and hydroxyl groups, whereas chloro or nitro
groups tend to inhibit anaerobic biodegradation and gas production.

Figure 3.3 Typical patterns of net gas production (CH4 + CO2) from organic chemicals
incubated anaerobically with diluted primary digested sewage sludge.
1, Easily degradable; 2, Degradable after a lag period; 3, little effect on gas production; 4,
inhibitory in initial phase of incubation; 5, inhibitory throughout incubation
(Battersby and Wilson, 1989).

100 1 2
Net gas production (% theoretical)

}3
Time 4
Inhibition

-100 5

Biodegradation during anaerobic digestion may virtually eliminate certain organic


contaminants from sewage sludge, but in general the destruction achieved is typically in the
range of 15 – 35 % (WRc, 1994). Aromatic surfactants including linear alkyl benzene
sulphonates (LAS) and 4-nonylphenol polyethoxylates (NPnEO) occur in sludge in large
concentrations. These compounds are not fully degraded during sewage treatment and there
is significant accumulation in digested sludge. For example, mass balance calculations
suggest that approximately 80 % of LAS is biodegraded during the activated sludge process
and 15-20 % is transferred to the raw sludge (Brunner et al., 1988). Approximately 20 % of
the LAS in raw sludge may be destroyed by mesophilic anaerobic digestion sludge. The
compounds, nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO)
are formed during sewage treatment from the microbial degradation of NPnEO. These

85
3. Organic Pollutants

metabolites are relatively lipophilic and accumulate in the sludge and are also discharged
with the treated sewage effluent. One of the most important consequences of anaerobic
digestion, however, is the production of nonylphenol (NP), which accumulates in digested
sludge. Approximately 50 % of the NPnEO in raw sewage is transformed to NP in digested
sewage sludge. The loadings of LAS and NP to soil in sewage sludge used on farmland are
significantly larger than for most of the other organic contaminants present in sludge and
there is concern about their potential environmental effects. This is particularly the case for
NP in sludge due to its potential oestrogenic activity (UKWIR, 1997). However, in the aerobic
soil environment, these compounds provide substrates for microbial activity and are rapidly
degraded so there is minimal potential risk to the environment or transfer to the human
foodchain. For example, LAS has a short half-life in soil in the range 7 – 22 days in
temperate field conditions (Holt et al., 1989) and the half-life for NP is <10 days (UKWIR,
1997). Current studies at Imperial College, funded by the Food Standards Agency in the UK,
are investigating the potential for plant uptake of NP into staple food crops from sludge-
treated soil.

Another class of organic chemicals, the phthalate acid esters, are also an abundant group of
compounds present in sewage because of their extensive use as plasticising agents. The
phthalates are also suspected as being potential environmental oestrogens (UKWIR, 1997).
Shelton et al. (1984) reported the complete degradation of the lower molecular weight
phthalate esters, and of butyl benzyl phthalate, within 7 days in laboratory scale anaerobic
digesters operated at 35 oC. Therefore, these phthalate compounds should generally be
removed by most municipal anaerobic digesters at the normal mean retention times
operated in practice (>12 days). The extent and rate of biodegradation during anaerobic
digestion is apparently related to the size of the alkyl side chain and compounds with larger
C-8 group are much more resistant to microbial attack. Therefore, di-n-octyl and di-(2-
ethylhexyl)phthalate (DEHP) are considerably more persistent to anaerobic microbial
mineralisation and are generally not removed by conventional anaerobic stabilisation
processes. However, phthalate esters are rapidly destroyed under aerobic conditions,
usually achieving >90% removal in 24 h in activated sludge wastewater treatment systems.
In soil, the reported half-life is <50 d (UKWIR, 1997).

Composting is a thermophilic aerobic stabilisation process and usually involves blending


dewatered sludge at approximately 25 % ds with a bulking agent, such as straw or wood
chips, to increase porosity of the sludge to facilitate microbial activitiy. The biodegradation of
relatively persistent organic compounds such has been reported for composted sludge (Wild
and Jones, 1989). For example, PAHs may be partially degraded by composting sludge and
average removals of 13 % and 50 % have been measured for benzo(a)pyrene and
anthracene, respectively, although phenanthrene persisted unchanged in laboratory
composting trials (Martens, 1982; Racke and Frink, 1989).

Thermophilic aerobic digestion processes and sludge storage for three months can achieve
similar overall removal rates for organic contaminants as those obtained with mesophilic
anaerobic digestion (WRc, 1994). Thermal hydrolysis conditioning of sludge prior to
conventional anaerobic stabilisation may have a significant influence on the removal of
organic contaminants from sludge, but this is a comparatively new enhanced treatment
process and effects on the destruction of organic contaminants have yet to be investigated.

86
3. Organic Pollutants

3.3 Quantitative assessment of organic pollutants in untreated UWW, treated UWW


and treated SS

For the main list of organic pollutants considered in this report there is little available data of
the concentrations in the influent to the wastewater treatment plant. Paxéus and Schröder
[1996] looked at over 50 organic compounds, in the influents and effluents of the
Gothenburg wastewater treatment plant. The high cost of testing explains the lack of data on
dioxins in urban wastewater.

Most of these compounds were reduced to below the limit of detection during the treatment
process. Some of the organic compounds, such as caffeine were reduced from a level of
37µg.l-1 to 4µg.l-1. Some of the phosphorus containing compounds were not reduced during
the treatment process (although the influents and effluents were quite low at 1µg.l-1). The
overall toxicity of the influent and the effluent were also measured and found to have
decreased by approximately 50% during the treatment process.

450
400
Dioxin concentration (ng TEQ

350 German limit =


100 ng TEQ kg-1 ds
300
250
200
150
kg-1 ds)

100
50
0
1944 1949 1953 1956 1958 1960 1998
Year

Figure 3.4 Dioxin content of archived samples of sewage sludge form Mogden WWTS,
UK
It can be seen (Figure 3.4) that there has been a significant reduction in the concentration of
dioxins since the 1950s and 1960s in sludge over recent years.

The concentrations of other organic contaminants in sludge, including, PCBs and PAHs,
have also declined significantly in sludge in the UK. This is due to the control of primary
sources of these substances. In 1984, McIntyre and Lester (1984) measured median and
99th percentile concentrations for PCBs in sludge (444 samples from UK sewage treatment
works) of 0.14 and 2.5 mg kg-1, respectively. Ten years later, Alcock and Jones (1993)
reported the total PCB content of 12 UK sludges from rural, urban and industrial sewage
treatment works ranged between 0.106 to 0.712 mg kg-1, with a mean value of 0.292 mg kg-
1
. These results indicate that overall PCB concentrations in UK sludges have declined
markedly in response to the ban on industrial production, use and discharge of these
substances. Similar trends are apparent in Germany (Table 3.11). In effect, this means that
the chemical composition of sewage sludge is already subject to stringent, albeit indirect,
controls that have been effective in minimising industrial sources and inputs of persistent
organic contaminants.

87
3. Organic Pollutants

Table 3.11 Mean concentrations of organic contaminants in German sewage sludge in


1988/89 relative to data collected until 1996 (Leschber, 1997)

Contaminant 1988/89 1991/96


Adsorbable organo-halogens mg kg-1 ds 250-350 140-280
Polychlorinated biphenyls(1) mg kg-1 ds <0.1 0.01-0.04
Polycyclic aromatic hydrocarbons(1) mg kg-1 0.25-0.75 0.1-0.6
ds
Di(2-ethylhexyl)phthalate mg kg-1 ds 50-130 20-60
Nonylphenol mg kg-1 ds 60-120 -
Dioxins and furans (ng TEQ kg-1 ds) <50 15-45
(1)
Single congeners

Table 3.12 Survey of organic pollutants in UWW and WWTS (µg.l-1)

Compound Country WWTS Reference

Influent Effluent
(µg.l-1) (µg.l-1)
PAHs Austria:
Total PAHs - EPA15 147-625 20-70 Gans et al.,1999
Germany: Hagenmaier et al,
Total PAHs 0.79 1986
Benzo(a)pyrene 0.08
Benzo(k)fluoranthene 0.05
Greece: Manoli et al, 1999
Benzo(a)pyrene 0.022 0.005
Fluoroanthene 0.24 0.029
Indeno (1,2,3-cd) pyrene 0.015 0.005
France 0.05-0.44 0.02-0.09 ADEME, 1995
Germany 33 Koch et al, 1989 &
Balzer et al 1991
UK 51.8 (5.6 to 30.8 (2.4- Morris et al, 1994
349) 147)
DEHP Austria 4.4 0.3 Hohenblum et al.,
2000
Germany 122 (7-232) 15 (5.6-184) Faltin, 1985
Anionic Italy 290-4800 - Braguglia et al,
Surfactants 2000
Detergents France 1-26 0.1-2.7 ADEME, 1995
LAS Austria 400-3500 11-55 Scharf et al., 1995
Germany 5400 67 Feijtel et al 1995
Greece 129 (35- Kilikidis et al. 1994
325)
Italy 4600 43 Feijtel et al 1995
Netherlands 4000 9 Feijtel et al 1995
Spain 9600 140 Feijtel et al 1995
UK 15100 10 Feijtel et al 1995
NPE Austria: Hohenblum et al.,
Nonylphenol- 2,096,000 363,000 2000
monoethoxylate
Nonylphenol- 13,093,000 639,000
diethoxylate
Italy: Di Corcia et al.
NP 4 1994
NPEO 27
NPEC 145
Sweden 0.5-6.0 Paxéus 1996a
Germany 0.02 0.002 Koppe et al, 1993

88
3. Organic Pollutants

Other organic
pollutants: France 0.1-0.4 <0.1-0.5 ADEME, 1995
Chlorophenols 300
Chlorinated 1.15
organics 10
Pesticides
VOCs
Germany Ternes et al, 2000
Iodinated X-Ray 4.3
contrast 3.3
substances: 0.18
iopamidol 0.17
diatrizoate 1.6
iothalamic acid 7.5
iomeprol
iopromide
Total Phenols Italy 2.5-300 Italian Regional
Environmental
Protection Agency
Dioxins Italy: 0.024-16.9 Italian Regional
Environmental
Protection Agency

PAHs: wastewater from 8 different sewage treatment influents was investigated in 1996 by
the UBA [Gans, et.al., 1999]. Similar PAHs content were determined, except for the influent
from a chemical plant, which had an approximately 1,000 times larger concentration. PAHs
especially, with a low molecular weight were found in high concentrations. Apart from the
higher PAH content of the wastewater from the chemical plant, no significant differences
could be detected between municipal and industrial influents. The PAHs content of the
effluent was about 10 times smaller than the influents [Gans et.al.1999].

The Danish regulation of the application of waste products [Ministry of the Environment and
Energy 1996] sets certain cut off values for the maximum concentrations of organic
contaminants in sludge to be distributed on agricultural land as shown in Table 3.13.
Concentrations of PAHs in Danish sewage sludge are also shown in Table 3.14 The PAH
concentration of the nine selected compounds were all found to have mean concentrations
above the concentrations permissible for use on agricultural land in Denmark.

Table 3.15 Danish standards for maximum concentrations of organic contaminants in


sewage sludge (Danish Ministry of the Environment and Energy, 1996)

Danish Standards 1997 - cut off values 2000 - cut off values
mg.kg-1 DS mg.kg-1 DS
LAS 2,600 1,300
nonylphenol (including nonylphenol 50 10
ethoxylates)
PAHs* 6 3
DEHP 100 50
*(total concentration of nine selected PAHs) Acenaphthylene, Fluorene, Phenanthrene, Fluoranthene,
Pyrene, Benzo(b,j,k)fluoranthene, Benzo(a)pyrene, Benzo(g,h,i)perylene and Indeno(1,2,3,-cd)pyrene

The values in bold are difficult to achieve, as they are far below current sludge
concentrations. If 50% of pyrene and phenathrene is from food sources and gives sludge
concentrations of > 300mg.kg -1 ds, then this emphasises how difficult these standards are to
achieve.

The mean concentrations of LAS, NPE and DEHP were found to be within the Danish limits
for use on agricultural land but the range of concentrations in all cases went over the cut off
limits; therefore many of the sludges would not be allowed to be used on agricultural land.

89
3. Organic Pollutants

The concentrations of some of the organic contaminants in the sludge were found to depend
strongly on the wastewater treatment process [Danish EPA]. The concentrations of LAS, NP
and NPE were significantly lower (P<0.005) following activated sludge treatment than in
mixed activated and digested sludge treatment, presumably due to extended aeration.

It can be seen that government and other institutions are trying to introduce limits for certain
pollutants and that concern for wastewater pollution reduction is increasing. Nevertheless, it
is noted that important discrepancies exist in analysis techniques, even within a country,
hence slowing the determination of limits, particularly for PAHs and PCBs. Due to the
expected increase in sludge production and the reinforcing of the legislation in relation to the
concentration limits for potentially toxic elements and organic pollutants, it seems necessary
throughout Europe to harmonise analysis techniques and the pollutants targeted in the
control of wastewater and sludge quality. Discharge standards to UWW collecting systems
for industries and possibly reformulation of certain domestic products should be determined
in order to reduce pollution entry into the systems.

Table 3.14a) Survey of organic pollutants in sewage sludge: mg kg-1 DS (a)PAHs


PAHs Country Mean Median Min. Max. Year/s of
Survey
B[A]P Austria 0.30 0.22 0.09 0.67 1994/95
I[1,2,3-cd]p 0.27 0.21 0.07 0.58 (24)
Σ PAHs* Germany 6.4 2.6 15.3 1996 (10)
B[a]p (municipal) 0.35 0.1 1.1 1996 (10)
Fl.thene 1.2 0.6 2.7 1996 (10)
I[1,2,3-cd]p 0.3 0.1 0.8 (10)
B[a]p 0.5 0.4 0.1 3.4 1995 (14)
B[a]p Denmark 0.15 0.07 <0.01 1.4 (28)
Fl.thene 0.3 0.1 <0.01 3.3
I[1,2,3-cd]p 0.67 0.23 <0.01 0.63
Fl.thene Spain 3.4 1.1 6.0 (19)
B[a]p France 0.04 11 1994 (6)
Fl.thene 0.15 31 1994 (6)
B[a]p Greece 0.24 0.24 0.1 0.36 (15)
Fl.thene 1.1 1.3 0.38 1.4
I[1,2,3-cd]p 0.11 0.12 0.05 0.15
Σ PAHs Sweden 1.2-2.2 0.7-1.4 1995/98
Fl.thene 0.01 0.7 (26)
(29)
Σ PAHs** UK 27.8 6.0 83.8 1994 (27)
B[a]p Fl.thene 2.6 0.1 7.5 1989 (33)
2.3 2.5 1.1 4 1991 (29)
Σ PAHs*** Switzerland 0.50 0.35 0.04 1.83 (29)
(municipal)
B[a]p Italy <0.05 2000 (34)
I[1,2,3-cd]p <0.05
Fl.thene <0.05
Σ PAHs Poland 72.3 74.4 32.7 114.3 1999 (2)
EU
B[a]p USA 13.8 4.7 154 1988
Fl.thene 9.95 154 (30/31)

Limits Agricultural Soils Sewage Sludge


Σ PAHs**** EU 6 (proposed) (9)
Pyrene WHO 480 (5)
B[a]p USEPA 21.4 (25)
B[a]p: Benzo[a]pyrene; Fl.thene: Fluoranthene I[1,2,3-cd]p: indeno(1,2,3-c,d)pyrene
* sum of 16 USEPA priority list PAHs (see Appendix B)
** sum of naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthracene,
pyrene, chrysene, benzo(a)anthracene
*** sum of benzo(b+k)fluoranthene, benzo(ghi)perylene, benzo(a)pyrene, fluoranthene, indeno(1,2,3-c,d)pyrene

90
3. Organic Pollutants

**** sum of acenapthene, phenapthene, fluorine, fluoranthene, pyrene, benzo(b+j+k)fluoranthene,


benzo(a)pyrene, benzo(ghi)perylene, indeno(1,2,3-c,d)pyrene

Table 3.14b) Survey of organic pollutants in sewage sludge: mg kg-1 DS (b)PCBs

PCBs Country Mean Median Min. Max. Year/s of


Survey
PCB (28,52,101, Austria 0.07 0.05 0.02 0.27 1994/95
138, 153,180) (24)
Germany 0.01-0.04 1991-96
0.5 0.05 15 (13)
1985-87 (7)
Denmark 0.05 0.03 <0.03 0.2 (28)
Spain 0.05 0.93 (20)
PCB France 0.03 0.4 1994 (6)
(101,118,138)
Sweden 0.1 0.1 1995/98
(26)
UK 0.34 0.01 21.5 (18)
EU
USA 1.46 1.48 14.8 1988
(30/31)

Limits Agricultural Soils Sewage Sludge


EU 0.8 (proposed) (9)
WHO 30 (5)
USEPA 6.6 (25)

Table 3.14c) Survey of organic pollutants in sewage sludge: mg kg-1 DS (c)DEHP


DEHP Country Mean Median Min. Max. Year/s of
Survey
Austria 23.4 34.4 (11)
Bis-(2ethylhexyl)- Germany 20-60 1991-96
phthalate <2.4 320 (13)
(7)
Denmark 38 25 3.9 170 (28)
Bis-(2ethylhexyl)- Sweden 6.7 28 (29)
phthalate
EU
Bis-(2ethylhexyl)- Canada 68.0 11 959 (3)
phthalate
USA 110 17 891 1988
(30/31)
Limits Agricultural Soils Sewage Sludge
EU 100 (proposed) (9)

91
3. Organic Pollutants

Table 3.14e) Survey of organic pollutants in sewage sludge: mg kg-1 DS (e)LAS

LAS Country Mean Median Min. Max. Year/s of


Survey
Austria 8107 7579 2199 17955 1994/95(24)
Germany 5000 50 16000 1985-87(7)
Denmark 2700 530 11 16100 (28)
Aerobic Spain 100 500 (1)
Anaerobic 12100 17800 (21)
Finland 9700 (17)
Italy 11500 14000 (4)
UK 8700 10400 60 18800 (12)
EU
Aerobic Anaerobic USA 152 (16)
4680 1680 7000 (22)
Limits Agricultural Sewage Sludge
Soils
EU 2600 (proposed) (9)

Table 3.14f) Survey of organic pollutants in sewage sludge: mg kg-1 DS (f)NPE

NPE Country Mean Median Min. Max. Year/s of


Survey
Austria 24 12 69 1994/95(24)
Germany 60-120 1988/89(13)
51 3.8 96.3 1996 (10)
NP1EO 20 5 80 (7)
NP2EO 10 <3 80 (7)
Denmark 15 8 0.3 67 (28)
Sweden 400 26 1100 1990 (32)
13-27 10-26 1995/98(26)
UK 326-638 256 824 (27)
EU
USA

Limits Agricultural Soils Sewage Sludge


EU 50 (proposed) (9)

Table 3.14g) Survey of organic pollutants in sewage sludge: mg kg-1 DS (g)PCDD/F


DIOXINS & Country Mean Median Min. Max. Year/s of
FURANS (NG Survey
TEQ/KG DS)
Germany 15-45 1991-96
(13)
Spain 55 42 7 160 1994-98 (8)
620 29 8300 1979-87 (8)
Sweden 24 23 25 (23)
UK 40.2 7.6 192 (29)
EU
USA 82.7 37.4 0.49 2321 1988
Dioxins 90.4 1820 (30/31)

Limits Agricultural Soils Sewage Sludge

EU 100 (proposed) (9)

92
3. Organic Pollutants

References
1. Berna JL et al, 1989 11. Hohenblum, P, et al 22. Rapaport RA, et al
2. Bodzek, B. et al, 2000. 1990.
1999. 12. Holt MS et al 1992. 23. Rappe et al 1989
3. Bridle, T.R. et al 1983 13. Leschber, R. 1997 24. Scharf, S, et al. 1997
4. Cavelli L, et al 1993 14. Litz. N, et al, 1998. 25. Smith, S.R. 2000
5. Chang, A.G. et al 15. Manoli, E. et al 1999. 26. Statistika
1995. 16. McAvoy DC, et al meddelanden 1998
6. Conseil supérieur 1994. 27. Sweetman 1994
d'hygiène publique de 17. McEvoy & Giger 1986 28. Tørsløv J, et al 1997.
France, 1998 18. McIntyre. A,E, et al 29. UKWIR 1995
7. Drescher-Kaden et al 1984 30. USEPA 1992
1992, 19. Moreda, JM, et al 31. USEPA 1999
8. Eljarrat. E, et al 1999. (1998a) 32. Wahlberg,.C, et al
9. European Union, 2000 20. Moreda, JM, et al 1990
10. Hessische (1998b) 33. Wild. S,R, et al 1989.
Landesanstalt fur 21. Prats D, et al 1993. 34. Braguglia et al 2000
Umwelt (1991-96).

Table 3.15 shows the occurrence of certain organic pollutants in sewage sludge in Germany.

Table 3.15 Occurrence of certain organic substances in sewage sludge, Germany


[Priority list USEPA and 6/464/EEC of EG].

Compound Occurrence
in sludge
Benzo(a)anthracene +++
Benzo(a)pyrene +++
Benzo(k)fluoranthene +++
Dibenzo(a,h)anthracene +++
Indeno(1,2,3-cd)pyrene +++
PCB-1242 ++
PCB-1254 +++
PCB-1221 ++
PCB-1232 ++
PCB-1248 ++
PCB-1260 +++
PCB-1016 +
2,3,7,8-Tetrachlordibenzo-p-dioxin ++
Frequency of occurrence: +++ frequent (90-100%), ++ less frequent, + low frequency

93
4 Health and Environmental Effects of Pollutants in UWW and SS

4. HEALTH AND ENVIRONMENTAL EFFECTS OF POLLUTANTS IN UWW AND SS

4.1 Potentially toxic elements

Copper, Cr, Zn, Se, are essential trace elements, however, they are potentially toxic
elements, and above certain concentrations, may interfere with or inhibit the actions of
cellular enzymes. Effects are summarised in Table 4.1, together with the Maximum
Concentration Limits (MCL) in drinking water (Source: EPA and WHO).

Potentially toxic elements at high concentrations, are acutely toxic to humans. High
concentrations are rare in urban waste water, but could possibly result from accidental spills,
although there is limited exposure from this route. The major concern is exposure to low
concentrations over longer time periods. This is chronic exposure and may have more subtle
effects.

The chemical form and corresponding bioavailability of potentially toxic elements to plants,
fungi, micro-organisms and animals are also important, affecting regulation regarding the
compound. Complex dietary interactions are inherently protective limiting the accumulation
of metals in animal body tissues (see Case Study a). The phytotoxic concentrations of Zn
and Cu in plant leaves less than the zootoxic concentration of these elements in plant
produce consumed by animals and humans. Technically based, precautionary soil limit
values for these metals protect crop yields and the human diet from the potentially toxic
effects of metals in sewage sludge, see Case Study (a).

94
4 Health and Environmental Effects of Pollutants in UWW and SS

Health effects of potentially toxic elements

Table 4.1: Summary of the acute and chronic effects of the pollutants
PTE Drinking Water Acute Health Effects Chronic Health Effects Carcinogenicity Notes
Standards
EU WHO US
EPA
Cu 0.1-3 2 1 Irritation of mouth and throat, Liver and kidney damage, "pink disease", No evidence
mg.l-1 mg.l-1 mg.l-1 headaches, dizziness, nausea, cirrhosis
diarrhoea, gastric ulcers,
jaundice, renal damage, death
Zn 0.1-5 5 Stomach and digestion Immune system damage, and interferes No evidence Taken up by plants,
mg.l-1 mg.l-1 problems, dehydration, impaired with the body's ability to take in and use phytotoxic
muscular coordination other essential elements such as copper
and iron
Cd 0.005 0.003 0.005 Digestive tract irritation, colitis, Half-life = 10-40 years. Lung, kidney, and Strong evidence in Taken up by plants,
mg.l-1 mg.l-1 mg.l-1 vomiting, diarrhoea, death. hematopoietic system damage due to build animals, weak phytotoxic
up, fragile bones, anaemia, nerve or brain evidence in
damage in animals humans
Cr 0.05 0.05 0.1 Allergic responses in skin, Damage nose and lungs, increases risks of Evidence in High potential for
VI mg.l-1 mg.l-1 mg.l-1 chromium VI irritates nose, non-cancer lung diseases, ulcers, kidney, humans and bioaccumulation in
lungs, stomach, and intestines, and liver damage. Birth defects and animals aquatic organisms
convulsion, death reproductive problems in mice
Hg 0.001 0.001 0.002 Nausea, vomiting, diarrhoea, Brain, lung, kidney, and damage to Evidence in mice Binds to dissolved
mg.l-1 mg.l-1 mg.l-1 increase in blood pressure, skin developing foetus, neurological disorders, matter not
rashes, eye irritation, renal depression, vertigo, and tremors phytotoxic, High
failure potential for
bioaccumulation in
aquatic organisms
Ni 0.05 0.02 0.04 Allergic reactions, lung damage Chronic bronchitis and reduced lung Evidence of lung Phytotoxic, very
-1 -1 -1
mg.l mg.l mg.l function, lung disease. Affects blood, liver, and nasal sinus mobile in water
kidney, immune system, reproduction and cancers in
development in mice and rats humans

95
4 Health and Environmental Effects of Pollutants in UWW and SS

Pb 0.05 0.01 0.015 Anaemia, constipation, colic, Non-specific: damage to nervous system, Evidence in Not usually
mg.l-1 mg.l-1 mg.l-1 wrist and foot drop, renal kidneys, and immune system. In children, animals phytotoxic,
damage. In children, symptoms can cause decrease mental ability and bioconcentration in
are irritability, loss of appetite, reduced growth. In adults, can cause a shellfish
vomiting, and constipation. decrease in reaction time and affect
memory, miscarriage, premature births, and
damage to male reproductive system
As 0.05 0.01 0.05 Nausea, vomiting, diarrhoea, Skin keratosis, decrease in the production Evidence in Taken up by plants,
mg.l-1 mg.l-1 mg.l-1 damage to tissues including of blood cells, bone marrow suppression, humans, of which are sensitive
nerves, stomach, intestines and abnormal heart function, liver/kidney increased risk of to lower
skin, damage, impaired nerve function, damage liver, bladder, concentrations than
to foetus in animals kidney, and lung animals,
cancer, may inhibit bioaccumulation in
some DNA repair fish and shellfish,
mechanisms persistent in the
environment
Ag 0.01 - 0.05 Breathing problems, lung and Argyria and may affect brain and kidneys No evidence
mg.l-1 mg.l-1 throat irritations, and stomach
pains, allergic reactions,
necrosis, haemorrhage, and
pulmonary oedema
Se 0.01 0.01 - Dizziness, fatigue, irritation, Brittle hair, deformed nails, and loss of Suspected human
mg.l-1 mg.l-1 collection of fluid in lungs, feeling and control in arms and legs, carcinogen: liver
bronchitis, rashes, swelling, reproductive effects in rats and monkeys, and lung tumours
and birth defects in birds observed in rats
and mice

EU: EC drinking water directive (1998)


WHO: WHO (2000) and Guidelines for drinking water quality Vol.2 (1996).
USEPA: ATSDR (2000) and Standards for maximum permissible values in sewage sludge/soils. Estimating concern levels for concentration of
chemical substances in the environment. Washington DC (1984).

96
4 Health and Environmental Effects of Pollutants in UWW and SS

4.2 Organic pollutants

Over 6,000 organic compounds have been detected in raw water sources many of which are
due to commercial activities. These compounds are present in many industries, processes
and by-products, and are wide spread in a number of domestic products. They may also
enter wastewater from surface run off. LAS and NPE are widely used in detergents and are
ubiquitous in the environment.

Examinations of the surfactant toxicity revealed that anionic and non-ionic surfactants are
non-toxic to man upon oral intake, but can be very toxic for marine life. Table 4.2 shows the
toxicity of anionic and non-ionic surfactants [Berth and Jeschke, 1987]

Table 4.2 Toxicity of anionic and non-ionic surfactants [Berth and Jeschke, 1987]

Surfactant Toxicity
LD50 fish (mg/l) LD50 Daphnia (mg/l)
LAS 3 - 10 8.9 - 14
NPE 1.5 - 11 4 - 50

Effect of Sludge Treatment Processes on Organic Contaminants

Sewage sludge is treated to reduce its fermentability, nuisance (particularly odour) and
vector attraction potential as well as to reduce bulk and improve its physical characteristics
to aid handling, dewatering and acceptability for use on agricultural land. These techniques
include physical, chemical and microbiological manipulation of the sludge and may involve
mechanical dewatering, heating, chemical reactions and microbiological transformation
processes that may influence the loss, or potential formation, of organic contaminants. Loss
mechanisms include (Wild and Jones, 1989; Rogers, 1996):

• Volatilisation;
• Biological degradation;
• Abiotic/chemical degradation eg hydrolysis;
• Extraction with excess liquors;
• Sorption onto solid surfaces and association with fats and oils.

Some chemicals are more susceptible to these transformation/loss mechanisms than others
and certain treatment processes can increase the concentration of conservative compounds
that are retained as volatile solids are removed during stabilisation action are due to the
formation of stable reaction intermediate compounds.

Sewage sludge potentially contains thousands of organic compounds derived from industrial,
domestic, atmospheric and natural dietary sources. The total organic matter content of
sludge is typically in the range 60-80%, depending on the extent of stabilisation treatment
and volatile solids destruction. The vast majority of the organic content is environmentally
benign material that confers part of the agronomic benefit associated with sewage sludge
use on farmland by improving the physical and structural characteristics of treated soil.
However, certain anthropogenic compounds are potentially toxic and would be detrimental to
human health if they were to transfer from sludge-treated soil to the foodchain in
toxicologically significant amounts. The range of organic compounds known to exist in
sludge is extensive and diverse. For example, Drescher-Kaden et al. (1992) reported that
332 organic substances, with the potential to exert a health or environmental hazard, had
been identified in German sludges and 42 of these were regularly detected in sludge.

The main route of entry of environmental contaminants into the human foodchain is by
uptake into the edible parts of crop plants. However, despite the increasing intensity and
extent of scientific investigation into the potential environmental consequences of organic

97
4 Health and Environmental Effects of Pollutants in UWW and SS

contaminants applied to farmland in sewage sludge, there is no evidence for soil-crop


transfer. This is because those compounds exhibiting some solubility and potential for plant
uptake are also susceptible to rapid degradation processes in soil or are lost through
volatilisation, whereas other more persistent compounds usually have very low solubilities
and are strongly adsorbed by the soil matrix in non-bioavailable forms. The principal concern
and theoretical mechanism of entry to the human foodchain of organic contaminants in
sewage sludge applied to agricultural land is from the surface application of liquid sludge
and the intake of organic contaminants by livestock grazing treated pasture and the
accumulation of lipophilic compounds in meat fat and milk.

However, in practice, there has been no demonstrable relationship between sludge


application and transfer of organics to animal tissues or milk. Furthermore, this theoretical
exposure route will diminish with the additional precautions being introduced to minimise the
risk of animal infections with enteric pathogens in sludge that prevent the application of
conventionally treated sludge products, such as liquid digested sludge, to grazed pasture.
Improved pasture hygiene obtained by sub-surface injection of liquid sludge also eliminates
the theoretical exposure of grazing livestock to organic contaminants in sludge. Current
trends suggest that, in future, surface application to grassland is likely to be in the form of
enhanced treated biosolids, such as thermally dried sludge, which do not adhere to grass
thus mitigating the intake of contaminants in sludge by ruminants.

New and recently identified organic compounds


Uptake of organic contaminants by crop plants from sludge-treated soil has been
demonstrated experimentally to be negligible and the human dietary intake of organics from
plant foods is not considered to be an important route of exposure. The theoretical potential
risk to humans from these compounds in sewage sludge arises from the direct ingestion of
surface applied sludge adhering to grazed pasture and the potential for transfer to milk and
meat fat consumed as food. However, it is emphasised that surface application of
conventionally treated sludges to grazing land has been phased out in the UK, it is not
practised in a number of European countries and may not be permitted in the revised the
Sludge Directive. The 3rd Draft of the Working Document on Sludge (CEC 2000) states that
deep injection followed by a no grazing interval of six weeks after application is acceptable
for sludge treated by conventional processes (eg mesophilic anaerobic digestion). Deep
injection burial of sludge below the soil surface improves pasture hygiene and avoids the
potential for sludge ingestion by grazing livestock. Advanced treated sludges may be spread
on grazing land, but current trends suggest thermal drying of sludge may expand and
pasture contamination and animal ingestion is significantly reduced by the application of
dried, or finely divided solid products, which do not adhere to grass. These developments
significantly reduce the potential risk of human dietary exposure to organic contaminants in
sewage sludge applied to farmland. A comprehensive list of compounds that could be
present in sludge and maintain their integrity during treatment and following application to
agricultural land has been developed by Alcock et al. (1999). The compounds selected
included:

Chlorinated paraffins – There are >200 commercial chlorinated paraffin formulations in use
as plasticisers in PVC and other plastics, extreme pressure additives, flame retardants,
sealants and paints. Total production of short chain paraffins in the EU is approximately
15000 t y-1. Illicit disposal of oils containing paraffins into the wastewater system may be a
significant route of entry into the environment. Approximately 50 % of the lubricating oils
used by industry in Sweden may be released into the air or WWTS.

Brominated diphenyl ethers (PBDEs) - This group of compounds is used, in descending


order of importance, for flame retardation in high impact polystyrene, and in flexible
polyurethane foam, textile coatings, wire and cable insulation and electrical connectors.
Their use has expanded in the last decade in response to more stringent fire regulations and
the increased use of plastic material and synthetic fibres. Total annual global consumption is
currently 40,000 t. A survey in Sweden (Sellstrom, 1993) indicated relatively high

98
4 Health and Environmental Effects of Pollutants in UWW and SS

concentrations of the TeBDE and PeBDE congeners were present in sludge (15 and 19 µg
kg-1, respectively).

Polychlorinated naphthalenes (PCNs) – The production of PCNs ceased in the US in 1977


and by the mid-1980s in western Europe. This group of 75 compounds was used for cable
insulation, wood preservatives, engine oil additives, capacitors and as feedstock for dye
production, similar to that for PCBs. The principal releases of PCNs into the environment are
probably waste incineration and landfill disposal of items containing PCNs. PCN
concentrations in sewage sludge may be in a similar range to individual PCB congeners. In
Swedish sludge, for example, PCN concentrations were in the range 0.15 – 0.16 µg kg -1 ds
(Nylund, 1992). Some PCN congeners have dioxin like activity and have been assigned
TCDD toxic equivalent values similar to those for coplanar PCBs (Hanberg, 1990) and so
have toxicological interest.

Quintozene (pentachloronitrobenzene) – A small amount of this compound is produced in


the EU (21.5 t y-1) and it is registered for use in the UK, Spain, Greece and Cyprus. It has
low water solubility and half-lives in soil and are reported to be in the range 5 – 10 months.

Polydimethylsiloxanes (PDMS) – These are nonvolatile silicone polymers used in industrial


and consumer products including lubricants, electrical insulators and antifoams. They are
hydrophobic and partition onto the sludge solids and concentrations in sludge were reported
in the range 290 – 5155 mg kg-1 in a survey of N American WWTS (Fendinger, 1997).
However, PDMS do not bioconcentrate or exhibit significant environmental toxicity, but they
are relatively persistent in soil and can take months to years to fully degrade.

Nitro musks (chloronitrobenzenes) – This is a group of synthetic dinitro- trinitro-substituted


benzene derivatives used as substitutes for natural musk in perfume and body care
products, washing agents, fabric softeners, air freshners etc. Musk xylene and musk ketone
and the most extensively used forms and current world production of musk xylene is more
than 1000 t y-1. In Europe, current consumption is estimated to be 124 t y-1 for musk ketone
and 75 t y-1 for musk xylene and the release of these compounds to the environment is
dominated by domestic discharges to sewer. Some biodegradation is likely during
wastewater and sludge treatment and the compounds will also biodegrade in soil with a
reported half-life of 12 days. There is only limited knowledge of toxicity to humans, but the
potential risks from sewage sludge use on farmland are probably minor relative to the
general exposure that is received from the use of these compounds in body care and
washing products.

Oestrogenic compounds – The endogenous oestrogens (17β-oestradiol and oestrone) and


synthetic steroids such as ethinyloestradiol, which is the active oestrogenic component in
oral contraceptives, are considered to be far more significant in relation to impacts on
aquatic ecosystems in discharged effluents from WWTS rather than from partitioning onto
particulates and associating with sewage sludge (Alcock et al., 1999).

Pharmaceuticals – Compounds designed for specific biological effects in medical practice


can enter the wastewater system by excretion or residues and metabolites in urine and from
intentional disposal. This is regarded as acceptable practice because of the dilution received
within the sewer system. Interestingly, 30 – 90 % of antibiotics administered to humans and
animals are excreted in active forms in urine. The potential toxicological and ecotoxicological
activities of these substances in the wider environment are generally unknown, but, because
of their biological function, they are generally designed to be rapidly metabolised and
degraded. Many commonly used analgesic drugs are rapidly biodegraded during sewage
treatment including aspirin, ibuprofen and paracetamol (Richardson and Bowron, 1985).
Most of these are soluble and exist primarily in the aqueous phase and transfer to sewage
sludge is probably of only minor concern, although it is not possible to predict partitioning
and fate during sewage treatment due to the absence of physico-chemical data for many of
the compounds.

99
4 Health and Environmental Effects of Pollutants in UWW and SS

Synthetic fats – In addition to Alcock’s list there have been recent concerns in the US about
synthetic fat substitutes that are used in food products. These compounds are not toxic to
humans, but are persistent and are not biodegraded in sewage and sludge treatment or in
soil (pers. com. T.J. Logan, N-Viro, USA).
Pharmaceuticals are covered in more detail in Case Study (d). Some of the bodycare
products are covered in more detail in Case Study (e).

Polyelectrolytes
Polyelectrolytes based on polyacrylamide and cationic copolymers are used extensively in
sludge treatment to aid dewatering. The polyelectrolyte concentration in mechanically
dewatered cakes is relatively high and typically in the range 2500 – 5000 mg kg-1 ds.
Furthermore, they only degrade relatively slowly by abiotic processes in cultivated soil at a
rate of 10 % per year (Azzam et al., 1983). Acrylamide is a common monomer associated
with polyelectrolytes and is potentially toxic to humans and is a reported carcinogen (IARC,
1994). Concern about the implications for human health from the residual monomers in
polyelectrolytes used in drinking water treatment has resulted in them being withdrawn from
this application in Japan and Sweden, and stringent controls on their use are in place in
Germany and France (Letterman and Pero, 1990). These factors give rise to potential
environmental concerns about the long-term accumulation of polyelectrolytes in sewage
sludge and sludge-treated soil.

The limited available evidence suggests that no environmental problems have been
identified from the application of polyelectrolytes to soil. Acrylamide monomer residuals are
rapidly biodegraded in the environment and are unlikely to represent a risk to human health
in sludge (Gustavsen, 1998). Furthermore, polyelectrolytes are frequently applied directly to
soil as soil conditioning agents to maintain soil structural conditions and as a carrier gel for
fluid drilling pre-germinated seeds in agricultural and horticultural practice (Fordham and
Biggs, 1985). In the fluid drilling technique seedlings of sensitive pregerminated crops
emerge directly from the injected polyacrylamide gel. This practical example illustrates that
polyelectrolytes do not have a phytotoxic action in soil. An investigation of the potential
impacts of polyelectrolytes on nitrification processes in soil (Cartmell et al., 1998) showed no
effect on nitrate accumulation at ten times the normal rate of addition of polyelectrolyte to
soil in sludge, but nitrification was partially inhibited when the dose was increased to 100x
the normal input. Polyelectrolyte was added directly to soil in this study to assess the worse-
cased effects on nitrification processes in a controlled laboratory incubation. In practice,
however, polyelectrolyte compounds are strongly sorbed to the sludge solids and this is
likely to significantly reduce their availability and potential toxicity to soil microorganisms.

Compared to metals, organic pollutants have only recently been identified as having
potential adverse human health effects. Most organic pollutants are present in the
environment at very low concnetrations. Exposure to these compounds, for example through
drinking water, is very low. However, as some of these compounds may bioaccumulate or
have effects at low concentrations chronic health effects are starting to be investigated for
some of these compounds. Table 4.3 presents acute and chronic health effects of the major
organic pollutants covered in this report, and the limits set for these compounds in drinking
water.

100
4 Health and Environmental Effects of Pollutants in UWW and SS
Table 4.3 Summary of health effects for organic pollutants
Compound MCL in Drinking water Acute Health effects Chronic Health effects Carcinogenicity Notes

EU WHO USEPA

DEHP 10 µg.l-1 8 µg.l-1 6 µg.l-1 Usually low acute Damage to liver and Some evidence in Synthetic substance,
Emulsified toxicity: mild testes, reproductive rats and mice, adsorbs to soil and
Hydro- gastrointestinal effects, birth defects mutagenic at high sediments,
carbons disturbances, doses bioconcentrates due to
nausea, vertigo lipophilicity
PCBs 1.0 µg.l-1 0.5 µg.l-1 Acne-like eruptions Similar to acute Some evidence in Adsorbs to soil and
Organo- and pigmentation of poisoning: irritation of rats sediments, persistent,
chlorine the skin, hearing and nose, throat, and GI bioconcentrate, and
vision problems, tract, changes in liver accumulate in fat
spasms function and
reproductive systems
PAHs 0.2 µg.l-1 0.7µg.l-1 0.2 µg.l-1 Red blood cell Developmental and Some evidence from Adsorbs to soil and
Benzo(a Benzo(a) damage, anaemia, reproductive effects, humans and animals sediments, weak
)- - suppressed immune birth defects degradation, lipophilic,
pyrene Pyrene system bioaccumulate
LAS 200 µg.l-1 Gastrointestinal Kidney and liver toxicant Synthetic compound, toxic
Surfactants problems to marine life: LC50= 3-10
mg/l, biodegrades easily in
aerobic conditions, no
accumulation in sediments
and biological tissues
NPE 200 µg.l-1 1-5 µg.l-1 Allergies, endocrine Has an oestrogenic Lipophilic, mainly affects
Surfactants disrupting chemical effect on fish aquatic organisms,
partially biodegraded in
the environment
metabolites are very toxic
and persistent
PCDD/PCDF 0.00003 Chloracne, rashes, Thymic atrophy, damage Lymphoma, Highly volatile, binds to
µg.l-1 discoloration, to the hormonal and melanoma in soil and particles,
USEPA excessive body hair, immune systems, humans, can accumulates in fat,
website large species spontaneous abortions, increase risk of persistent, birth defects in
differences in toxicity, alteration in glucose several types of animals
very specific metabolism cancer in man.
EU: Water treatment directive
WHO:Guidelines for drinking water quality Vol.2 (1996).
USEPA:Standards for maximum permissible values in sewage sludge/soils. Estimating concern levels for concentration of chemical substances in the enviroment. Washington
DC (1984). USEPA website: http://www.epa.gov/safewater/mcl.html

101
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

5. REVIEW OF EU AND NATIONAL MEASURES TO REDUCE THE POTENTIALLY


TOXIC ELEMENT AND ORGANIC POLLUTANT CONTENT OF WASTEWATER AND
SEWAGE SLUDGE.

5.1 Approaches to reducing pollutant content of wastewater and sludge


As has been shown so far in this report UWW treatment is not sufficient to deal with all
pollution. Most of the pollutants are concentrated in sewage sludge although different
contaminants end up to varying degrees in effluent from WWTPs. This effluent ends up in
aquatic environments. Concentrating pollutants in sewage sludge, while it may protect
receiving waters, presents a number of problems for its disposal or use on agricultural land.

Because of this, a variety of instruments have been attempted at national level, with varying
success, on different levels to reduce UWW pollution closer to at source. These instruments
are consistent with an overall strategy of waste minimisation, polluter pays, and reduction at
source and include individual regulatory, economic and voluntary and educational
instruments.
Table 5.1 Summary of Available Instruments
Instruments Regulation Economic Voluntary Educational

Direct Licensing of “Downstream” Agreements and Research into


Measures disposal to Charges and Management alternative
(Applying to UWW taxes on Systems products and
direct inputs Licensing of disposal to directed at processes,
to UWW) product use UWW waste Management
Integration of Subsidies for minimization or and Waste
Water alternative alternative Minimisation
Management technologies, collection Training
and UWW into substances or
Land Use and collection
Spatial Planning services
Trading of
pollution
reduction credits
Indirect Product and “Upstream” Agreements, Research into
Measures Substance Bans Taxes and Management alternative
(applying to Product and Charges on Systems and products and
indirect or Substance Use Particular Inputs Codes of processes,
diffuse Licensing Subsidies for Practice aimed Management
sources) Integration of alternative at alternative and Waste
Water management management Minimisation
Management and products strategies Training
and UWW into Trading of Labelling and
Land Use and pollution Specific and
Spatial Planning reduction credits General
Publicity
Measures

The following selected examples demonstrate strategies for the minimisation of waste at
source through these instruments:

• Regulatory Instruments:
• The Prohibition of Mercury Clinical Thermometers in France
• Economic Instruments:
• Wastewater Tax in Germany
• Charges on Cadmium in Fertilisers in Sweden

102
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

• Subsidies to Waste Collection in the Dry Cleaning Industry in France


• Voluntary Initiatives:
• Targeted Waste Collection in France
• Waste Minimisation Strategy in Leather Industry in Italy
• The Anjou Recherche Programme and Special Conventions in France
• Local Initiatives, Promotion of Environmental Management and Cleaner Production in
Denmark.
• Educational Initiatives
• Provision of Consumer Information in France
• Eco-labeling and LAS in Scandinavia
• Awards Company Innovation in Waste Management and Minimisation in France

These measures may be differently targeted, to general and particular discharges or to


product use and substitution, to specific processes and industries and households, or to
specific localities and catchment areas.

5.2 Regulatory Instruments

The use of traditional command and control instruments involves licensing of the use and
discharge of material to UWW. This approach is notoriously difficult to monitor and control
effectively. In the case of particularly difficult pollutants, targeted product bans can be a more
cost effective solution where clear alternatives are available and the production of the
material in question is relatively easy to regulate.

The Prohibition of Mercury Clinical Thermometers in France

Mercury is used in a broad area of applications. Industrial uses of mercury may be found in
the electro-technical industry to produce batteries or fluorescent tubes or in dental practices
for fillings. Other industries require mercury for the production of instruments such as
manometers, barometers and thermometers. It is estimated that the total production of
mercury in France for industrial productions amount to an average of 60 tonnes per year.

Impact: Mercury is of particular health concern for not only are humans exposed to mercury
directly when the product breaks, but they also may be exposed after it is disposed and
accumulates in UWW and sludge. It can also leach from landfills through the water waste
pathway or be directly released in the wastewater system after disposal in sinks and toilets –
raising concern for the risk of human exposure and environmental contamination. It is also
estimated that before the introduction of the ban on the marketing of clinical mercury
thermometers, an average of 15 – 20 million mercury-thermometers were in circulation in
France. These are equivalent to 12 tonnes of mercury – about 20% of the yearly amount
produced. It is also estimated that an average 1.5 – 5 million of these thermometers were
broken every year, releasing between 3 and 10 tonnes of mercury in the environment yearly
and causing significant health and environmental concern. (Romp, 1993 in Öko Institut,
Berlin).

Measure: Under the new French regulation [Arreter of 24 December 1999, Journal Officiel,
31 Decembre], the marketing of clinical mercury thermometers is prohibited both nationally
and at EU level, as from March 1, 1999. However, the enactment does not prohibit export to
non-EU nations. The main objectives of the ban being that of minimising mercury waste and
prevent its release into the environment, hence reducing risk to humans.

Costs: Although difficult to evaluate precisely, the implementation of the regulation resulted
in two types of costs: 1) Reprocessing Costs associated to the reprocessing mercury
thermometers and 2) Replacement Costs for the purchase of new (electronic or eardrum)
devices. The average cost of an electronic thermometer ranges between 11 and 30 EURO

103
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

per unit, whilst a professional device costs around 305 EURO. The cost of an eardrum
thermometer (an infra-red device) ranges around 69 EURO. The professional timpanic
device costs between 305 and 610 EURO. Assuming that at least 15% of mercury
thermometers are collected in the first year, the total cost of the scheme amounts to about
3.81 million EURO.
Effectiveness: Although still at its early stage, the ban has been very successful and other
nations such as Germany and Sweden are already following similar policy measures. It is
estimated that the ban will reduce mercury waste by 12 tonnes a year – a reduction of 20%
of the total annual mercury production in France. However, such action should also be taken
for other industrial sectors using mercury - and French policy is seemingly moving towards
this direction – so as to further minimise the quantity of mercury present in the environment
and reduce the risk to human health and the environment.

Economic Instruments

Economic instruments may be used to provide a continuing incentive for reduced use of a
material and even product substitution. Nevertheless; evidence suggests that taxes and
charges need to be carefully designed and targeted so as to promote continuing waste
reduction. The social and economic implications of taxes and charges may make their
introduction controversial, and the costs of their administration can make them as complex to
administer as command and control regulation.

Wastewater Tax in Germany

This measure is a “downstream” charge on discharges, and demonstrates how the creation
of economic incentives alone may not be more effective in promoting reductions than
command and control measures.

Measure: The Federal Wastewater Tax was adopted in September 1976, comprising a tax
on sewage discharges; the amount payable was established on the basis of the amount and
harmfulness of the waste. The objective of the tax was better regulation of discharges and to
promote a reduction in wastewater pollution over all

Effectiveness: In terms of offering an overall incentive to reduce discharges, the impact of


the measure was found to be limited. A study carried out by Jass (1990) conclude that while
the charge had lead to considerable improvements of the purification of sewage and the
environmental technology, it had not constituted any incentives for further improvement.
Sewage taxes only created an incentive to comply with the command-and-control regulation,
but nothing more (Lubbe-Wolf, 1996 in Cremer and Fisahan, 1998)

Charges on Cadmium in Fertilisers in Sweden

This is an example of a specifically targeted measure. Sweden has had environmental


charges on nitrogen and phosphorus in commercial fertilizers since 1984. The “downstream”
charge on phosphorus was abolished in January 1994 and replaced by an “upstream”
charge on cadmium.

Measure: An important reason for the introduction of the cadmium charge was that it creates
an ongoing incentive to reduce the concentrations (Swedish EPA, 1991) in fertilizers. Since
November 1994, the charge rate is SEK 30 (EURO 3.3) per gramme of cadmium if the
cadmium content exceeds 5 mg per kg phosphorus (about 2.2 mg Cd per kg P2O5) (Swedish
EPA, 1997).

Impact: According to the Swedish Board of Agriculture, the content of cadmium in fertiliser
has gradually fallen from 35-40 mg Cd per kg phosphorus (before the introduction of the

104
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

charge) to about 23 mg in 1994/95 and 16 mg in 1995/96. The Board conclude that the Cd
charge in combination with the demand (for a low content of Cd in fertiliser) by the
agricultural sector has kept Cd levels on a low level (Jörnstedt, 1998). Drake and Hell-Strand
(1998) concluded that the combination of governmental policy (including the charge and a
standard) and voluntary efforts has been successful in reducing the content of cadmium in
phosphorus fertilisers. However, it was not possible to estimate the relative importance of
the different measures.

Costs: State tax gross revenues in 1996 were around 10 million SEK (1 million EURO), and
the administrative costs are estimated to be around 1% of the gross revenues (Drake and
Hellstrand, 1998). The tax is administrated by the National Tax Board, together with the tax
on nitrogen. Importers and producers report quantities and contents every month. The only
control made seems to be ‘tax audits’ (concerning the accounting of the firms involved). In
1999, 25 such audits were performed (corresponding to about one ‘man-year’). The
authorities do not measure the actual cadmium content of fertilisers. Some problems with
illegal imports by small firms of fertilisers from Poland and the Baltic states (probably of
Russian origin) are reported (Jörnstedt, 2000).

Subsidies to Waste Collection in the Dry Cleaning Industry in France

A very good example of an economic instrument is where competent authorities find it


cheaper or more effective to subsidise alternative production processesses or waste
collection strategies than to treat a particular pollutant.

For the businesses using chlorinated solvents, currently only two main options are available
to deal with the waste: regeneration of the solvent (10%) and incineration (90%). The
problem with regeneration is that the process may affect the added stabilisers, which are
required for the stability of the solvent at high temperature and humidity. Hence, it is
necessary to treat the regenerated solvent with new stabilisers. Nevertheless, it is usually
cheaper than destruction of the waste, which in France costs around 4100 FF per tonne.
However, generally only larger firms employ this solution.

Measure: Associations have been created in the dry cleaning sector in order to organise
widespread regeneration of solvents, and these are starting to cover other solvent using
sectors. These organisations co-ordinate the collection and treatment of wastes. The
Agences de l'Eau subsidise dry cleaners who adhere to these associations in order to help
finance the cost of the collection of their wastes.

Costs: A typical dry cleaning facility produces 400 kg of chlorinated waste per year and the
cost of collection and treatment is around 3500 FF per year, which represents about 1% of
their revenue [ADEME, 1995].

5.4 Voluntary Instruments and Government Industry Cooperation:

“Voluntary” instruments encompass a range of policy initiatives, from industry initiatives


based on EMAS and other management and auditing systems, to agreements between
organs of the state and industry. Voluntary Instruments however are very rarely just that, and
often operate as part of a broader scheme of regulation, economic incentives (including
subsidies) and public education exercises. The division of responsibility and costs between
government and industry varies from case to case.

Some instruments amount to an indirect subsidy to industry, others enforce the polluter pays
principle by creating an incentive to manage waste through the adoption of producer
responsibility, as in the packaging waste directive. The following examples include a range
of instruments adopted by government and industry in cooperation, including targeted

105
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

collection of problematic wastes, voluntary and regulatory or economically inspired waste


minimisation strategies. All imply some proactive governmental intervention.

Targeted Waste Collection in France

This measure constitutes a specific drive and effort by authorities to collect dangerous and
harmful waste from homes. While effective in its own terms it is not a long-term solution to
the problem of discharges to UWW. It may be effective to deal with continuing risks of
contamination from smaller and diffuse sources, and be used in connection with the adoption
of a longer-term waste minimisation and collection strategy and public education campaign.

Measure: One of the first targeted waste collection initiatives carried out in France was in
1989, where 11,500 kg of waste products were collected over 16 days (see Table 5.2).

Table 5.2 Quantities of products containing pollutants collected at Savie in 1989


[ADEME, 1995]

Product Amount (kg] Percentage of total


Waste Collected
Paint 5590 48.6%
Solvents 2360 20.5%
Medicines 1010 8.8%
Pesticides 1005 8.7%
Chemical laboratory products 70 0.6%
Thermometers 65 0.5%

Costs: A more recent example is given by the 2 day collection in 1994 in the area of
Boisset-Gaujac (Gard) where 114 kg of chemical products, 169 kg of paint, 12 kg of
aerosols, 27 kg of solvents, and 29 kg of pesticide products were collected and dispatched
separately for treatment at a cost of about 12,000 French francs [ADEME, 1997]1.

Effectiveness: Experience has shown that is it more efficient to appropriately equip waste
reception centres for handling special wastes rather than organising random collection days.
In contrast to targeted waste collection, the adoption of a comprehensive waste minimisation
strategy directed at particular sectors has demonstrated longer term and verifiable results.

Waste Minimisation Strategy in Leather Industry in Italy

This is another example of targeted intervention by public authorities, this time engaging a
particular sector in the long-term management of industry specific problems.

Italy is the principal European location for the leather and tannery sector in terms of
establishments, employment and production. Tanneries are mostly small and medium sized
enterprises, with only 10% of them employing more than 20 people. The industrial area
covered by the plan is located in the Valle del Chiampo, in the province of Vicenza. The area
embraces 10 municipalities, of which Arzignano is the most important with more than half of
the tanneries. The tannery area is the largest in Europe and supplies 50% of the Italian
production. Manufacturing includes shoes, furniture and other leather goods (Vicenza Dept.
of Environment, 1997)

Impacts: The tannery industry is considered to have important environmental effects on


both water and air, primarily because of toxic wastes generated by the large amounts of
chemicals employed during the various phases of the tanning process. The main pollutants

106
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

being chromium III, sulphur, chlorides, solvents and organic wastes. (Vicenza Dept. of
Environment, 1997). The tanning process comprises two phases - covering and fixing, where
the pelts are sprayed with paints and chemicals for treatment. It is estimated that around
80% of the solvents used become hazardous waste and 1997data from the Dept. of
Environment of Vicenza indicate that the solvents used for the finishing process amount to
20.000 tonnes per year, 85% for the covering phase, 15% for the finishing phase. Metoxy
propanol is the solvent most used in tanneries and is classified as Class III hazard
substance under Italian law, which has 5 classes of hazardous substances for which
maximum allowed emissions are set.

Measure: In 1997, the Dept. of Environment of Vicenza introduced new measures to tackle
the environmental problems of the spray finishing process. The intervention focused on two
main aspects: 1) the introduction of innovative machinery, such as the more efficient low
pressure airbrushes or high pressure airless brushes instead of high pressure devices; plus
2) the use of chemicals dissolved in solution. ‘Gruppo Conciario Veneto’ a tannery
association comprising 4 companies (La Veneta, Conciaria Adriatica, Sacpa and Veneta
Conciaria Valle Agno), with a total of 340 employees, 26.500 m2 of indoor plant and a 1997
turnover of 103 million. EURO, adopted a scheme reducing use of, and ultimately replacing,
the solvent metoxy propanol with alternative substances. Other substitutes are currently
being tested.

Effectiveness: As a result of the waste minimisation scheme, the use of Metoxy was
significantly reduced from 7,300 kg in August 1998 to 1,300 kg in December 1998 (- 82%),
but has been replaced by the less hazardous isopropyl alcohol (Class IV), which has in turn
increased in consumption. However, the total quantity of solvent used decreased from
10,650 kg to 5,007 kg per month (- 53%) and therefore less toxic waste has been generated
and released by the tannery (no quantitative data available).

Costs: The reduction in utilised solvents also brought significant economic benefits, with a
reduction in monthly consumption equivalent to 64%, from 10,590 EURO in August 1998 to
3,794 EURO in December 1998. These economic savings appear to be the main incentive
and persuasive tool to company innovation.

The Anjou Recherche and ‘Eaux Industrielles Initiatives’: Special Conventions in


France

These cases are further examples of targeted intervention at the local level, representing a
programme of sources and discharge identification, and the first example of a truly
“voluntary” initiative through the adoption of negotiated approaches to the reduction of
problematic discharges.

Measure: Anjou Recherché has studied five regions of France which have full statistical data
and 34 UWW collecting systems. This research programme allows many SME polluters to
be identified. Following the identification of industries that are potential polluters, a contract
is drawn up between local industry and the mayor of the area. The contracts are called
special conventions for discharge, and about 2000 have now been set up, mainly in the
South West region of France around Toulouse. The contract determines pollution reductions
and modifies discharge conditions into the UWW collecting system.

In Tours the "eaux industrielles" initiative was established in 1988. This initiative aimed to
control the quantity of discharges into the UWW collecting system based on monthly
analyses on the sludge quality are carried out to control for pollution. In 1996 it was found
that copper and mercury concentrations were very close to the recommended limit and much
higher than the averages for France (Table 5.3).

107
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

Table 5.3 Average concentrations (g t-1) in potentially toxic elements in the Tour
sludges [from ADEME, 1997] *French Standard NF U 44 041

Average Average French Standards


concentration concentration
(Tours) (France)
References Limits
Cd 5.3 5.3 20 40
Cr 96 80 1000 2000
Cu 805 334 1000 2000
Hg 7.3 2.7 10 20
Ni 106 39 200 400
Pb 153 133 800 1600
Se 3.5 7.4 100 200
Zn 977 921 3000 6000

Visits to the businesses potentially capable of releasing copper were undertaken and it was
found that the problem initiated from a mirror manufacturing company. Effluents were
composed of degreasing waters, discharges from the silver and copper adding steps.
Certain observations were made: the neutralising pH in the treatment of the degreasing
waters was not alkaline enough to precipitate the metals and the pH was not checked
regularly enough. Thirty days after this intervention, the copper concentration showed
significant reduction. For mercury, medical activities were investigated, as seen with the
Anjou Recherché Case Study and it was discovered that the pollution was mainly due to
discharges from two hospitals and one analytical laboratory.

Effectiveness: As the WWTP receives less contaminated wastewater, the manufacturer pays
less for the treatment of wastewater. Furthermore, it avoids the cost of landfilling the sludge,
as it can then be used in agriculture, decreasing overall costs.

Local Initiatives, Promotion of Environmental Management and Cleaner Production in


Denmark.

In Denmark, about 45 industries perform wet treatment of textiles, i.e. pre-treatment, dying,
printing and/or after treatment. The majority of these companies are located in the County of
Ringkjøbing. This type of business consumes large amounts of water, energy and
chemicals.

Impacts: Total consumption of chemicals is approximately 22,000 tonnes per annum


(1998), of which approximately 18,000 tonnes per annum consists of basic chemicals
(especially salts, acids and bases). The dye stuffs make up approximately 900 tonnes per
annum and the residue consists of excipients such as detergents, phthalates etc. The
wastewater from wet treatment is typically heavily dyed and has large contents of salt,
detergents, post-treatment agents and other chemicals. The total amount of wastewater
within this business makes up 6.6 billion cubic metres per annum. Most of the dye works
discharge the wastewater at the municipal WWTPs but there are 4 dye works which have
their own water treatment plants with a subsequent discharge to recipient waters. (Genbrug
af procesvand fra reaktivfarvning af bomuld, Miljøprojekt nr. 374 1998, p. 15. Miljø- og
Energiministeriet)

Measure: The County of Ringkjøbing, in close collaboration local authorities and the
Federation of Danish Textile and Clothing Industries set up a working party to launch and co-
ordinate evaluation of chemicals used in the textile dye process. This working party
established a score system to govern chemicals. The score system is based on four

108
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

parameters. Parameter A represents the estimated amount of the chemicals discharged into
the environment as wastewater. Parameter B is a score on biodegradability, C is a score on
bioaccumulation, and D is a score on toxicity. Importantly, a lack of information about a
certain product will automatically result in a high score. The score system was implemented
in 1992-1993 and the dye works in the County of Ringkjøbing undertook to inform the
supervisory authorities about their consumption of chemicals according to the score system.

The reporting system allows both administrators and company managers to select priority
chemicals and subject them to close examination, on the basis of information filled in the
chemical supplier’s specification sheets. For example, in "Egetæpper a/s" a company which
dyes and manufactures tufted carpets produces an annual score report. This report is used
by the company and the local environmental authorities scope environmental problems,
analyze the consumption patterns, and to find opportunities for product substitution and
cleaner production technologies. In particular, the company's purchasing policy requires an
environmental impact assessment , including the score allotted, before products are bought..

Impacts: The number of products with a high score used in the production at Egetæpper
a/s has been reduced considerably between 1992 and 1997. This is partly because some of
the products are no longer used by the company and partly because huge efforts have been
made in order to procure missing data on the effects these products have on the
environment. Egetæpper a/s' environmental report from 1995, the consumption of dye stuffs
and excipients has been listed and in this report it is stated that:

109
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

5.5 Education and Information

Education and Information Campaigns can be general or specific, comprising public


education campaigns and specific labelling initiatives. The first example is a general
information campaign addressing discharges to water the impact of which is difficult to
assess. The second is a consumer information campaign that seeks to promote product
substitution. The third is both an incentive and an information measure in the form of a prize
for effective environmental performance.

Provision of Consumer Information in France

Measure: Centre d’Information sur l’Eau based in Paris launched a campaign to alert people
to the problems caused by disposing of compounds down the sink or the toilet. In order to do
so, they distribute a leaflet where they note that the following substances should not be
disposed of into UWW which include;

• leftover weed killers or fertilisers


• out of date or opened medicines
• car oils
• hydrocarbons
• leftover paint or varnish
• pesticides and other protecting products

The leaflet also stresses that collection systems are in place in many areas and that
information about these is available, and that using a waste disposal unit when connected to
the UWW collecting system is prohibited, as is discharging rainwater from gutters into the
UWW collecting systems when a separate system is in place in the area. The centre had
over 7000 enquiries in 1998.

Eco-labeling and LAS in Scandinavia

Measure: Eco-labeling. Initiatives such the ‘Nordic Swan’ and ‘Good Environmental Choice’-
were developed by the Swedish Society for Nature Conservation (SSNC) and the Danish
Society for the Conservation of Nature (DSCN) respectively. These were aimed at phasing
out undesirable chemicals in washing powders and have significantly reduced the use of p
LAS (Linear Alkyl Benzene Sulphonate), and Nonylphenol. Eco-labelling campaigns were
launched by both the SSNC and DSCN, against washing powders containing LAS, whilst at
the same time promoting the use of ‘Swan’ or ‘Good Environmental Choice’ labelled washing
powders. In the past decade, the eco-label ‘Good Environmental Choice’ has become one of
SSNC most important tools for dealing with environmental problems. The initial campaign
was launched in 1988 with the publication of one of many green consumer guides, which
included information about household chemicals - some of which were found to be
replaceable with more suitable alternatives.

Use: LAS is the most important surfactant used in Europe and is found in considerable
quantities in washing powders (up to 50%). Some 300000 tonnes of LAS were sold in
Europe in 1999, but concerns for its environmental threat have risen since LAS is toxic to
aquatic animals and plants. LAS is only degradable in the presence of oxygen, which is not
always present in wastewater treatment plants. In addition, it is estimated that about 15-20%
of the amount of LAS entering a water treatment plant ends up in sludge with no further
degradation (S. Hagenfors, 2000).

Effectiveness: Products which do not contain LAS or Nonylphenol and have gained
considerable market share since the launch of the campaign. “In Sweden, products with this
label accounted for 95% of sales by 1997 and consumer choice lead to a decline in use of

110
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

LAS from 6,300 tonnes per year to 260 tonnes per year” (Danish Environmental Agency
2000). The published guide was a success and prompted consumers to demand for more
detailed information about domestic products and their potential environmental impact.
Coincidentally one the main environmental issues in the region at the time was that of
widespread eutrophication of Scandinavian water bodies which subsequently induced a
demand by consumers for environmentally friendly products. In brief, public awareness
made the market for eco-labelled products grow in Sweden, so that after the first
manufacturer (Unilever) launched its eco-labelled detergent, other multi-nationals had to
follow.

In Sweden, eco-labelling has however been limited in terms of product range and multi-
national manufacturers have not introduced other eco-labelled products, with the exception
of a few minor producers that specialise in ‘green’ products. In other Scandinavian countries,
the market share of ‘Swan’ products is significantly smaller, with 15% in Finland and less in
Norway and Denmark; the difference in share thought to be due to less public awareness
campaigning. Yet, in the last ten years, the Swedish market for eco-labelled products has
undergone important modifications. It is estimated that presently 60% of the chemical
ingredients in soap, shampoo, detergents have been substituted or removed, the remaining
40% of chemicals falling within the list of substances approved by the ‘Swan’ and ‘Good
Environmental Choice’ guidelines. The 38000 tons of chemicals subject to substitution have
been replaced by 29000 tons of approved substances, the difference (9000 tons) having
been removed. The substitute chemicals are all approved by eco-labels and are more
biodegradable in sewage treatment plants and sludge, meaning less environmental risk and
less treatment costs. As a result, it is estimated that the use of LAS in Sweden has been
reduced by 95% (S. Hagenfors, 2000).

In addition, the development of the eco-label ‘Swan’ has prompted Stockholm Water Co. to
initiate a plan for the identification of measures to reduce hazardous household wastes being
flushed down the drain and into WWTP. This lead to the establishment of ‘environmental
stations’ or collection points and to the launch of a thorough public awareness and
information campaign about the impacts of household products on the aquatic environment

Awards for Company Innovation in Waste Management and Minimisation

In 1996, the trophy ADEME "Economic and clean technologies" went to the STEN society,
which is a metal finishing company which managed zero cadmium discharges by
concentrating the cadmium-containing effluents through evaporation and recovered the
metal through electrolysis [ADEME, 1997].

5.6 Conclusion

The review of National Practices with respect to UWW demonstrated a range of problems,
and identified some strategies for dealing with diffuse and small-scale sources of water
pollution.

Without upstream control, UWW treatment cannot treat all wastewater pollutants, resulting in
effluent and sludge quality problems. A range of measures are likely to be most effective in
mitigating problems, and the appropriate policy mix will vary according to the pollutant,
industry structure, local conditions and social factors, and there should be room for local
discretion.

Product Bans in particular may be appropriate where product substitution is a possibility.


Economic Instruments such as taxes and charges can, if carefully designed and targeted,
provide appropriate incentives for alternative approaches by industry and producers of
waste. Where the costs of treatment are transparent, it is more likely that least cost

111
5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge

alternatives will be pursued through the use of subsidies to waste reduction or collection.
Targeted Voluntary and Educational Initiatives may assist but the full costs and benefits of
specific instruments are difficult to assess.

Full Cost Recovery for Waste and Water Services (under the Water Framework Directive)
will assist in making the costs of dealing with particular pollutants more transparent.
Nevertheless, the use of economic and alternative instruments and strategies should be
recognized as the legally appropriate implementation measures in both EU and National
Legislation, and the competent authorities should be legally empowered to establish and
participate in alternative measures, including substitution and recovery schemes.

112
Section 6. Case Studies

6 CASE STUDIES

(a) Platinum Group Metals in Urban Environment

(b) Sustainable Urban Drainage

(c) Artisanal activities in Vicenza, Northern Italy

(d) Pharmaceuticals in the Urban Environment

(e) Personal Care Products, Fragrances in Urban Waste Water and Sewage

Sludge

(f) Surfactants in Urban Wastewaters and Sewage Sludge

(g) Use of Polyelectrolytes; The Acrylamide Monomer in Water Treatment

(h) Landfill leachate

(i) Potentially Toxic Elements (PTE) transfers to Sewage Sludge

(j) Effect of Chemical Phosphate Removal on PTE Content in Sludge

113
Section 6. Case Studies

(a) Platinum Group Metals in the Urban Environment

Introduction

The platinum group of metals (PGMs), sometimes referred to as the platinum group
elements (PGEs), comprise the rare metals platinum (Pt), palladium (Pd), rhodium (Rh),
ruthenium (Ru), iridium (Ir) and osmium (Os) and are naturally present in a few parts per
billion (µg/kg) in the earth’s crust. The elements are noble chemically unreactive metals, and
are found in nature as native alloys, consisting mainly of platinum.

Recently these metals have gained importance as industrial catalysts including vehicle
exhaust catalysts (VECs). This use and possible implications for human health were the
subject of an earlier review undertaken by Imperial College, London for the UK Department
of the Environment (Farago et al, 1995; 1996).

Increasing understanding of the environmental damage of vehicle emissions has led to the
introduction of stringent emission control standards throughout the western world. Since
1974 all new cars imported or produced in the United States have had catalytic convertors
fitted, cutting down hydrocarbon and carbon monoxide emissions. In 1977 they were fitted to
a substantial proportion of all cars sold in America, where at the time, this application
accounted for 32% of the total Pt usage (Herbert, et al., 1980).

Vehicle exhaust catalysts have also been used in Japan since 1974. Vehicle exhaust
catalysts were also introduced in Germany in 1985, in Australia in 1986, and into the UK at
the beginning of 1993 in response to the emission standards equivalent to the US standards
which were introduced in the EC at that time. Other uses of PGMs are noted in later
sections.

Sources

The PGMs are found in nickel, copper and iron sulphide seams (Bradford, 1988). They are
currently mined in South Africa, Siberia and Sudbury, Ontario. World mine production of the
PGMs, of which 40-50% is platinum, has steadily increased since 1970. This reflects the
increasing world-wide use of PGM vehicle catalysts (IPCS, 1991). From 1988-1992 world
mine production was essentially constant at around 255 tonnes per year (WMS, 1994). The
amount of PGMs present in the earth’s crust down to a depth of 5km, and hence
technologically attainable, are still enormous when compared with present requirements, but
only a fraction of the pertinent ores is sufficiently rich for commercial exploitation. Of the total
of 3x1011 tonnes of PGMs in the earth’s crust, 3x103 tonnes have been mined, and 7x1010
tonnes are minable (Renner and Schmuckler, 1991).

The total worldwide supply of Pt for 1999 and 2000 was 138 tonnes and 153 tonnes
respectively for Pd 230 tonnes and 224 tonnes respectively, and for Rh 14.2 tonnes and
20.9 tonnes respectively (Johnson Matthey, 2000)

Uses of platinum group metals.

By far the greatest use of PGMs both in Europe and worldwide is in vehicle catalysts, with
additional major uses in the chemical industry, electrical and electronics industries,
petroleum industry, the manufacture of jewellery, as a cancer treating drug in medicine, as
alloys in dentistry and in the glass industry.

Demands by application for 1999 and 2000 for PGMs are shown in Table a.1. (Johnson
Matthey, 2000)

114
Section 6. Case Studies

TABLE a.1 Platinum Group Metals Demand by Application (Worldwide)

Application kg 1999 (kg) 2000 (kg)


PLATINUM
Autocatalysts: gross 45600 51000
Autocatalysts: recovery -12000 -13000
Jewellery 79400 83300
Industrial 38400 41400
Investment 5100 -1420
Total Demand (Pt) 159000 146000
PALLADIUM
Autocatalysts: gross 166700 146000
Autocatalysts: recovery -5530 -6520
Dental 31500 24700
Electronics 56100 58600
Other 16600 15000
Total Demand (Pd) 265000 238000
RHODIUM
Autocatalysts: gross 14400 16000
Autocatalysts: recovery -1870 -2240
Chemical 964 992
Electronics 170 170
Glass 851 1050
Other 312 312
Total Demand (Rh) 14900 16200
RUTHENIUM
Chemical 2440 1930
Electrochemical 2040 2270
Electronics 5560 6580
Other 1160 1360
Total Demand (Ru) 11200 12100
IRIDIUM
Automotive 964 397
Chemical 198 170
Electrochemical 794 680
Other 936 1450
Total Demand (Ir) 2890 2690

115
Section 6. Case Studies

Trends over time in platinum and palladium uses by application for Europe are shown in
Table a.2 and a.3.

TABLE a.2 Platinum demand by application in Europe (kg)


Platinum demand 1992 (kg) 1994 (kg) 1996 (kg) 1998 (kg) 2000 (kg)
Autocatalyst: gross 16300 17200 14600 15500 17900
Autocatalyst:recovery -142 -284 -567 -851 -1130
Chemical 1420 1420 1700 1700 2410
Electrical 851 709 709 1280 2270
Glass 425 851 1130 709 709
Investment:small 992 1276 142 142 0
Jewellery 2410 2840 3540 4540 5670
Petroleum 567 709 425 425 284
Other 1560 1840 2130 2410 2840
Totals (Pt) 24400 26500 23800 25800 30900

TABLE a.3 Palladium demand by application in Europe (kg)


Palladium demand 1992 (kg) 1994 (kg) 1996 (kg) 1998 (kg) 2000 (kg)
Autocatalyst: gross 1130 7370 24400 38800 51600
Autocatalyst:recovery 0 0 142 -142 -425
Chemical 2100 1700 1840 1840 2690
Dental 8500 7230 7230 5950 3120
Electronics 5950 7230 8500 7660 7370
Jewellery 992 851 851 1420 1280
Other 425 709 567 709 567
Totals (Pd) 19100 25100 43200 56300 66200

Of particular interest is the increased demand for palladium in Europe, largely in response to
the introduction of Euro Stage III legislation from January 2000; palladium – rich catalysts
will meet stricter emission limits for petrol models, resulting in a further move away from
platinum technology (Johnson Matthey 2000).

Catalytic convertors

A catalytic converter is a unit about the size of a small silencer that fits into the exhaust
system of a car. The metal catalyst is supported on a ceramic honeycomb monolith and
housed in a stainless steel box similar in shape to that of a conventional silencer. About 1-3g
of PGM is contained in some vehicle exhaust catalysts, approximately 50g of PGM per cubic
foot of catalyst (Steger, 1994). Due to the commercial sensitivity of these products it is
difficult to obtain data on the exact amounts in each of the many different formulations of
catalyst. The honeycomb made of cordierite contains 300 to 400 square channels per
square inch (6.45cm2), and is coated with an activated high surface area alumina layer
called the washcoat (Farruato, 1992) containing small amounts of the precious metals,
platinum, palladium and rhodium in varying proportions. The conventional three-way
catalysts typically contain 0.08% platinum, 0.04% palladium and 0.005-007% rhodium
(Hoffman, 1989).

These metals convert over 90 percent of carbon monoxide (CO), hydrocarbons (HC) and
nitrous oxides (NOx) into carbon dioxide (CO2), water (H 2 O) and nitrogen (N2). Platinum is
an effective oxidation catalyst for carbon monoxide and hydrocarbons, but it is more
sensitive to poisoning than palladium and so can only be used in cars which use unleaded
petrol. Palladium is becoming increasingly used instead of platinum due to the higher costs
of the latter. The rhodium oxidises the hydrocarbons and reduces the NOx emissions. Base

116
Section 6. Case Studies

metals are also incorporated, cerium being the most frequently used; others include calcium,
strontium, barium and iron.

Chemical fingerprinting of ground autocatalyst materials has been undertaken by laser


ablation and analysis by ICP-MS for 31 elements (Rauch et al, 2000). Variations in
composition were found to occur in agreement with the known fact that variations occur from
one manufacturer to another and from one year to another. An association between PGMs
and Ce in road sediments was ascribed to the emission of PGMs as abraded washcoat
particles onto which PGMs are bound and of which Ce is a major component.

Recycling

Of the total platinum consumption in the United States, approximately thirty per cent is
accounted for by vehicle catalysts (IPCS, 1991). The recovery of spent autocatalysts from
vehicles at the end of their lives is regarded as important and substantial secondary sources
of platinum as well as palladium and rhodium (Torma and Gundiler, 1989). The quantity of
spent autocatalysts greatly increased in the United States from 1984 to 1988. These
scrapped autocatalysts present an important secondary source of the platinum group
metals.

On current projections it is expected that 3.5 million catalysts will be available for recycling in
the UK by 2000.

Platinum group metals in the environment.

The average concentration of platinum group metals in the lithosphere is estimated to be in


the region of 0.001-0.005 mg.kg -1 for Pt, 0.015 mg.kg -1 for Pd, 0.0001 mg.kg -1 for Rh, 0.0001
mg.kg-1 for Ru, 0.005 mg.kg-1 for Os and 0.001 mg.kg-1 for Ir (Greenwood and Earnshaw,
1984).

Although a rapid increase in Pd in sediments from the Palace Moat, Tokyo, Japan was
reported by Lee (1983) between 1948 and 1973, it seems unlikely that this was connected
with car catalytic convertors since there were few in use in Tokyo by 1973.

Concentrations of Pt and Pd in Boston Harbour have been investigated to evaluate Pt and


Pd accumulation and behaviour in urban coastal sediments (Tuit et al, 2000). Increased
levels of both metal of approximately 5 times above background concentrations were
ascribed to anthropogenic activity with catalytic convertors a major source. It was concluded
that anthropogenic enrichments can significantly influence coastal marine inventories of
PGMs. The study also indicated that Pt associated with catalytic convertors is much more
soluble than expected or alternatively that there is an additional source of dissolved Pt to the
harbour. Further study of the biogeochemical behaviour of Pt and Pd was recommended.

Urban pollution with PGMs from catalytic convertors

Emissions of PGMs arise as a result of deterioration of the catalytic convertors, mainly due
to thermal or mechanical strain and acid fume components, and are intensified by
unfavourable operational conditions (misfiring, excessive heating) which may even destroy
the converter (Schäfer and Puchelt, 1998).

Emission rates range between several ng and µg of Pt per km driven depending on whether
they were measured in motor experiments or calculated on the basis of environmental
concentrations (König et al., 1992). Platinum is mainly emitted as a metal or an oxide with

117
Section 6. Case Studies

particle sizes in the nm range, bound to small articles of washcoat material (Schlögl et al.,
1987).

Several workers have reported accumulation of Pt, Rh and Pd in road dusts and soils
(Zereini et al, 1993; Schäfer et al 1995; Farago et al 1996; Heinrich et al, 1996; Schäfer et
al, 1996).

Mostly inert under atmospheric conditions, the reactivity of Pt increases significantly if these
nanoparticles are brought into contact with soil components. Lustig et al., (1996)
demonstrated that humic substances considerably enhance the reactivity of Pt clusters in
the nm-range under atmospheric conditions. Using road-dust from a tunnel, it was
demonstrated that within hours Pt can be fixed to several humic acids with different
molecular weights. The low solubility of Pt in deionized water increases significantly even
under reducing conditions when certain anions or complexing agents are used (Nachtigall et
al., 1996).

A detailed study has been undertaken in several sites in southwest Germany, selected on
the basis of traffic density and morphology, including roads in Stuttgart with 120,000 vehicles
per day and near Heidelberg with 100,000 vehicles per day (Schäfer and Puchelt, 1998). At
these two locations, Pt concentrations in the 0-2 cm surface soil adjacent to the road ranged
from several hundred µg/kg to local background values (≤ 1 µg.kg-1) at less than 20 m from
the road. Maximum Pd and Rh values were 10 and 35µg.kg-1 respectively. The PGM
concentration decreased significantly with depth.

However the maximum PGM concentrations in soils at Heidelberg were only 25 percent
those at Stuttgart, even though the traffic density was only 20% lower. The authors
suggested that this could be due to frequent traffic jams at the Stuttgart site “leading to
excessive emissions due to unfavourable working conditions of the engines”.

Urban road dusts collected in Stuttgart at the same time showed concentrations of Pt
ranging up to 1000 µg.kg-1, 110 µg.kg-1 Rh and 100 µg.kg-1 Pd; these reflect short-term
inputs of PGMs. A ratio of around 6 Pt: 1 Rh in traffic influenced soils and dusts has been
reported by Schäfer et al (1996).

Schäfer et al (1999) measured time-dependent changing PGM depositions and contents of


dusts and soils at a typical urban location at Karlsruhe in Germany. Daily deposition rates at
2 m distance from the traffic lane were within the range 6-27 ng m2 Pt, 0.8-4 ng m2 Pd.
Concentrations of PGMs in the dusts sampled over an 8 monthly period illustrated the
steady inputs. Using data for Pt concentration in soil at a site near Pfarzheim and a daily
passage of around 15,000 Pt emitting cars per day, the authors calculated for a total number
of 11 million converter-equipped vehicles over 2 years, a total emission of at least 3,000 ng
of Pt per km along the traffic lane, giving a mean emission rate of 270 ng/km per vehicle.
This value significantly exceeds the Pt emission rates of 2-86 ng.kg-1 measured in stationary
motor vehicle experiments (König et al, 1992).

A recent estimate of total Pt emission in the vicinity of roads in Germany over the period
1985-2018 was 2,100 kg (using emission factors of 0.65 µg.kg-1 for highways, 0.18 µg.kg-1
for federal and national streets and 0.065 µg.kg-1 for district and city streets) (Helmers and
Kummerer, 1999). These different emission rates reflect the increase in Pt load of exhausts
with increasing speed of the car.

Accumulation of Pt was clearly shown in road dusts and surface soils adjacent to roads in
the UK in 1994 (Farago et al, 1996, 1998). In the heavily trafficking London Borough of

118
Section 6. Case Studies

Richmond, Pt concentrations ranged up to 33 ng.g-1 in road dusts and 8 ng.g-1 in soils. Pt in


road dusts was highest at major road intersections (mean 21 µg.g-1) compared with along
major roads (13 ng.g-1) and intermediate and minor roads (2ng.g-1). The local background
concentration for soils was 1 ng.g-1, similar to that obtained in rural Scotland.

More recently a study in the city of Nottingham, UK, compared Pt and Pd concentrations in
garden soils and road dusts taken in 1996 and 1998 and archived samples taken in 1982
(which represented levels before the introduction of catalytic convertors) (Hutchinson, 2001).
Significant increases for both Pt and Pd were found in road dusts (see Tables a.4 and a.5
and Figure a.1) with values ranging up to 298 ng.g -1 and 556ng.g-1 respectively for Pt and Pd
in 1998 .

Table a.4 Summary results for Pt in garden soils (0-5cm) and road dusts from
Nottingham (ng.g-1) aResidential streets with low traffic densities; b Includes major roads
with high traffic densities (from Hutchinson, 2001)

Year Sample N Range Mean Geomean Median


Nottingham
1982 Soil 42 0.27-1.37 0.61 - 0.59
1996 Soil 42 0.19-1.33 0.80 0.75 0.73

1982 Road dust 10 0.46-1.58 0.90 0.80 0.75


1996 Road dusta 8 0.82-6.59 2.78 2.29 2.06
1998 Road dustb 20 7.3-297.8 96.78 69.55 76.72

Table a.5 Summary data for Pd in garden soils (0-5 cm) and road dusts in Nottingham
(ng.g-1) a Residential streets with low traffic densities; b Includes major roads with high traffic
densities (from Hutchinson, 2001)

Year Sample N Range Mean Geomean Median


Nottingham
1982 Soil 42 0.64-0.99 0.05 - 0.04
1996 Soil 42 0.21-1.11 0.18 - 0.10

1982 Road dust 10 0.69-4.92 1.24 - 0.22


1996 Road dusta 8 0.19-1.43 0.75 0.64 0.60
1998 Road dustb 20 5.6-556.3 92.9 40.95 35.84

An EU-funded study under the Environment and Climate Programme, CEPLACA, involved
laboratories in Madrid, Gothenburg, Sheffield, Rome and Neuherberg. Changes in catalyst
morphology over time were studied using SEM/EDX and laser induced breakdown
spectrometry (LIBS) (Palacious et al, 2000). Catalysts were used up to 30,000 km in a roller
dynamoneter following a driving cycle representing urban and non-urban driving conditions.
Releases of PGMs were found to decrease with time. For new petrol catalysts mean
releases were 100, 250 and 50 ng.km-1 for Pt, Pd and Rh respectively. In diesel catalysts Pt
release ranged from 400-800 ng.km-1.

The effect of catalyst ageing was large. At 30,000 km releases were reduced to around 6-8
ng/km Pt, 12-16 ng/km Pd and 3-12 ng/km Rh for petrol catalysts. In diesel catalysts, the Pt
release ranged from 108-150 ng/km.

119
Section 6. Case Studies

The difference between diesel and petrol was ascribed to the different composition of the
washcoat and the different running conditions of diesel engines.

Soluble forms of PGMs emitted (in dilute HNO3) were significant for the fresh catalyst but
less than 5% of the total amount. A previous study had reported 10% of the total Pt emission
to be water soluble for fresh petrol catalysts (König et al, 1992).

At 30,000 km the amount of soluble PGMs released was similar or slightly higher than at 0
km. One possible explanation suggested for the relatively high amount of soluble PGMs
related to the relatively high chloride concentration in fresh washcoat (i.e. one example
quoted of 3.4 wt %). The authors suggested that the formation of soluble PtCl6, PdCl2 , PdCl4
or RhCl 3 could be favoured at the high temperature and humidity that can be reached in the
catalyst. The chloride concentrations in aged catalysts are normally very much lower.
However, further laboratory tests using spiked solutions showed the instability of these
chloro-complexes in the final exhaust fumes solution. It was thus thought possibly that the
soluble or labile PGM fraction of the exhaust could be higher than those measured
(Palacious et al, 2000).

An important conclusion from this study was that “no clear relation could be observed
between the labelled amount of PGMs in the different catalysts studied and the measured
amount released through car exhaust fumes. Different catalytic converter manufacturers,
different car engines, even if running under the same conditions during the sampling period,
and the well-characterized non-uniform behaviour of the catalyst could account for the lack
of an observed correlation”.

Emissions of Platinum in effluents from hospitals

Effluents from hospitals contain platinum from excreted anti-neoplastic drugs, cisplatin and
carboplatin, though workers in Germany have concluded that these are only of minor
importance to environmental inputs from other sources and in particular from the use of
catalytic convertors (Kümmerer and Helmers, 1997). These drugs were introduced 25 years
ago to treat various tumours and are usually administered in the hospital environment. The
platinum passes into hospital sewage which is then treated with household sewage in
WWTS.

The authors monitored effluent samples from the University Hospital of Freiberg and two
communal hospitals and found total inputs of platinum of around 330g/year from the
University Hospital and 12 g/year from the Community Hospital. These equated to a
consumption per bed per day of 600 µg Pt for the University Hospital and 85 µg Pt the
community hospital. Extrapolation on a national basis, this amounted to an upper limit for the
input in Germany of 141 kg Pt per year (c. 645,000 hospital beds (German Statistical
Federal Agency, 1994) and a lower limit of 20 kg/year, with an average calculated value of
28.6 kg/year. Comparisons with other sources are shown in Table a.6.

Table a.6 Sources and sinks of platinum in Germany (from Kümmerer and Helmers,
1997)
Source Amount Pt (kg/year) Reference
Catalytic converters 15 König et al., 1992
emissions Zereini, F., personal
communication 1996
Hospital effluents 28.6 Kümmerer and Helmers, 1997
Sewage sludge 100.4 - 400.8 Laschka and Nachtwey German
Statistical Federal Agency, 1995

120
Section 6. Case Studies

A broader study based on hospitals in Belgium, Italy, Austria, the Netherlands and Germany
aimed to provide reliable data with which to quantify sources of platinum in the environment
from hospitals with other sources (Kümmerer et al, 1999). This study was supported by the
LIFE95/D/A41/EU/24 Project of the European Community.

It was shown that 70% of the Pt administered in carboplatin and cisplatin is excreted and will
therefore end up in hospital effluents. Pt concentrations measured in the total effluent of the
different hospitals ranged widely from less than 10 ng.l-1 (the detection limit) in the Belgian
and Italian hospitals to cca. 3,500 ng.l-1 for the Austrian and German hospitals. In all cases
the influent of the WWTS was below 10 ng.l-1 as a result of dilution within the waste water
system.

Annual emissions by hospitals and cars in Germany, Austria and the Netherlands are listed
in Tables a.7 and a.8 and compared in Table a.9.

Table a.7 Emission of platinum by hospitals (D=Germany, A=Austria, NL=The


Netherlands)

D 1994 D 1996 A 1996 NL 1996


Total hospital beds (approx) 645000 645000 77500 60000
Maximum Medical Performance 45000 45000 6500 N/A
Pt per bed and year (mg)
- maximum medical service spectrum 154.0 130.4 58.7 22.3
- medium medical service spectrum 14.0 14.0 N/A N/A
Pt emissions by hospitals
- maximum medical service spectrum 6.9 5.8 0.38 1.3
- medium medical service spectrum 8.4 8.4 N/A N/A
Total emissions by hospitals (kg) 15.3 14.2 N/A N/A
All hospitals as maximum medical service 99.3 84.1 4.6 1.3
spectrum

121
Section 6. Case Studies

Table a.8 Emissions of platinum by cars


D 1994 D 1996 A 1996 NL 1996
Number of cars 32 000 000 32 000 000 3 593 588 5 740 489
With catalytic converter 12 800 000 19 200 000 1 607 699 3 307 300

% with catalytic converter 40.0 60.0 44.7 57.6


Kilometres/car 15 000 15 000 14 374 13 538
Total Kilometers (cat only) 1.92 x 1011 2.88 x 1011 2.311 x 1010 4.491 x 1010
Emission ( g km-1) 0.65 0.65 0.5 0.5
Total emission by cars (kg) 124.80 187.20 11.55 22.46

Table a.9 Platinum emissions comparison: hospitals vs. cars


D 1994 D 1996 A 1996 NL 1996
Maximum medical service spectrum 5.6 3.1 3.3 6.0
Medium medical service spectrum 6.7 4.5 N/A N/A

Total 12.3 7.6 3.3 6.0


All hospitals calculated as maximum 79.6 44.9 39.4 6.0
medical service spectrum

In this study the highest concentrations of Pt in WWTP influents were found at the beginning
of rain periods and at the end of cold periods when snow was melting. It was then concluded
that the main inputs of Pt into municipal sewage were from urban and road run-off from
traffic and other Pt emitting sources and not from hospital emitted sewage (Kümmerer et al,
1999).

Emissions from other Sources


Kümmerer et al (1999) further concluded that “emissions by traffic and hospitals cannot
explain the whole amount found in sewage and other sources emitting platinum directly into
sewage have to be considered like glass and electronics industries or jewellery
manufacturing. For the catalytic ammonia oxidation 92 kg platinum are reported to be lost
from the catalyst” (Beck et al., 1995). If all of this is emitted into the atmosphere and
washed off from roads and other paved areas in urban areas, which make up 11% of the
total area of Germany (Losch, 1997), 10 kg from this source would be the input into sewage.
If there are local industries like jewellery and electronic industries (Lottermoser, 1994) which
use platinum to a certain extent they might be the most important local contributor to the
platinum content of a certain municipal sewage and sewage sludge. Thus, unspecified input
directly from industrial processes into sewage must be taken into account. These possible
sources include jewellery manufacture, dental laboratories, electronic industries, glass
manufacturing, production of platinum-containing drugs and industrial catalysts.

Knowledge on these sources, the species involved and their environmental properties is
sparse if not non-existent.

A study of PGMs in sewage sludge incineration ashes from the municipal WWTS at
Karlsruhe, Germany, showed Pd concentrations to have increased from 64 to 138 µg.kg-1
from 1993 to 1997, with Rh increasing from 4.8 to 6.3 µg.kg-1; Pd varied from 300 to 450
µg.kg-1 with no significant trend although these concentrations were 10-fold higher than in
1972 (Schäfer et al, 1999). The authors drew attention to the Pt/Rh ratio in the sludge of c.
20:1 which differs greatly from that of 6:1 typically found in environmental samples
influenced by traffic emissions. They then estimated that, as more than 90% Rh is used for
the production of catalytic convertors, and as Pt and Rh are emitted in a ratio of 6:1, that the
contribution of traffic to the Pt concentration in sludge is only c. 30%, a result similar to that
found in Munich by Laschka et al (1996). They thus suggested that the greater part of Pt in
sewage sludge must come from sources other than catalytic convertors, such as hospital

122
Section 6. Case Studies

and medical effluents or industrial emissions. They drew attention to the fact that “in cities
with a jewellery industry, noble metal concentrations in sewage sludge far exceeded normal
values even before the introduction of catalytic convertors” (Lottermoser, 1994).

Laschka and Nachtwey (1997) analysed Pt on primary and secondary effluents and in
primary and digested sludge from two sewage treatment plants in Munich, where platinum
pollution from industry, hospitals and traffic is considerable. Samples were taken before and
after rainfall in October 1994 and July 1995. In general Pt concentrations in effluents were
higher during rainy weather compared to dry weather. The Pt loading in secondary effluents
was lowest for the period Monday/Tuesday (i.e. after the weekend), which was considered
typical for industrial loads; the authors concluded that during dry weather, the platinum load
originated mainly from industry. Comparison of the average Pt load in primary and
secondary effluents in Munich, indicated a removal rate of 74% and 70% in the treatment
plants. These elimination rates were lower than those typical for other metals such as Pb
and Cd, which was attributed by the authors to the stabilizing effect of chloride (>100mg.l-1 in
domestic sewage, or to the low Pt content of untreated sewage (<0.1 µg.l-1).

This study confirmed the enrichment of Pt in sewage sludge, which was present in materials
from the 2 Munich treatment plants in concentrations ranging from 86 to 266 µg.kg-1.
Sludges from other large towns and centres of industry had previously been found to contain
10 to 130 µg.kg-1 Pt and from smaller rural plants <10 to 50 µg.kg-1 Pt (Lottermoser, 1994).
In this earlier study, an exceptionally high value of 1070 µg.kg-1 had been found in sludge at
Pforzheim, a town with a jewellery industry.

The study of Laschka and Nachtwey (1997) concluded that “in a large industrial centre such
as Munich, automobile traffic is not the dominant source of Pt in municipal sewage”.

A recent review article by Helmers and Kümmerer (1999) has attempted to quantify the
sources, pathways and sinks of Pt in the environment. The authors noted that there was as
yet not enough data to reliably investigate Pd and Rh fluxes, noting the lack of good quality
assurance for Pd analysis and the paucicity of environmental data on Rh. An examination of
archived sewage sludge ash from Stuttgart, Germany showed a continuous increase in Pt
concentrations since 1984. With an estimated 5 x 1010 kg of sewage sludges for Germany in
the early 1990’s and c. 250 mg.kg-1 Pt in sewage sludge, this amounts to some 12,500 kg of
Pt, some 2 orders of magnitude higher than the Pt flux emitted by traffic. Much smaller Pt
concentrations (mean 35 mg kg-1) have been found in smaller German purification plants.

Assuming that 50% Pt emitted by cars is received by sewage systems and taking into
account the amounts of Pt in effluents from hospitals being completely received by sewage
systems, the authors calculate that for Germany Pt received in the influents of WWTS from
both these major sources amounted to 42.9 kg in 1994 and 56.4 kg in 1996. They thus
considered an additional input of around 10 kg Pt per year from industrial sources.

If around 70% of the Pt influent is removed within the WWTS into sludge, the remaining 30%
is emitted into freshwater (see Table 10). In Germany 30% of the sewage sludge is used on
agricultural land and 70% disposed of as sludge or incinerated sludge ash. Losses to the
atmosphere from incineration are not yet known.

Table 10. Partition of anthropogenic Pt fluxes (in kg) within German WWTS
Year Received by Remaining in Disposal with Deposited Released into
the WWTS the sewage sludges or agriculturally freshwater
sludges ashes with sludges
1994 42.9 30.9 21.6 9.3 12
1996 56.4 40.6 28.4 12.2 15.8

123
Section 6. Case Studies

Helmers and Kümmerer (1999) consider the possibility of extrapolating these results to other
European countries, taking into account traffic densities, catalytic convertor policies etc., with
the qualification that “since there is no highway speed limit in Germany, highway Pt
emissions of other countries may be halved in comparison with the German situation”
(Helmers, 1997).

Solubility and bioavailability of PGMs in the environment

Current scientific opinion would seem to agree that PGMs emitted as autocatalyst particles
remain bound to these and have limited mobility in the road and soil environment (Rauch et
al, 2000). Experimental studies under laboratory conditions, in which ground catalysts have
been added to soils under varying conditions of pH, chloride and sulphur concentrations
have indicated that post-deposition processes in soils and waters are of minor importance
and that “the risk of a health endangering contamination of the environment, and especially
groundwater, at present seems negligible, as the PGM species behave relatively inertly”
(Zereini et al, 1997). However transformation of PGMs into more mobile forms has not been
ruled out and indeed Rauch et al (2000) suggest that this may occur “in the roadside
environment, during transport through the stormwater system or in the urban river”.

In the absence of detailed study, it would seem impossible at this stage to apportion soluble
PGM species in the influents and effluents of WWTS’s to specific PGM sources from traffic,
hospital or industry, or to transformation/mobilisation of Pt and other PGMs in the
environment and/or waste water system, or indeed in the processing plant.

124
Section 6. Case Studies

Conclusions

Platinum group metals are present in the influents of WWTS as a result of

• exhaust emissions from motor vehicles using catalytic convertors (both petrol and
diesel) and subsequent runoff from road surfaces and roadside soils;
• emissions in effluents from hospitals using the anti-cancer drugs cirplatin and
carboplatin,
• industrial uses including jewellery manufacture, electronics and glass manufacture.

Several studies over the past decade have shown a steady increase in the use of PGMs.
Reliable quantitative information has shown that in general by far the greatest input of Pt and
Pd into the environment and into WWTS is from vehicle exhaust catalysts, with hospital
effluents accounting for some 6 to 12 per cent Pt. In large industrial centres, such as
Munich, inputs from other sources (presumed industrial) may exceed those from catalytic
convertors and hospitals. Quantitative knowledge of these sources is not currently available.
The solubility of PGMs entering the environment and the influents of WWTS is thought to be
low, though reactions within the soil/dust and wastewater environments need further study.
Interactions with chloride ions and humic substances may well increase solubility and thus
bioavailability.

Around 70 per cent of Pt in the influents to WWTS is removed with treatment into sludge,
which may then be applied to agricultural land or incinerated. Where land application is
practical, studies into uptake into pasture and foodcrops are recommended. The 30 per cent
of Pt emitted into freshwater systems will potentially increase Pt levels in drinking water
supplies.

At present there is no evidence of health risks arising from increasing levels of PGMs in the
roadside environment, in sewage sludge or in drinking water. However, as levels of use
continue to rise, it would seem prudent to focus research into factors influencing their
solubility and bioavailability, their uptake and input into food crops and drinking water and
into multiple exposure routes into the population.

125
Section 6. Case Studies

(b) Case Study- Sustainable Urban Drainage

Summary

Urban runoff source control practices have been the centre of an ongoing discussion
involving maintenance and quality issues. This review will provide a brief overview of
available techniques and structures and summarise their design characteristics. A
discussion on performance will focus on water quality but comments on maintenance will
also be included to allow the reader to form an overall opinion. A number of source control
application case studies in Europe will be discussed from the point of view of performance.

Introduction

Urban Runoff has traditionally been treated as a water quantity problem and the usual
approach to solving it has been a system of buried pipes designed to convey water
downstream as soon as possible (CIRIA, 1999). Several problems in this traditional
approach have been identified including possible flooding in downstream areas due to
alteration of natural flow patterns, water quality issues that are not dealt with within the pipe
system and largely ignored amenity aspects (such as water resources, landscaping potential
and provision of varied wild habitat). These considerations have led to an effort of rethinking
surface water drainage methods within the following framework:

• Deal with runoff as close to the source as possible


• Manage potential pollution at source
• Protect water resources from pollution
• Increase amenity value

This framework and the practices and drainage systems that were developed from it, are
collectively referred to in the UK as “sustainable urban drainage systems” (SUDS) (CIRIA,
1999) or more generally “source control” (Urbonas and Stahre, 1993) or “best management
practices” (BMPs) 1 (Jefferies et al., 1999). They essentially confirm with the emergence of
Agenda 21 as a local action-planning basis for strategic and integrated approaches “to halt
and reverse the effects of environmental degradation and to promote sound environmental
development” (United Nations, 1992). Source Control includes structures such as:

• Dry Detention Basins


• Infiltration Devices
• Oil and Grease Trap Devices
• Sand Filters
• Vegetative Practices
• Filter Strips
• Grassed Swales
• Wetlands, Constructed
• Wetlands, Natural and Restored
• Wet Retention Ponds

1
The fact that this Report adopts the widely used terms SUDS and BMPs to refer to source
control and distributed storage practices does not imply that it necessarily considers them either
“sustainable” or “best”. The positive and negative aspects of these practices will be discussed in the
following paragraphs.

126
Section 6. Case Studies

Basic design characteristics and principles of use of the most widely used of these systems
will be presented in the following paragraph and are summarised in Table 1.

Source Control Systems

The techniques presented will be grouped in four categories according to the CIRIA
recommendations: (a) filters and swales, (b) permeable surfaces (c) infiltration devices and
(d) ponds (CIRIA, 1996; CIRIA, 1999). The overall structure of an urban catchment with
source control can be seen in the schematic in Figure b.1.

Figure b.1. Urban Runoff and Catchment (after CIRIA, 1996)

127
Section 6. Case Studies

Filters and Swales:


These are vegetated landscape features with
smooth surfaces and downhill gradient.
Swales are long shallow channels while filters
are gently sloping areas of ground. They
mimic natural drainage patterns slowing and
filtering the flow and are used for the drainage
of small residential areas and roads. The flow
depth should be smaller than the height of the
grass to ensure filtration. Operational
practices include regular mowing and clearing
litter. Special care should be taken not to
allow the swale to erode after heavy storms.
Grass swales have been used extensively in
North America, but have only recently
appeared in Europe. Information on treatment
performance comes mainly from the US (as
summarised in Ellis, 1991) and indicates
removal potential for solids, potentially toxic
elements and hydrocarbons). In the UK
however the quality improvement potential of Figure b.2. Grass Swale (after CIRIA 1996)
the swales is ignored. A typical swale
structure can be seen in Figure b.2.

Permeable surfaces:
These include porous pavements, gravelled
areas, grass areas and other types of
continuous surfaces with an inherent system of
voids. The water passes through the surface to
the permeable fill, allowing for storage,
transport and infiltration of water. The actual
amount of water stored is dependent on the
voids ratio, the plan area and the structure’s
depth. It acts as a trap for sediment thus
removing a large number of pollutants from the
runoff, but keeps them within the particular site.
The principal mechanism for pollutant retention
is thought to be adsorption onto materials
within the pavement construction (Pratt, 1989).
Maintenance should ensure that the voids are
not filled by sand and silt and such an
operation may prove costly, as the surface
structure can deteriorate under external
pressure. The US, France, Holland, Austria
and Sweden have used porous surfaces for Figure b.3. Porous Pavement (after CIRIA
both traffic and pavement areas (Diniz, 1976; 1994)
Hogland, 1990). A typical structure can be
seen in Figure b.3.

128
Section 6. Case Studies

Infiltration devices:
Soakways and infiltration trenches are below
ground and are filled with a coarse material.
They drain water coming in the infiltration
device from a pipe or a swale directly to the
surrounding soil. Their operation is based on
increasing the natural capacity of the soil for
infiltration but effectiveness is ultimately limited
by soil permeability. The volume of storage
therefore is dependent on soil infiltration
potential. Physical filtration can remove solids,
while biochemical reactions caused by
microorganisms growing on the fill or the soil
can degrade hydrocarbons. The level of
treatment depends on the size of the media
and the length of the flow path (CIRIA, 1999).
Extensive use of soakways in Sweden and the
US as well as in the UK generally provide
positive feedback on maintenance and
operation (Pratt, 1989; CIRIA, 1996). Areas
that are drained through infiltration structures of Figure b.4. Soakway (after CIRIA, 1996)
different types include car parks, roads, roofs
pavements and pedestrian sidewalks. Pollution
levels in these types of urban runoff can be
however significant and there is therefore
serious risk of introducing the pollutants to the
groundwater. Additionally the introduction of
water to the soil may cause geotechnical
problems. Figure b.4 describes a typical
soakway.

(d) Basins and Ponds:


These are areas of storage of surface runoff
that are free from water under dry weather
conditions. Structures can be mixed with a
permanently wet area for wildlife or
treatment of runoff and an area that is
usually dry to allow for flood attenuation.
The ponds are normally situated near the
end of the system due to detention and land
price constraints (Makropoulos et al., 1999).
Flow detention would lead to settlement of
the particles and associated pollution loads.
Additionally some bacterial die-off and
soluble particle removal could be expected
(CIRIA, 1994). Annual clearance of the
aquatic vegetation and silt-removal every
five to ten years should be thought of as an
average operational practice. Figures b.5
and b.6 give an idea of on and off stream
detention and the pond-wetland principle
respectively. Figure b.5. Typical on and off stream
storage ponds (after CIRIA, 1994)

129
Section 6. Case Studies

Figure b.6. Typical arrangement of a reed bed treatment pond (after CIRIA, 1994)

Performance

Systematic evaluation of the application of these systems is scarce in literature. Research


has been focusing on mathematical modelling of the system’s quality performance and
actual data is generally not available in Europe. Scotland is a notable exception. BMPs have
been promoted for the past five years in response to the need to combat pollution from
diffuse sources in urban areas. To meet this need, a programme of investigations is being
undertaken into the performance of BMPs, which have been built in Scotland. An initial
awareness survey by Abertay University and SEPA indicated high levels of apparent
knowledge of BMPs, but subsequent investigations showed that in many instances
knowledge was very superficial and often inadequate. Jefferies et al. (1999) discuss
experimental findings and theoretical considerations of that investigation and show that, in
most systems, pollutants will form sludge. This in turn must be disposed of, and indeed good
household practices may be the only truly sustainable drainage practice. Pollutants removed
from runoff in a system such as a pond may accumulate in sediments and biota. Potentially
toxic elements and trace organics in rainfall runoff are to some extent associated with soil
particulates, as discussed earlier in this report, and will thus tend to be removed by
sedimentation. The soluble fraction of pollutants will also to some extent precipitate following
changes in pH, oxidation-reduction potential or temperature (Kiely, 1997). The activity of the
pollutants however is not ended with their concentration in the sediments. Polluted sediment
may be resuspended or pollutants may be released during high stream flows (Pitt, 1995).
The quality of groundwater may also be affected by exfiltration of contaminants from BMP
systems. Studies in the US have shown that, when disposed in soakways,
organophosphates have appeared in watercourses 400 metres away only two hours after
disposal (ENDS, 1993). The entire range of toxic pollutants identified as possible input to
urban rainfall runoff may leak this way to the groundwater. A new problem has appeared in
the form of methyl butyl tertiary ether (additive to unleaded petrol), which is ten times more
soluble in water than other constituents in petrol and thus would tend to spread readily in
groundwater (Kiely, 1997). When soil is used as a filtration medium in source control
systems (as in infiltration trenches and even grass swales), it must be regularly checked as
the adsorbed pollutants may be remobilised under various conditions. Furthermore, possible
degradation of pollutants inside the systems may give rise to hazardous by-products which
may be more soluble or toxic than the original forms (Hallberg, 1989). Biotransformation of
TCE for example results in hazardous products such as vinyl chloride, which is a confirmed
human carcinogen (Burmaster, 1982). Table b.1 summarises the main functions and water
quality attributes of source control.

130
Section 6. Case Studies

Table b.1. Functions and water quality attributes of different source control structures
(after CIRIA, 1994)

METHOD PRIMARY SECONDARY WATER QUALITY ATTRIBUTES


FUNCTION
Infiltration Collection and Sediment and Can remove pollutants associated
pavements disposal of pollutant removal with sediments and dissolved
surface water pollutants but may be lead to increase
in nutrient levels
Swales Conveyance of Storage sediment and Can remove suspended and possibly
surface waters pollutant removal; dissolved pollutants but may be a risk
disposal to groundwater quality if not sealed
Infiltration Disposal of Storage; sediment and Can remove suspended and possibly
basins surface water pollutant removal dissolved pollutants but may be a risk
to groundwater quality
Storage Storage of Sediment and Can remove pollutants associated
ponds surface water pollutant removal with sediments and provide some
biological treatment
Wetlands Pollutant removal Storage Can remove and treat various
pollutants

France has also had experience in particular aspects of SUDS (for detention basins and
ponds). Nascimento et al. (1999) provide an overview of the French experience in detention
basins use and performance. In France, detention basin use dates back to the 1960s,
together with the construction of the “Villes Nouvelles”. Their use was limited, but these
facilities are increasingly popular as indicated in Deutsch et al. (1990) (Reported in
Nascimento et al., 1999). Recent research has focused in the quality side of performance of
the ponds with the QASTOR database created by CEREVE as a centre point (Saget et al.,
1998). The database aims to collect and analyse all French national data related to urban
wet weather discharge that have been collected in 19 catchments since 1970. The efficiency
of detention basins in reducing pollutants is the result of a large number of variables
including physical, chemical and biological characteristics of pollutants, precipitation regime,
detention time and quality of maintenance services (Nascimento et al., 1999). Table b.2
identifies the potential annual and short-term efficiency of detention basis recorded by Adler
(1993) as reported in Nascimento et al, (1999). The Table draws from studies conducted by
the French institution CEMAG-REF. The presented data were for basins installed in
separate drainage systems and the results indicate that such storage facilities can have a
reasonable performance even over quite short time scales.

Table b.2. Efficiency of detention basins (after Nascimento et al., 1999)

Yearly Inflow Yearly Outflow Reduction Reduction after


(kg/ha imp) (kg/ha imp) (%) 2h
(%)
Pb 0.893 0.054 94.0 65
Zn 5.12 0.66 87.1 77
Cd 0.0310 0.0051 83.7 -
Cu - - - 69
Hydrocarbons 65 4 94.2 -

However, despite such evidence, when the issue of integrating detention basins into the
urban context is concerned, the outcome may be very different according to the specific
case. For the UK the high pollutant loading to urban detention basins, which has been
reported, has led to concerns about long-term siltation (and loss of effective storage volume)
and water quality (especially in terms of health risks). Sansalone (1999) describes the

131
Section 6. Case Studies

results of measurements taken in a field scale infiltration trench. Figure b.7, summarises
some of the findings, indicating significant potentially toxic element removal efficiency
exceeding 80% after 1 year of runoff loadings.

The Technical University of Denmark (Mikkelsen, et al. 1996a and 1996b) has been involved
in a series of tests to examine the effects of stormwater infiltration on soil and groundwater
quality. They found that potentially toxic elements and PAHs present little groundwater
contamination threat, if surface infiltration systems are used. However, they express concern
about pesticides, which are much more mobile.

Recent and ongoing studies in the US have tried to identify the potential hazards from the
use of infiltration systems.

Figure b.7 Infiltration Trench removal performance and % of influent exfiltrated to


soil for a series of 4 runoff events compared to bench scale results (lab) after 1 year
of equivalent loading (after Sansalone, 1999)

In particular, a multi-year research project sponsored by the US EPA addresses the potential
problem of groundwater contamination due to stormwater infiltration (Pitt, Clark and Palmer,
1994; Pitt et al., 1997; Pitt, Clark and Field, 1999). In the case of pesticides the research
found that heavy repetitive use of mobile pesticides, such as EDB, on site with infiltration
devices likely contaminates groundwater. Fungicides and nematocides must be mobile in
order to reach the target pest and hence, they generally have the highest contamination
potential. Pesticide leaching depends on patterns of use, soil texture, total organic carbon

132
Section 6. Case Studies

content of the soil, pesticide persistence, and depth to the water table (Shirmohammadi and
Knisel 1989). A pesticide leaches to groundwater when its residence time in the soil is less
than the time required to remove it, or transform it to an innocuous form by chemical or
biological processes. The residence time is controlled by two factors: water applied and
chemical adsorption to stationary solid surfaces. Volatilization losses of soil-applied
pesticides can be a significant removal mechanism for compounds having large Henry’s
constants (K h), such as DBCP or EPTC (Jury, et al. 1983). However, for mobile compounds
having low Kh values, such as atrazine, metolachlor, or alachlor, it is a negligible loss
pathway compared to the leaching mechanism (Alhajjar, et al. 1990).

Restricted pesticide usage in areas with high infiltration potential has been recommended by
some U.S. regulatory agencies. The slower moving pesticides were recommended provided
they were used in accordance with the approved manufacture’s label instructions. These
included the fungicides Iprodione and Triadimefon, the insecticides Isofenphos and
Chlorpyrifos and the herbicide Glyphosate. Others were recommended against, even when
used in accordance with the label’s instructions. These included the fungicides Anilazine,
Benomyl, Chlorothalonil and Maneb and the herbicides Dicamba and Dacthal. No
insecticides were on the “banned list” (Horsley et al, 1990).

In the case of potentially toxic elements, problems may appear when infiltrating
stormwater using a rapid infiltration system (Crites 1985), such as a dry well. Most metals
have very low solubilities at the pHs found in most natural waters and they are readily
removed by either sedimentation or sorption removal processes (Hampson 1986). Many are
also filtered, or otherwise sorbed, in the surface layers of soils in infiltrating devices when
using surface infiltration. Table 3 discusses the pollutants found in stormwater that may
cause groundwater contamination problems when allowed to infiltrate through infiltration
devices.

133
Section 6. Case Studies

Table b.3. Groundwater Contamination Potential for Stormwater Pollutants (after Pitt et al., 1994)

Compounds Mobility Abundance Fraction Contamination Contamination Contamination


(worst case: in storm- filterable potential for potential for potential for sub-surface
sandyl-1ow water surface infilt. and surface infilt. with injection
organic soils) no pre-treatment sedimentation with minimal pre-treatment
Nutrients nitrates mobile low/moderate high low/moderate low/moderate low/moderate
Pesticides 2,4-D mobile low likely low low low low
γ-BHC (lindane) intermediate moderate likely low moderate low moderate
malathion mobile low likely low low low low
atrazine mobile low likely low low low low
chlordane intermediate moderate very low moderate low moderate
diazinon mobile low likely low low low low
Other VOCs mobile low very high low low low
organics 1,3-dichlorobenzene low high high low low high
anthracene intermediate low moderate low low low
benzo(a) anthracene intermediate moderate very low moderate low moderate
bis (2-ethylhexyl) intermediate moderate likely low moderate low? moderate
phthalate
butyl benzyl phthalate low low/moderate moderate low low low/moderate
fluoranthene intermediate high high moderate moderate high
fluorene intermediate low likely low low low low
naphthalene low/inter. low moderate low low low
penta- chlorophenol intermediate moderate likely low moderate low? moderate
phenanthrene intermediate moderate very low moderate low moderate
pyrene intermediate high high moderate moderate high
Potentially nickel low high low low low high
toxic cadmium low low moderate low low low
elements chromium inter./very low moderate very low low/moderate low moderate
lead very low moderate very low low low moderate
zinc low/very low high high low low high
Salts chloride mobile Seasonally high high high high
high

134
Section 6. Case Studies

Conclusions

The control of diverse pollutants requires a varied approach, including source area controls,
end-of-pipe controls, and pollution prevention. All dry-weather flows should be diverted from
infiltration devices because of their potentially high concentrations of soluble potentially toxic
elements, pesticides, and pathogens (Pitt et al., 1999) Similarly, all runoff from
manufacturing industrial areas should also be diverted from infiltration devices because of
their relatively high concentrations of soluble pollutants. In areas of extensive snow and ice,
winter snowmelt and early spring runoff should also be diverted from infiltration devices.

All other runoff should include pre-treatment using sedimentation processes before
infiltration, to both minimize groundwater contamination and to prolong the life of the
infiltration device (if needed). This pre-treatment can take the form of grass filters, sediment
sumps, wet detention ponds, etc., depending on the runoff volume to be treated and other
site-specific factors. Pollution prevention can also play an important role in minimizing
groundwater contamination problems, including reducing the use of galvanized metals,
pesticides, and fertilizers in critical areas. The use of specialized treatment devices can also
play an important role in treating runoff from critical source areas before these more
contaminated flows commingle with cleaner runoff from other areas (Pitt et al., 1999).
Sophisticated treatment schemes, especially the use of chemical processes or disinfection,
may not be utilised, provided there is no danger of forming harmful treatment by-products
(such as THMs and soluble aluminium).

The use of grass swales and percolation ponds that have a substantial depth of underlying
soils above the groundwater is preferable to using dry wells, trenches and especially
injection wells, unless the runoff water is known to be relatively free of pollutants. Surface
devices are able to take greater advantage of natural soil pollutant removal processes.
However, unless all percolation devices are carefully designed and maintained, they may not
function properly and may lead to premature hydraulic failure or contamination of the
groundwater (Pitt et al., 1999).

It should be clear that although SUDS have great potential in both quantity and quality
control in urban runoff, each case should be assessed individually, and an incremental
approach containing both high tech and low-tech solutions is the most likely development
scenario (Butler and Parkinson, 1997). Direct application of such methods across different
regions and countries is not always appropriate and must also include consideration of the
local socio-economic and administrative circumstances associated with the operational
design, which can be primary inhibitors to the implementation of innovative technology.

135
Section 6. Case Studies

(c) Artisanal Activities:


Pollutant Sources and load in Urban Wastewater in Vicenza, Northern Italy;
Gold Jewellery – Best Environmental Practice

Pollutant sources and load in urban wastewater in Vicenza, northern Italy

Introduction

In Northern and Central Italy there is a high density of small-scale, artisanal enterprises and
activities. For example, in the region of Veneto (North-Eastern Italy), artisanal activities
account for 20% of the regions exports. The area of Vicenza, a provincial town in the Veneto
region, represents one of the largest agglomerations of artisanal activities in Italy. With a
population of 109,000 inhabitants, the municipality of Vicenza has a total of about 1600
small to medium-scale enterprises (SMEs).

The environmental impact of artisanal activities is less clearly understood than the impact
from industrial activities. While there are a large number of point sources, each source
contributes a very low wastewater flow rate, closer to the wastewater discharge from
residential units than from industrial sites. Nevertheless wastewater from artisanal activities
may be dramatically different to that from residential units, both in terms of pollutant
concentration and the presence of specific pollutants.

Due to the presence of specific pollutants, wastewater discharge is regulated in the same
way as industrial wastewater (i.e. in terms of pollutant concentration limits), even though
artisanal wastewater flow rates may be orders of magnitude lower than industrial ones
[Italian law by decree n. 152, 1999]

EBAV (Ente Bilaterale Artigianato Veneto, a non-profit bilateral organisation representing the
interests of both artisanal workers and enterprises) sponsored a study on the origin and
contribution of pollutants to urban wastewater. The aim of the study was to assess the load
of pollutants from different artisanal activities, in comparison to the total load originating from
the urban wastewater system. In addition, the pollutant load from artisanal activities was
subdivided into load from discharged wastewater and load from concentrated liquid wastes
(which are separated and collected by external firms), to assess if wastewater segregation
could significantly affect pollutant load from artisanal activities.

Description of the study


The EBAV study was carried on in the period 1994-1995 in the municipality of Vicenza.
According to local authorities, the only notable change (in terms of residential population and
type of SMEs) since the time of the study, has been the rapid increase in the number of
“service” enterprises (for example software companies), which do not contribute specific
wastewater. Therefore, this growing number of “service” companies does not affect the
conclusions of the study, which still may be considered valid today.

Wastewater for the whole Vicenza area is treated by four WWTS (Table c.1). The total
capacity is about 137,900 p.e. (population equivalent) with a total flow rate of about 23.2
million m3 year-1.

136
Section 6. Case Studies

Table c.1 capacity of the four municipal wastewater treatment plant of Vicenza
municipality p.e.=population equivalent

WWTS Capacity (p.e.) Treated flow rate m3 year-1


CASALE 71,900 10,202,000
LAGHETTO 3,500 394,000
LONGARA 3,500 826,000
S. AGOSTINO 59,000 11,800,000
Total 137,900 23,222,000
In this area there are about 1,579 artisanal enterprises discharging their wastewater into the
UWW collecting system. Table c.2 shows the most common artisanal activities in the area of
Vicenza and the number of enterprises involved in each activity. For each activity a
representative number of enterprises was selected for further investigation. Typically one
wastewater sample was drawn from each enterprise. In some cases an additional sample of
concentrated, segregated wastewater was also drawn.

Table c.2 Main artisanal activities in the area of Vicenza


Type of activity No. of samples No. of enterprises in the
municipality of Vicenza
Food workshops 10 53
Car-repairers 20 (14+6*) 175
Ceramic and photoceramic 7(6+1*) 23
Artisanal galvanic shops 8(5+3*) 18
Printing shops 21(14+7*) 140
Wood manufacturing 18(3+15*) 92
Marble manufacturing 5 140
Metallurgists and mechanics 15(8+7*) 155
Dental practices 21 88
Gold manufacturing shops 34 258
Hairdressers 19 310
Laundrettes and dry-cleaners 25 88
Textile shops 2 16
Artisanal glass manufacturing 3 23
TOTAL 208 1579
*concentrated wastewater, segregated and committed to external firms

Total load
Along with artisanal wastewater samples, influent and effluent samples from the four
municipal WWTS were analysed for a large number of pollutants including: B, Cd, Cr(III),
Cr(VI), Mn, Ni, Pb, Cu, Zn, and anionic surfactants. From each of the four WWTS a large
number of influent and effluent samples were taken and analysed. Using the specific
wastewater flow rate and the influent concentration, the pollutant load was calculated for
each plant. Table c.3 reports the total load as sum of the pollutant loads of the WWTS,
assuming that urban wastewater is treated by only one hypothetical centralized plant.

Total pollutant load in Table c.3 is reported as average value, based on the average
concentration from 20-50 samples. In addition, the maximum load and the upper 95%
confidence interval are given. The last column reports the average removal efficiency based
on the comparison of influent and effluent pollutant concentrations.

137
Section 6. Case Studies

Table c.3 Pollutant load to the hypothetical centralized WWTS of Vicenza municipality

POLLUTANT TOTAL LOAD REMOVAL


(g/day) EFFICIENCY(%)
AVERAGE MAX(95%) MAX
Cd 64 75 960 40
Cr(III) 636 759 13244 75
Cr(VI) <LOD. <LOD <LOD
Mn 4921 4930 15623 37
Ni 7092 7940 44421 30
Pb 636 737 12527 60
Cu 3546 3976 16061 80
Zn 11221 13657 60174 70
<LOD = below limit of detection

iv) Pollutant load from specific artisanal activities

A typical example of the analytical work performed for each category of artisanal activity is
reported in Tables c.4 and c.5 for car repair shops. A rough statistical analysis of the results
has been performed to obtain the average concentration and the upper limit of the 95%
confidence interval (Max 95%). In addition the maximum value (Max) is also reported.

Table c.4 Pollutant concentrations (mg l-1) in discharged wastewater of 14 car-repair


shops
Pollutant Average Max 95% Max
CI
COD 329 547 1800
Cd 0.01 0.03 0.14
Cr(III) 0.1 0.2 0.8
Cr(VI) 0 0 0
Mn 0 0 0
Ni 0 0 0
Pb 0 0.1 0.4
Cu 0.1 0.1 0.5
Zn 4.5 11.1 55

Table c.5 Pollutant concentrations (mg l-1) in the segregated wastewater of 6 car-
repair shops

Pollutant Average Max Max


95%CI
COD 10293 15346 19120
Cd 0.3 0.7 1.3
Cr(III) 0.2 0.3 0.5
Cr(VI) 0 0 0
Ni 2.5 6.1 12
Pb 22.1 52 102
Cu 33 74.6 144
Zn 31.9 73.8 145

Pollutant load was calculated for the selected enterprises and extrapolated to the total
number of enterprises for each category. Even though each enterprise was equipped with its
own treatment plant, pollutant loads were calculated on the basis of concentrations in the
untreated wastewater, hypothesizing a scenario where no pre-treatment is performed and

138
Section 6. Case Studies

the wastewater is discharged directly into the UWW collecting system. Similar calculations
were performed using concentrations and volumes of segregated wastewater (spent baths).
So, for the enterprises that separate wastewater for treatment by external firms (for recovery
and detoxification), two potential pollutant loads were given with reference to the two
hypothesized scenarios:

• all the wastes (concentrated and diluted wastewater) are discharged into the urban
wastewater system without pre-treatment (Table c.6 D and S);
• the spent baths are treated externally, whereas wastewater is directly discharged into
the urban wastewater system (Table c.6 D only).

Car-repairers (175 shops)

The most significant pollutants are: suspended material, COD, oils, surfactants, organic
solvents, copper, and zinc.

Considering both discharged and segregated wastewater the total pollutant load for Zn, Cd,
Cu and, above all, Pb is very high. However upon careful segregation of concentrated
wastewater (D only), the pollutant load is significantly reduced. The careful segregation of
spent baths induces a decrease of about one order of magnitude in the percentage of lead
originating from car repair shops.

Ceramics and photoceramics (23 shops)

The principal pollutants from these artisanal activities are: suspended solids, lead, ammonia,
nitric nitrogen, and surfactants. As can be seen in Table c.6 the pollutant load from the
ceramic and photoceramic shops is minimal due to the low wastewater flow rate. Only lead
seems to represent a significant load. In the case of ceramic shops, segregation of
concentrated wastewater is not very significant in terms of reducing pollutant load.

Galvanic (18 shops)

The principal pollutants from these enterprises are: suspended solids, chromium (VI),
nickel, lead, copper, and cyanide. Segregation and external treatment of concentrated
wastes does not appear to significantly reduce the lead load because this load originates
mainly from the discharged diluted wastewater.

Printing shops (140 shops)

Printing activities generate several pollutants: suspended material, COD, cadmium,


chromium, lead, copper, zinc, sulphites, sulphates, chlorides, ammonia, total phenols,
aldehydes, aromatic organic solvents, and surfactants. Due to the low contribution to the
overall UWW flow rate (0.15%), only Cd and Cu loads from the printing activities are
significant with respect to the total load. Segregation of concentrated wastewater reduces
the load of metals to negligible values.

Wood processing and furniture making shops (92 shops)

The most significant pollutants originating from this activity are: suspended solids, COD,
lead, copper, zinc, total phenols, organic solvents, and surfactants. Table c.6 shows that by
simply segregating concentrated wastes the pollutant load to the WWTS from wood
processing and furniture manufacturing shops is dramatically reduced. Other specific wood
processing pollutants such as arsenic were not analysed.

139
Section 6. Case Studies

Metallurgists and mechanics (155 shops)

Several pollutants originate from metallurgists and mechanic shops: suspended solids,
COD, cadmium, chromium, nickel, lead, zinc, copper, sulphates, chlorides, phosphorus, oils,
solvents, and surfactants. Pollutant concentrations in wastewater are typically much lower
than in segregated wastewaters (see Table c.7) which have high average concentrations of
pollutants such as; nickel, lead, copper and zinc. Separation of concentrated wastes
reduces the load to the WWTS significantly.

Goldsmiths (258 shops)

The area of Vicenza represents one of the most important districts for gold manufacturing in
Italy, with up to 258 artisanal goldsmith shops. The main pollutants originating from gold
manufacture are: COD, boron, cadmium, copper, zinc, and surfactants. However goldsmiths
shops are characterized by very low wastewater flow rates, with an average of about 1 cubic
meter per day per unit.
In terms of contribution to the pollutant load, the 258 goldsmiths shops represent a high
contribution of Cd, Cu, and Zn. This is mainly due to the fact that goldsmith shops used to
add spent concentrated baths to the diluted wastewater in order to recover precious metals
during the wastewater treatment before discharging it into the sewer.

Food workshops (confectioners, ice-cream parlours, bakeries) (53 shops)

The most significant pollutants originating from this activity are: COD, fat, oils, and
surfactants. Cu and Zn are the only metals to be above the limits of detection in wastewater.

Dental technicians (88 shops)

Principal pollutants originating from this activity are: suspended solids, COD, and
surfactants. The contribution of the 88 shops to the total metals pollutant load is generally
low, due to the low contribution in terms of flow rate, that is an average of about 0.07% of
the total UWW flow rate. Mercury is an important pollutant in wastewater linked to dental
practices, which is not considered in this particular study but is referred to in section 2.1.2 of
this report.

Hairdressers (310 shops)

This is the category with the largest number of shops in the Vicenza’s municipality. The main
pollutants originating from hairdressers are: suspended solids, COD, and surfactants.

Laundrettes and dry-cleaners (88 shops)

The main pollutants originating from laundrettes and dry-cleaners are: suspended solids,
COD, surfactants, chlorides, and solvents.

The most significant load of pollutant from the 88 laundrettes and dry-cleaners is for Cd
although overall the levels for this pollutant were very low .

140
Section 6. Case Studies

Table c.5 Pollutant load from specific artisanal activities. D=discharged wastewater,
S=segregated wastewater, (- = not reported).

Flow Average Pollutant Load (g/day)


rate m3
per day
Cd Cr III Mn Ni Pb Cu Zn
Car repair shops 153 4 6.3 <LOD 21.9 218.1 299.7 716.1
(D & S)
Car repair shops 153 1 5 <LOD <LOD 25 11.3 436.8
(D only)
Ceramics and 33 0.1 7.2 <LOD <LOD 19.7 0.1 1.6
photoceramics (D & S)
Ceramics and 33 0.1 4.9 <LOD <LOD 12.8 0.1 1.2
photoceramics (D only)
Galvanic shops 72 0.3 1 - 47.8 9.8 29.8 7.9
(D & S)
Galvanic shops (D only) 72 0.2 <LOD - 30.1 9.4 11.4 7.9
Printing Shops 97 1.8 3.8 <LOD - 3.8 69.5 27.5
(D & S)
Printing Shops 97 <LOD <LOD <LOD - <LOD <LOD 26
(D only)
Wood Processing 35 <LOD 4.8 <LOD - 34.7 16.2 32.9
(D & S)
Wood Processing 35 <LOD <LOD <LOD - <LOD 1.5 24.5
(D only)
Metallurgists and 70 1.4 30 13 1107 163.5 187.5 978.2
Mechanics (D & S)
Metallurgists and 70 0.2 <LOD <LOD <LOD <LOD 13.2 23.8
Mechanics (D only)
Goldsmiths 266 20.5 0.9 <LOD - <LOD 267.7 237.8
(D only)
Food Workshops 120 <LOD <LOD <LOD <LOD <LOD 3.2 31.1
(D only)
Dental Technicians 43 0.2 0.3 0.6 - <LOD 0.7 17.6
(D only)
Hairdressers 289 <LOD <LOD <LOD <LOD <LOD 24.5 111.6
(D only)
Laundrettes and Dry 210 1.5 - <LOD 2.8 2.9 3.3 54.5
Cleaners (D only)
The highest values for each pollutants are highlighted in bold.
NB all samples were also tested for Cr VI but they were all below the limit of detection with the
exception of Galvanic shops considering both discharged and segregated wastewater (average load
Cr VI14.4g/day)

Impact of all artisanal activities on urban wastewater treatment plants

Pollutant loads from all artisanal activities of Vicenza municipality were calculated, summing
the loads of each specific activity as reported in Tables c.7 and c.8.

141
Section 6. Case Studies

Table c.7 Total pollutant loads from artisanal activities in the Vicenza municipality,
considering both discharged and segregated wastewater

POLLUTANT TOTAL POLLUTANT LOAD FROM PERCENTAGE


ARTISANAL ACTIVITIES (g/day) OF TOTAL LOAD
TO WWTS
average max(95%) max
B 2909 4774 38832
Cd 30 66 529 46.59
Cr(III) 54 106 243 8.55
Cr(VI) 14 49 43
Mn 14 19 38 0.28
Ni 1180 3153 8114 16.63
Pb 452 1064 2676 71.12
Cu 903 1872 6387 25.48
Zn 2231 3998 10589 19.88
MBAS 53404 93158 353795 25.45
flow rate m3/day 1633 2526 5559 2.57
p.e. 7697 13295 46221 5.58
<LOD = below limit of detection

Table c.8 Total pollutant loads from artisanal activities in the Vicenza municipality,
considering discharged wastewater only
POLLUTANT TOTAL POLLUTANT LOAD FROM PERCENTAGE
ARTISANAL ACTIVITIES (g/day) OF TOTAL LOAD
TO WWTS
average max(95%) max
B 2909 4774 38832
Cd 24 51 498 36.9
Cr(III) 11 27 100 1.8
Cr(VI) <LOD. <LOD. <LOD.
Mn 0.6 1.7 13 0.01
Ni 33 92 206 0.5
Pb 50 127 491 7.9
Cu 338 621 3873 9.5
Zn 987 1827 6963 8.8
chlorinated solvents 6400 17739 140800
MBAS 50911 87609 342922 24.3
flow rate m3/day 1633 2526 5559 2.6
p.e. 5867 10508 42102 4.3
<LOD = below limit of detection

In terms of flow rate the contribution of all artisanal activities is typically low (2.6%). It
remains relatively low (4%) in the worst scenario case, where the artisanal activities
discharge at the upper limit of the confidence interval of their cumulative wastewater flow
rate, while the total UWW flow rate remains at the average value. In contrast, the percentage
contribution of artisanal activities to the total load is very high for pollutants such as: Pb, Cd,
Cu, Zn, Cr III, and surfactants.

Figures c.1 and c.2 compare the load of each specific activity to the total load of a
hypothetical centralized WWTS, for potentially toxic elements and surfactants, respectively.
Figure c.1 clearly shows that only car-repairers, goldsmiths shops, metallurgists and
mechanics contribute significant amounts of potentially toxic elements to UWW, with respect

142
Section 6. Case Studies

to the total metal load of the all activities. The main activities responsible for the surfactant
load in UWW are; hairdressers, goldsmiths, and food workshops (Figure c.2).

Figure c.1 Heavy metal load from artisanal activities

9000

8000
7000
average load (g/day)

6000

5000
4000

3000

2000
1000

0
AL AU CE GA GR LG MA ME OD OR PR PU TS VE tot

AL: Food workshops


AU: Car repairers
CE: Ceramics
GA: galvanic
GR: Printing shops
LG: Wood manufacturing
MA: Marble manufacturing
ME: Metallurg.and mechanics
OD: Dental practices
OR: Goldsmiths
PR: Hairdressers

Figure c.2 Surfactant load from artisanal activities

60000

50000
average load (g/day)

40000

30000

20000

10000

0
AL AU CE GA GR LG MA ME OD OR PR PU TS VE tot

143
Section 6. Case Studies

With the exception of surfactants and cadmium, the high pollutant loads from artisanal
activities are notably reduced when the concentrated wastes are not considered (Table
c.23). The poor effect of waste segregation on surfactant load is explained by the fact that
the major surfactant contribution derive from activities that do not practice waste
segregation: hairdressers, goldsmiths shops, and food workshops (Figure c.2).

Impact of artisanal activities on sewage sludge characteristics

Assuming that the fate of sewage sludge produced from the hypothetical centralized WWTS
is used in agriculture, the maximum admissible pollutant concentration in sludge must be
considered. From this value a maximum admissible pollutant concentration in the UWW may
be calculated according to the following equation:

Ci Qf 100 %H 2O
C
R% Q
where C is the maximum influent concentration permitted for sludge disposal
Ci is the maximum pollutant concentration allowed in sludge to land
R% is the removal efficiency (%) in the treatment plant
Qf is sludge flow rate in m3 day-1 calculated on the basis of the production of 1.87 l/inhabitant
with 95.5% of humidity
Q is the influent wastewater flow rate
% H2O is the water content of the sludge (95.5%)

Table c.9 Pollutant contribution of artisanal activities to the admissible load for sludge
disposal in agriculture, considering both discharged and segregated wastewater

Pollutant Regulatory limits for Admissible(*) Admissible(*) percentage of total


agricultural use concentration load admissible load
(mg/kg dry sludge) (%)
D.Lgs 99/92 Veneto (mg/l) (g/day) average
Cd 20 10 0.01 580 5.11
Cr(III) 500 0.15 9670 0.56
Ni 300 200 0.17 10549 11.18
Pb 750 500 0.21 13599 3.33
Cu 1000 600 0.28 17582 5.14
Zn 2500 2500 0.66 42045 5.34
(*)on the basis of equation (1)

144
Section 6. Case Studies

Table c.10 Pollutant contribution of artisanal activities to the admissible load for
sludge disposal in agriculture considering only discharged wastewater

Pollutant Regulatory limits for Admissible(*) admissible(*) percentage of total


agricultural use conc load admissible load
(mg/kg dry sludge) (%)

D.Lgs 99/92 Veneto (mg.l-1) (g/day) average


Cd 20 10 0.01 580 4.04
Cr(III) 500 0.15 9670 0.12
Ni 300 200 0.17 10549 0.31
Pb 750 500 0.21 13599 0.37
Cu 1000 600 0.28 17582 1.92
Zn 2500 2500 0.66 42045 2.35
(*)on the basis of equation (1)

In Tables c.9 and c.10 the concentration limits imposed by law for sludge used in agriculture
are reported. From these limits the concentration limit in the influent and the consequent
admissible load were calculated. In the last column the impact of artisanal activities on the
sludge characteristics are reported in terms of percentage load from artisanal activities with
respect to the total admissible load for sludge disposal (calculated using average values).

Table c.10 considers the highest possible pollutant loads in the hypothesis that waste
segregation does not take place. Even in this pessimistic hypothesis, the impact of artisanal
activities is typically low. The highest metal contribution is for Ni, representing 11% of the
admissible load. In the worst case scenario, considering all the maximum loads, artisanal
activities by themselves almost reach the admissible Cd and Ni loads.

The average impact on sewage sludges, without considering the concentrated spent baths
(Table c.9) is less than 5% for all the metals.

Validation of the Case Study with results from a recent study on hairdressers’ shops
in a different area of Veneto region

To validate the results obtained in the study described above, EBAV undertook an additional
study specifically addressed to activities of hairdressers and beauticians. This study,
performed during 1999-2000, considered a group of shops representing all the hairdressers
and beauticians located in the district of Valdagno (Vicenza), which discharge their
wastewater into the UWW collecting system of the municipality of Trissino (Vicenza). In this
validation study the number of shops examined was about 22% of those present in the area,
compared to only 6% of hairdressers in the Vicenza Case Study. Typically one wastewater
sample was drawn from each shop. A rough statistical analysis of the results has been
performed to obtain the average concentration; then the average values have been
increased by 10% to take into account the effects of highly polluted wastewater (due to
typical products such as shampoos or dyes).

In Table c.11 the average pollutant concentrations are reported, as well as the average
wastewater flow rate per unit. In this case wastewater production was even lower than in the
case of Vicenza (600 l.day-1 vs 900 l.day-1). The contribution of hairdressers’ shops to the
total wastewater flow rate entering the Trissino WWTS was 0.33%, whereas in Vicenza area
this was about 0.45%. From the average concentrations (with a safety increase of 10%) and
from wastewater flow rates the pollutant load from the total 135 shops to the Trissino WWTS
was calculated. Where data was available (chromium and surfactants), this load was
compared with the total pollutant load to the WWTS. Data from Valdagno area confirm the
negligible contribution of chromium load, and other potentially toxic elements as well, to the

145
Section 6. Case Studies

WWTS. Analysis of surfactants (anionic and non-anionic) in wastewater samples showed


that the contribution of beauty shops in Valdagno district to the total surfactants load still
remains lower than the estimated contribution in Vicenza municipality, where only anionic
surfactants were considered.

The data presented above, while confirming the negligible contribution of this artisanal
activity to the total load of metallic pollutants, suggest that the extrapolation of the results
from Vicenza Case Study may result in an overestimation of the contribution of artisanal
activity to the pollutant loads in the WWTS systems.

Table c.27 Pollutant concentrations and pollutant loads from hairdressers and
beauticians in the district of Valdagno (Vicenza)
POLLUTANT AVERAGE POLLUTANT LOAD* PERCENTAGE OF LOAD
CONCENTRATION (g/day) TO WWTS
(mg/l) (%)
Cr(III) <0.1 <5 <0.1
Anionic surfactants 44 3915 8.2
Non ionic surfactants 51 4590 6.2
Total surfactants 99 8775 7.2
Flow rate 0.6 (m3/day x shop) 81 (m3/day) 0.33
*based on average + 10%

Conclusions

Cases like the Vicenza district, with artisanal activities deeply rooted in residential areas are
common in Italy and in other EU regions. As shown in the validation case of Valdagno, in
other districts the contribution of artisanal activities to the pollutant load of the UWW system
may be lower.

The principal pollutants originating from these artisanal shops are potentially toxic elements
such as Cd, Ni, Pb, Cu, and Zn, and surfactants.

The main conclusion of this study was that, by segregating concentrated liquid wastes, the
contribution of artisanal activities to the pollutant load was dramatically reduced, at least for
potentially toxic elements. However, only some of the artisanal activities in this Case Study
practised wastewater segregation. One issue raised by artisanal representatives was the
economic cost of segregation of wastewater. It is felt that the stringent environmental
requirements concerning wastewater from Italian artisanal shops, considered industrial
wastewater, do not compensate efforts for waste segregation.

Artisanal activities that did not practice segregation of concentrated liquid wastes include
goldsmiths, hairdressers and food manufacturing shops, which are also the main enterprises
responsible for the surfactant load in wastewater. As a consequence, neglecting the
contribution of segregated liquid wastes did not significantly affect the total load of
surfactants from artisanal shops. This load typically represents one fourth of the total
surfactant load to the WWTS. It may be anticipated that, if careful segregation of the
concentrated liquid wastes were extended to all the artisanal activities, a dramatic decrease
of potentially toxic element and surfactant load from the artisanal activities would be
obtained. Even though the wastewater flow rate from artisanal shops would not decrease
significantly, the pollutant load could be reduced to negligible values with respect to the total
pollutant load.

146
Section 6. Case Studies

GOLD JEWELLERY PRODUCTION IN ITALY- BEST ENVIRONMENTAL PRACTICE

Introduction

In Italy there are about 6,000 small to medium gold and jewellery manufacturing shops, most
of which are concentrated in three main production districts: Arezzo (Tuscany), Vicenza
(Veneto) and Valenza Po (Piemonte). In the period 1995-1999 the Italian Government and
the Association of Artisanal Activities sponsored a large research programme, carried out by
the National Research Council, in support of Craft Goldsmiths Production and Trade. The
programme tackled problems relating to:

• innovation in production cycles,


• fast analytical tools for the assay of precious metals and their alloys,
• safety and health of artisanal workers,
• environmental impact of gold manufacturing shops.

The Italian Water Research Institute (IRSA) carried out a survey on management practices
for wastewater, produced in small to medium gold manufacturing shops in Arezzo (Marani,
1997). According to the Association of Goldsmiths, the results obtained in the survey of
Arezzo district may confidently be extended to draw conclusions about national practices in
goldsmiths’ shops. There is no information on the losses of Au, Ag, PGMs from the gold and
jewellery shops to the wastewaters in this research programme. More data on PGM is
presented in Case Study (a).

The gold manufacturing district of Arezzo

Gold manufacturing processes

The most prevalent processes are those starting from wire or plate to produce rings, chains
and medals. Hollow bars may be used to produce lighter objects. Gold or silver goods may
also be produced using micro-casting or electrolytic processes (electro-forming). All
production cycles have common final steps: object assembly, polishing, finishing and
cleaning.

Wastewater origin and characteristics

Different production cycles and processes generate wastewater in the gold manufacturing
shops. Casting operations to prepare wire or plate do not typically require aqueous
solutions, with exception of small volumes for washing crucibles. In contrast, the preparation
of hollow bars requires nitric acid, hydrochloric acid, caustic soda, and ammonia solutions.

The wastewater resulting from micro-casting comes from water used to break the gypsum
mould and rinse waters. The “gypsum” waters are segregated from the other wastewater
produced in the workshops and recycled after a settling step.

Wastewater from electro-forming is derived from specific activities, as well as from


operations common to other processes. The former wastes may be highly turbid wastewater,
exhaust baths and rinsing waters, mainly derived from the galvanic cycle. Wastewaters
characterised by high turbidity are filtered to eliminate the suspended material and then re-
circulated several times before collecting them with the other wastewater. Regarding
galvanic waters, acid wastes are separated from the wastes containing cyanide. The
concentrated cyanide baths are collected by external firms, whereas the diluted rinse waters
can be either pre-treated in a separate circuit, then added to the main wastewater stream or

147
Section 6. Case Studies

re-circulated after elution through an ion exchange column (anionite). The concentrated
cyanide solutions produced by column regeneration are sent to external firms.

In the final steps of assembly and finishing, the operations producing liquid wastewater are:

• acid pickling,
• galvanic treatments,
• surface shining,
• washing steps.

Usually spent pickling baths are treated by external firms. The waters derived from surface
shining generally contain metal powder. In addition, the final step generates large amounts
of wastewater as well as surfactants present in the spent baths.

Finally hand and floor washing waters, do not typically require pre-treatment and could be
sent to the sewer. However as they may contain gold and silver powder they are not directly
discharged into the sewer. Instead they are sent to the internal wastewater treatment plant.
Here the insoluble precious metals are concentrated in the sludge which, is dried and sent to
specialised firms for recovery of precious metals.

Wastewater may be divided into four classes:

Soapy waters contain high concentrations of detergents, along with fatty substances and
metal powder. Other pollutants such as phosphates and ammonia typically originate from
the detergents used in these workshops.

The acids contained in the acid wastewater are: sulphuric acid, nitric acid, hydrochloric acid,
hydrofluoric and fluoboric acid. This wastewater may also contain high concentrations of
potentially toxic elements such as copper, zinc, iron and nickel.

“Gypsum” waters containing suspended gypsum particles, are recycled several times after
sedimentation of the suspended material. Then they are committed, together with the
sedimented gypsum, to external firms for final disposal.

The cyanide waters contain free cyanide and soluble cyano-complexes of gold and silver.
For safety reasons these waters are treated separately to oxidize the cyanide before
sending them to the wastewater treatment plant.

148
Section 6. Case Studies

Wastewater management and fate


About 40% of the goldsmiths’ workshops of Arezzo province do not declare any wastewater
production. These workshops:
• have a particular production step that does not produce wastewater;
• accumulate little quantities of wastewater to be treated by external firms specialized
in wastewater treatments;
• treat their own wastewater with systems that permit the complete recycle of the
treated water in the productive cycle;
• evaporate the wastewater, obtaining a concentrate to dispose with other solid
wastes.

Regarding the remaining 60% of workshops with authorisation to discharge their


wastewater, Table c.28 reports the number (and relative percentage) of workshops that
discharge their wastewater into the UWW collecting system or into surface waters. In terms
of flow rate, the 694 workshops discharge about 121600 m3.year-1 of wastewater. Assuming
an average number of 6.3 workers per unit, the average specific wastewater flow rate is
about 0.5 m3.week-1 per worker.

Table c.28 Destination of wastewater of workshops having discharge authorisation

Destination No. of workshops % of workshops


UWW collecting 567 81.7
system
Surface waters 29 4.2
Unknown 98 14.1
TOTAL 694 100

Survey on a representative group of goldsmiths’ shops


The workshops were selected with the aim of choosing representative establishments in
terms of number of workers and in terms of type of manufacturing processes. Twelve small
to medium workshops were selected for the study. The survey included both interviews on
production processes, wastewater flow rate, wastewater treatment, direct sampling and
analysis of treated and untreated wastewater. Typically, several wastewater samples were
collected from each workshop, in March, May and October of 1996. The chemical
characterisation of samples was performed analysing a large number of parameters,
including: boron, potentially toxic elements like Cd, Cr, Cu, Ni, Pb, and Zn, and surfactants.

Conclusions
In examining the pollutant concentrations in these wastewaters (considering the results
obtained for the 12 shops sampled), the pollutants most often detected with concentrations
higher than admissible limits for discharge are: surfactants, copper, zinc, cadmium and
boron. Surfactants, copper and zinc are detected in all samples whereas boron and
cadmium are present in 75 % and 60% of samples respectively. Surfactants, derived
generally from washing processes, are present in wastewater with an average concentration
of 34 mg.l-1 MBAS and a maximum value of 118.5 mg.l-1 MBAS. The average boron
concentration found in the wastewater of small jewellery shops examined is 13.5 mg.l-1, with
a maximum value of 100 mg.l-1. The presence of boron in these wastewaters may be due to
processes such as soldering (where boron is used as borace), voiding and washing, or
through the use of other materials e.g. hydrofluoboric acid, detergents.

For potentially toxic elements, the average concentrations of copper and cadmium detected
in wastewater are 14.2 mg.l-1 Cu and 0.4 mg.l-1 Cd, with maximum values of 61 mg.l-1 Cu
and 1 mg.l-1 Cd. Zinc concentration is highly variable, which is probably due to the different
manufacturing steps of the shops, with an average value of 22 mg.l-1 but a maximum value
of 270 mg.l-1.

149
Section 6. Case Studies

(D) Pharmaceuticals in the Urban Environment

Introduction

Pharmaceutical substances are a group of compounds, which until recently, have not been
of major concern with regards to their environmental effects. These compounds are
developed for their biological effect (primarily in humans), to cure disease, fight infection or
reduce symptoms. If these substances enter the environment they may have an effect on
aquatic and terrestrial animals, due to these biological properties and the fact that some of
them may bioaccumulate. Unlike other organic compounds, such as PCBs whose use has
been discontinued over the last 20 years, pharmaceuticals are used widely and they and
their metabolites may easily enter the UWW system. Pharmaceuticals use is also expected
to increase in Europe with the increasing avearge age of the population.

Current research demonstrates that drugs and their metabolites entering water supplies and
the food chain may pose a real threat, both to the ecosystem and to human health, and risk
assessments are slowly being carried out. However, many problems must be overcome,
such as the fact that these compounds are very changeable and are usually present in
mixtures and at low concentrations. Furthermore, pharmaceuticals have a wide variety of
structures and activities and that they may act synergistically (Alcock, 1999). There are
many different pharmaceuticals substances and approximately 3000 pharmaceutical
compounds are discharged into UWW collecting systems (ENDS, 2000). Sewage sludge is
predominantly disposed of on agricultural land, as is manure from farms and both of these
products will contain large amounts of pharmaceutical substances. Unfortunately, very little
is known about the fate of these compounds in the environment and the potential long-term
impacts. Many pharmaceutical substances though, have the same characteristics as organic
compounds; i.e. they are lipophilic, which tends to be a requirement to be able to pass
membranes, and some are designed to be persistent so that they are not inactivated before
achieving their healing effect (Halling-Sørensen, 1998).

Sources and fate in the environment


There are two major groups of pharmaceuticals; human and veterinary drugs, and they will
enter the environment through different pathways (Figure d.1).

A large amount of pharmaceutical products from both categories are prescribed each year.
For example in Germany, 100 tonnes of human drugs were prescribed in 1995 (Ternes,
1998c). This probably reflects the amounts prescribed in other countries of Western Europe,
relative to population size. Over the counter pharmaceutical sales will also increase this
figure. It is likely that a high concentration of drugs may find their way into wastewater,
making wastewater and sewage sludge major vectors for the entry of these compounds into
the environment. However, this will depend on the chemico-physical behaviour of the
pharmaceuticals in question.

150
Section 6. Case Studies

Figure d.1: Scheme for the main fates of drugs in the environment after application
[after Ternes, 1998c.]

The main entry routes of pharmaceutical substances into the environment are through;
disposal of wastewater treatment end products: effluent and sewage sludge; and manure
spreading onto agricultural land or even from the excreta of grazing animals (Figure d.2).
Fish farms also use medical substances as feed additives, but most of the food is not eaten
and is deposited straight onto the sea-bed (Halling-Sørensen, 1998).

151
Section 6. Case Studies

Figure d.2: Anticipated exposure routes of veterinary and human medicinal


substances in the environment [after Halling-Sorensen, 1998].

The compounds
For the purpose of risk assessments, pharmaceutical compounds have been divided into
four activity groups: antibiotics, antineoplastic drugs, antiparacetic drugs, and hormone
disrupters. However, there are many other groups of pharmaceutical compounds, such as
lipid regulators, which have been found ubiquitously in the environment and are highly
persistent compounds (Daughton, 1999).

152
Section 6. Case Studies

Antibiotics:
Antibiotics are widely used as medicines for human and animals treatment, also used widely
as growth promoters in veterinary use. According to the Swiss environmental research
institute, in the EC 54000 tonnes of antibiotics were used in human medicine in 1997.
Veterinary use amounted to 3500 tonnes of medicines and 1600 tonnes of growth promoters
(ENDS, 2000). Due to the effect of bans the use of growth promoters is expected to decline.
According to a study carried out by Halling-Sorensen (1998), most antibiotics are not very
persistent in the environment, particularly in soils, and the most widely used growth
promoters have been shown to have no effect on invertebrates, even at relatively high
concentrations. However soil bacteria may be more sensitive (ENDS, 2000).

Veterinary drugs tend to end up in manure and so have the potential to contaminate soils
where manure or slurry is spread. Levels of antibiotics in soil around a pig farm studied
reached up to 1400µg.kg-1, due to presence of antibiotics in the animals’ feed (ENDS, 2000).
The increased use of antibiotics has led to an increase in drug resistant micro flora. This
resistance is actually favoured by low concentrations of antibiotics (Jorgensen, 2000), thus,
the presence of antibiotics in the environment may be an important problem.

Anti-neoplastic drugs
These anti-cancer drugs are mainly used in hospitals rather than in households. They are
primarily used for chemotherapy and are found sporadically, in a range of concentrations in
the environment (Daughton, 1999). Anti-cancer drugs act as non-specific alkylating agents,
which means that no receptors are required, hence, they have the potential to act as
mutagens, carcinogens, teratogens, and embryotoxins (Daughton, 1999). The most widely
used substance is cyclophocamide (CP). In Denmark, approximately 13 to 14 kg of CP is
used in hospitals each year, and approximately 6 kg are prescribed by pharmacies
(Christensen, 1998). Thus, it is assumed that a total of 20 kg are used per year
(Christensen, 1998). Anti-cancer drugs are also referred to in the Case Study on Platinum
Group Metals.

Analgesic drugs
Analgesic drugs are used for pain relief and are probably the most commonly used
medicines.

Endocrine-disrupting substances
There is increasing concern about compounds that interfere with the hormonal system.
Endocrine disrupting substances block or trigger oestrogenic effects by binding to receptors.
Receptor-specific responses are particularly problematic as they can affect people for which
they are not intended (Christensen, 1998). An endocrine-disruptor may have an ‘agonistic
effect’ where it binds to the receptor instead of the natural hormone and causes a response,
or it may have an ‘antagonistic effect’ where the binding of the compound prevents the
natural one from binding and producing the required response (Environment Agency of
England and Wales, 1998). Other effects may also occur, showing that the process is very
complex and affects many systems in the body.

Endocrine-disrupting non pharmaceutical substances include phthalates, some PCBs, and


some pharmaceutical compounds, such as oestrogens. Many of these may be persistant in
sewage sludge and could enter the food chain as they are potentially taken up by plants and
animals. The effects of endocrine-disruptors were discovered about 10 years ago and may
occur in concentration ranges of a few nanograms per litre (Jørgensen, 2000). Humans use
hormones to cure diseases, as well as in contraception and hormonal replacement therapy.
Table d.1 shows some categories of substances with endocrine-disrupting properties:

153
Section 6. Case Studies

Table d.1: Categories of substances with endocrine-disrupting activities [Environment


Agency, 1998].

Category Examples Uses Modes of action


Natural
phytoestrogens Isoflavones, lignans Present in plants Oestrogenic and anti-
oestrogenic
Female sex 17β-oestradiol, Produced in animals Oestrogenic
hormones oestrone
Man-made
Polychlorinated PCBs, dioxins By-products from Anti-oestrogenic
organic incineration and chemical
compounds processes
Organochlorine DDT, dieldrin, lindane Insecticides Oestrogenic and anti-
pesticides oestrogenic
Alkylphenols Nonylphenol Production of NPE and Oestrogenic
polymers
Alklphenol NonylPhenol Surfactant Oestrogenic
ethoxylates Ethoxylate (NPE)
Phthalates Dibutyl phthalate Plasticiser Oestrogenic
Bi-phenolic Bisphenol A In polycarbonate plastics Oestrogenic
compounds and epoxy resins
Synthetic steroids Ethinyl oestradiol Contraceptives Oestogenic

Of these, oestrogens are of a major concern, as they are excreted in an inactive form but
are found to be reactivated in sewage effluent. Oestrogens are organic molecules derived
from cholesterol, which can bind to receptors and cause a physiological response
(Montagnani et al., 1996). The purpose of the endocrine system is to regulate metabolic
activity, which requires a degree of interaction with the nervous system (Montagnani et al.,
1996). Because oestrogen receptors are located in the cell nucleus, oestrogen-like
molecules can thus enter the cell and could potentially interact with DNA, causing damage
which may lead to tumour formation (Montagnani et al., 1996). Prolonged exposure to these
compounds may induce female characteristics in males. There is increasing speculation that
these compounds may be linked to reduction in male fertility and reproductive complications
(Montagnani et al., 1996).

In the UK, research has shown that male fish exposed to the natural hormone: 17β-
oestradiol, oestrone, and the synthetic hormone: ethinyloestradiol, from domestic sewage
effluent, developed hermaphrodite characteristics (Alcock et al., 1999). It was also found that
these hormones were present in the biologically active form, having been transformed and
reactivated after excretion and not degraded during wastewater treatment (Alcock et al.,
1999). However, research carried out by the Ministry of Agriculture, Food and Fisheries
(MAFF) along the river Lea, UK determined that although estrogenic substances are likely to
be present in wastewater effluents, the development of female characteristics in male fish
present in WWTS lagoons is unlikely to be due to these substances, as the transformation is
only possible at a very early stage in their development (Montagnani et al., 1996). Due to the
widespread use of estrogenic substances and their entry into the environment via sludge
and effluent from WWTS, aquatic environments may be acting as a sink for these
substances. Natural and synthetic estrogens are extremely widely present/used. Although
the contribution these compounds make to oestrogenic effects is thought to be small, they
are are of concern because of their highly persistent and potent nature (ENDS, 2000).

154
Section 6. Case Studies

Consumption of pharmaceutical compounds

As already stated, it is difficult to obtain information on the quantities of pharmaceuticals


used for most countries but in Denmark consumption of the most commonly used drugs is
available (Table d.2).

Table d.2: Major drugs and drug groups and their consumption in Denmark, in 1997
[ENDS, 2000, Christensen, 1998, and Halling-Sørensen, 1998].

Active ingredient Major use Amount used (kg)


Aspirin Analgesic 305250
Paracetamol Analgesic 248250
Ibuprofen Anti-rheumatic 33792
Pencicillin V Antibiotic 19000
Furosemide Diuretic 3744
Terbutaline Anti-asthmatic 475
Enalapril Anti-hypertensive 416
Citalopram Anti-depressant 368
Diazepam Anti-depressant 207
Salbutanol Anti-asthmatic 170
Bendroflumethiazide Diuretic 167
Zopiclone Anti-hypertensive 144
Amlodipidine Anti-hypertensive 132
Oestradiol Hormone replacement 119
Nitrazepam Anti-hypertensive 116
17β-estradiol Oral contraception 45
Budesonide Anti-asthmatic 39
Gestodene Birth control pill 37
Cyclophosphamide Anti-cancer 20
Xylometazoline Nasal decongestant 13
Digoxin Heart drug 4
Desogestrel Birth control pill 3
Medicine groups
Antibiotics 37700
Analgesics 28300
Hypotensiva 410
Diuretica 3800
Anti-asthmatics 1700
Psychleptics 7400

It was also found that a total of 110 tonnes of antibiotics were used as growth promoters,
feed additives or as medicines, on livestock and fish farms (Halling-Sørensen, 1998). In
1994, the overall production of antibiotics in Germany was 1831 tonnes, of which Penicillin
contributed 624 tonnes (Hirsch, 1999). It should be noted that the amount of antibiotics used
for human and veterinary purposes, 37.7 tonnes and 110 tonnes respectively, is in the same
range as the amounts of certain pesticides used (Hirsch, 1999). A paper published by Goll
van (1993) estimates that if the total amount of growth promoters used in the Netherlands
was spread on their 2 million hectares of agricultural land, this would give a yearly average
of 130mg of antibiotics and metabolites/m2 (Halling-Sørensen, 1998).
The pharmaceutical substances predominantly used in hospitals must also take into account
compounds such as X-ray contrast media. Iodinated X-ray contrast media are very stable
biochemically, so they tend to be excreted unmetabolised. In Germany, 500 tonnes per year
of X-ray contrast media are used and iopromide (CAS 73334-07-3) alone accounts for 130
tonnes per year (Ternes, 2000). Other X-ray contrast substances used in the EU are:

155
Section 6. Case Studies

diatrizoate (CAS 131-49-7) an ionic X-ray diagnostic drug, iopamidol (CAS 60166-93-0) and
iopromide (CAS 73334-07-3) both non-ionic X-ray diagnostic substances, iothalamic acid
(CAS 2276-90-6) and ioxithalamic acid (CAS 28179-44-4) both ionic X-ray diagnostic
substances.

Detection of pharmaceutical compounds

Other biologically active compounds are common in wastewater, and there is increasing
evidence that such substances are widely present in the environment. Danish research has
found that up to 68 different drug residues can be detected in the environment. Compounds
such as caffeine, nicotine, aspirin, and paracetamol are all frequently detected (ENDS,
2000). More studies are now looking at the prevalence of these drugs and their metabolites
in wastewater and sewage sludge. For example, clofibric acid (2-(4-chlorophenoxy)-2-
methylpropionic acid), which is a breakdown product of lipid-regulating drugs, is highly
persistent and resistant to wastewater treatment, as usually only 15-51% is removed (ENDS,
2000). Lipid regulating drugs are commonly prescribed and it is thought that the daily load of
clofibric acid to UWW collecting systems in Denmark, is around a few kilograms (ENDS,
2000). Concentrations of clofibric acid have also been detected in sewage effluent in
micrograms per litres, and in nanograms per litres in water bodies such as rivers and lakes
(ENDS, 2000). In the UK, clofibric acid has been detected in the 1 µg.l-1 range in the aquatic
environment, and in Germany, it has been detected at concentrations up to 165 ng.l-1
(Ternes, 2000).

Antibiotics have been also widely detected. In Germany, concentrations up to 5 µg.l-1 were
found in WWTS effluents, which is comparable to the data collected by Richardson and
Bowron in 1985 (Hirsch, 1999). Five of the 18 compounds investigated were frequently
detected in German WWTS effluent and rivers: erythromycin, roxithromycin, clarithromycin,
sulfamethoxazole, and trimethoprim. The highest concentration was detected for
erythromycin degradation products, at a median value of 2.5 µg.l-1 in WWTS effluent and a
maximum value of 6 µg.l-1 (Hirsch, 1999). The other four antibiotics were only detected at
levels below 1 µg.l-1 (Hirsch, 1999). Median values for the concentrations detected in surface
waters are one order of magnitude lower than those detected in WWTS effluent (Hirsch,
1999), (see Figure d.3).

156
Section 6. Case Studies

Figure d.3: Presence of antibiotics from investigated surface waters in Germany


[Hirsch, 1999].

Analyses for tetracycline and penicillins found no detectable amounts in five WWTS effluents
or surface waters (Hirsch, 1999). Tetracyclines tend to form stable complexes with calcium
and other ions, thus contaminating the sediment rather than the water (Hirsch, 1999).
Penicillins tend to be easily eliminated, as they are very susceptible to hydrolysis of the β-
lactam ring (Hirsch, 1999). Ground water samples were also slightly contaminated by
sulphamethoxazole and sulphamethazine (not used in human medicine), due to infiltration
from application of contaminated sewage sludge or manure to agricultural land. The samples
collected contained concentrations of sulphonamide residues up to 0.48 µg.l-1 (Hirsch,
1999).

X-ray contrast media are also widespread in German wastewater influent and effluent.
Loads of the most frequently used compounds, such as iopromide were found to exceed
1µg.l-1 during the working week but decreased at weekends as X-rays did not tend to be
performed (Ternes, 2000). Maximum concentrations detected were greater than 3 µg.l-1 (up
to 15 µg.l-1 for iopamidol). Median values were around 0.25-0.75 µg.l-1, which indicates their
ubiquity in German wastewater treatment effluents (Ternes, 2000). The compounds detected
depended on the region and on the practices of particular hospitals in that area.

Antiseptics are another major group of pharmaceutical compounds commonly used both in
households and in medical practices. It has been found that major antiseptics, such as
chlorophene and biphenol, are present at concentrations up to 0.05 µg.l-1 in wastewater
(Ternes, 1998b). However, biphenol tends to be eliminated at rates of 98% during treatment
and chlorophene at 63% (Ternes, 1998b). These compounds, particularly clorophene, are
detected in rivers at similar concentrations. This is probably due to the fact that they are also
used in many household detergents and disinfectants, as well as in veterinary medicine on
farms, so leading to widespread contamination of the aquatic environment.

Analgesics. Salicylic acid, a major metabolite of acetylsalicylic acid, is also detectable in


German wastewater at high concentrations (54µg.l-1 over 6 days), but treatment degrades
most of it, as the compound is no longer detectable in WWTS effluents (Ternes, 1998b).

157
Section 6. Case Studies

Oestrogens. There is increasing concern about the widespread presence of oestrogenic


substances in wastewater and other water bodies. The daily production rate of natural
oestrogens by humans is in the microgram range, up to 400 µg of 17β-estradiol for women
(Ternes, 199b). The maximum daily excretion rate is 64 µg for oestriol (Ternes, 1999b).
Oestrogens are mainly excreted as inactive polar conjugates (Ternes, 1999b). Vitellogenin
(precursor for production of yolk in all oviparous vertebrates) induction in male or juvenile
fish has become a “biomarker” for the presence of estrogenic substances in the aquatic
environment (Larsson, 1999). In the UK, caged fish downstream of an WWTS were found to
produce vitellogenin. Two possibilities were investigated: the presence of ethinylestradiol
and NPE. The effluent from a Swedish WWTS showed high levels of oestrogenic
compounds (Larsson, 1999). It was found that exposure to large amounts of
ethinyloestradiol caused accumulation in fish, as fish concentrations were found to be 104-
106 times higher than those detected in the water (Larsson, 1999). The estimated use of
ethinyloestradiol is 3.5mg/day, which is close to the concentration found in the WWTS
effluent (2.9mg/day), showing very low degradation of this compound during treatment
(Larsson, 1999).

In the UK, analysis of sampled effluents found that natural hormones (17β-oestradiol and
oestrone) are present in the range 1.4 to 76 ng.l-1, whereas the synthetic hormone
(ethinyloestradiol) was only found in 3 out of the 7 effluents analysed and at comparatively
low levels: 0.2 to 7 ng.l-1 (Alcock et al., 1999). The source of these is thought to be mainly
from human excretion products. It was also found that the hormones were present in the
biologically active form, suggesting that they had been transformed and reactivated after
excretion (Alcock et al., 1999).

In Germany, raw sewage was found to contain 0.015 µg.l-1 of 17β-estradiol and 0.027 µg.l-1
of oestrone and it was also found that oestrone and 17α-ethinyloestradiol were not efficiently
removed during wastewater treatment (Ternes, 1999a). In contrast, 17β-oestradiol and 16α-
hydroxy-oestrone were eliminated with a higher efficiency: around 64-68% (Ternes, 1999a)
(See Figure d.4).

Figure d.4: Elimination percentages and loads of estrogens during passage through a
municipal sewage treatment plant located near Frankfurt/Maine over 6 days [Ternes,
1999a].

In discharges from the treatment plants, all compounds could be detected in the ngl-1 range
(Ternes, 1999a), however oestrone was predominant with concentrations up to 0.07 µgl-1

158
Section 6. Case Studies

and a median value of 0.009 µgl-1. The compounds 17α-ethinyloestradiol and 16α-hydroxy-
estrone were found at the detection limit of 0.001 µg l -1 (Ternes, 1999a). Oestrone was the
only compound detected in 3 of the 15 rivers sampled at concentrations between 0.7 and 1.6
ng l-1 (Ternes, 1999a). Therefore, it seems that these compounds, particularly natural
oestrogens, are not degraded in the treatment system and tend to accumulate in sludge and
effluent. However, the loads entering receiving waters are quite low. DEHP is also an
endocrine-disrupting compound. In Sweden, it has been found in all sewage sludge samples
analysed, with concentrations between 25-660 mg kg-1 dry weight (Alcock et al., 1999).

In Italy, drinking water, rivers, and sediments have been analysed to determine the extent of
environmental contamination by pharmaceuticals (see Table d.4), (Zuccato, 2000).

Table d.4: Concentrations of medicinal drugs in drinking water, river water, and
sediments [Zuccato, 2000].

DRUG DRINKING WATER (ngl-1) RIVER WATER (ngl-1) RIVER SEDIMENTS (ng kg-1)
Po (Piacenze Po
Lambro Adda Lambro Adda
Milan Lodi* Varese and, (Piacenze,
(Milan)* (Sondrio) (Milan) (Sondrio)
Cremona)* Cremona)*
Atenolol <LOD <LOD <LOD 169·9-241·9 49·5-84·3 <LOD <LOD <LOD <LOD
Bezafibrate <LOD <LOD <LOD 134·3-202·7 15·1-22·4 1·6 130 <LOD <LOD
Ceftriaxone <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Clofibric acid <LOD 3·2-5·3 <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Cyclophospha
<LOD <LOD <LOD 2·2-10·1 <LOD <LOD <LOD <LOD <LOD
mide
19·6-
Diazepam <LOD
23·5
0·2 0·7-1·2 0·5-0·7 <LOD <LOD <LOD <LOD
Erythromycin <LOD <LOD <LOD <LOD-17·4 0·7-0·9 <LOD 630 400-600 10
Furosemide <LOD <LOD <LOD 85·1-88 <LOD <LOD <LOD <LOD <LOD
Ibuprofen <LOD <LOD <LOD 90·6-92·4 <LOD-4·0 1·0 220 <LOD <LOD
Lincomycin <LOD <LOD <LOD 6·8-13·8 1·2-4·6 <LOD 130 <LOD <LOD
Oleandomycin <LOD <LOD <LOD <LOD-0·8 0·4-4·8 2·7 <LOD <LOD <LOD
Ranitidine <LOD <LOD <LOD <LOD-9·4 <LOD <LOD 150 <LOD-410 <LOD
Salbutamol <LOD <LOD <LOD <LOD-3·1 <LOD-4·6 <LOD <LOD <LOD <LOD
Spiramycin <LOD <LOD <LOD 8·4-68·3 <LOD <LOD 2900 <LOD-380 380
Tilmicosin <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Tylosin <LOD 0·6-1·7 <LOD <LOD-2·2 <LOD <LOD 2640 <LOD-130 <LOD
(<LOD = below the limit of detection)

It can be seen that most drugs were measurable in these media, showing widespread
contamination. The concentrations measured could potentially give rise to human exposure
in the ng day-1 range, which is 3-4 orders of magnitude lower than the concentrations
capable of producing pharmacological effects (Zuccato, 2000). Hence, acute exposure is
assumed to be unlikely, but long-term effects must still be studied.

In Germany, occurrence of drugs in WWTS and rivers has been studied (Ternes, 1998c).
Results showed maximum values in average loads of up to 3kg.day-1 for salicylic acid in the
influent and up to 114g.day-1 for carbamazepine in the effluent (Ternes, 1998c).

159
Section 6. Case Studies

Figure d.5: Elimination of different drugs during passage through a municipal sewage
treatment plant near Frankfurt/Maine over 6 days [Ternes, 1998c].

From Figure d.5, it appears that more than 60% of the compounds in the influent were
usually removed during treatment of wastewater: ranging between 7-99% removal (Ternes,
1998c). Only carbamazepine, clofibric acid, and phenanzone were less efficiently eliminated
(Figure d.6). However, complete elimination was not usually achieved; thus receiving waters
may potentially be contaminated. Subsequently, a screening programme of 49 different
German WWTS effluents was carried out, in addition to river sampling. Lipid regulating
agents were found in the majority of the WWTS effluents, and in many river samples but in a
much lower concentration (Ternes, 1998c). Polar metabolites of the compounds were
usually detected. For example, clofibric acid was detected at levels up to 1.6 µg.l-1 in WWTS
effluent and in the ng.l-1 range in rivers, which illustrates the importance of metabolites
(Ternes, 1998c). Anti-inflammatories , such as, ibuprofen and naproxen, were also detected.
Diclofenac was present in the highest concentration at median levels of 0.81 µg.l-1 in treated
effluent effluent and 0.15 µg.l-1 in rivers (Ternes, 1998c). In the case of betablockers, the
highest median concentration was found for metoprolol at 0.73 µg.l-1 in WWTS effluent and
0.45 µg.l-1 in rivers (Ternes, 1998c). β2-sympathomimetics were also present but in very low
concentrations. Anti-cancer agents such as cyclophosphamide and ifosamide were detected
at levels of 0.02 µg.l-1 and 0.08 µg.l-1 respectively in WWTS effluent; however, they are
associated with presence of hospital effluents, and are not widespread (Ternes, 1998c).
Carbamazepine, an anti-epileptic drug was widespread in the aquatic environment, with a
high median value of 2.1 µg.l-1 in effluent and 0.25 µg.l-1 in rivers (Ternes, 1998c). Annual
prescriptions of carbamazepine amount to approximately 80 tonnes per year in Germany, it
then becomes metabolised and glucuronides are excreted. However treatment of
wastewater cleaves these metabolites back to the parent compound, increasing the
environmental concentrations (Ternes, 1998c).

Table d.6 shows specific studies on pharmaceuticals in the environment and the
concentrations found for the different substances (Halling-Sørensen, 1998).

160
Section 6. Case Studies

Ground water pollution has been detected in some instances, mainly due to leaching from
landfill sites containing pharmaceutical wastes (Halling-Sørensen, 1998). In Berlin, clofibric
acid has been detected in drinking water at concentrations between 10 ng.l-1 and 165 ng.l-1
and in all surface water samples around Berlin, suggesting extensive contamination (Halling-
Sørensen, 1998).

River water is often polluted with pharmaceutical compounds. Most groups of compounds,
i.e. antibiotics, antineoplastic agents, and ethinyloestradiol, have been detected between 5-
10 ng.l-1. A study conducted by Richardson and Bowron (1985), investigated the exposure of
human pharmaceuticals in the river Lea in England and found that over 170 substances are
used in excess of 1 tonne per year in the river’s catchment. This allowed them to predict a
concentration of at least 0.1µg.l-1 in the river water (Halling-Sørensen, 1998).

161
Section 6. Case Studies

Table d.6: Pharmaceutical compounds identified in environmental samples [after


Daughton, 1999]

Compound Use/Origin Environmental occurrence


Acetaminophen Analgesic/anti- Removed efficiently by WWTS, max. effluent 6µgl-
1
inflammatory , not detected in surface waters
Acetylsalicylic acid Analgesic/anti- Ubiquitous, removal efficiency 81%, max. effluent
inflammatory 1.5µgl-1, in surface water 0.34µgl-1.
Betaxolol betablocker Max. effluent 0.19µgl-1, in surface water 0.028µgl-
1
.
Benzafibrate Lipid regulator Removal efficiency 83%, max. effluent 4.6µgl-1, in
surface water 3.1µgl-1.
Biphenylol Antiseptic, fungicide Extensive removal in WWTS.
Bisoprolol betablocker Max. effluent 0.37µgl-1, in surface water 2.9µgl-1.
Carazolol Betablocker Max. effluent 0.12µgl-1, in surface water 0.11µgl-
1.
Carbamazepine Analgesic, anti- Removal efficiency 7%, max. effluent 6.3µgl-1, in
epileptic surface waters 1.1µgl-1.
Chloroxylenol Antiseptic In influents and effluents <0.1µgl-1.
Chlorophene Antiseptic Influent 0.71µgl-1, removal not very efficient
Clenbuterol β2-sympathomometic Max. effluent 0.08µgl-1, in surface waters 0.05µgl-
1.
Clofibrate Lipid regulator River water 40ngl-1, not detected in effluent or
surface waters.
Clofibric acid Metabolite of Removal efficiency 51%, max. effluent 1.6µgl-1,
clofibrate surface waters 0.55µgl-1, up to 270ngl-1 in
German tap waters
Cyclophosphamide antineoplastic Max. effluent 0.02µgl-1, not detected in surface
waters, high in hospital sewage: up to 146ngl-1
Diatrizoate X-ray contrast media Resistant to biodegradation, median in German
surface waters 0.23µgl-1, locally very high
concentrations can occur.
Diazepam Psychiatric drug Max. effluent 0.04µgl-1, not detected in surface
waters.
Diclofenac-Na Analgesic/anti- Removal efficiency 69%, max. effluent 2.1µgl-1, in
inflammatory surface waters 1.2µgl-1.
Dimethylaminophen Analgesic/anti- Removal efficiency 38%, max. effluent 1µgl-1, in
azone inflammatory surface waters 0.34µgl-1.
17α-ethinylestradiol Oral contraceptive Up to 7ng.l in WWTS effluent, not detected in
German surface waters above 0.5ngl-1.
Etofibrate Lipid regulator Not detected in WWTS effluent and surface
waters
Fenfluramine Sympathomimetic No studies but is known to be an endocrine-
amine disrupting substance
Fenofibrate Lipid regulator Efficiently removed, max. effluent 0.03µgl-1, not
detected in surface waters.
Fenofibric acid Metabolite of Removal efficiency 64%, max. effluent 1.2µgl-1, in
fenofibrate surface waters 0.28µgl-1.
Fenoprofen Analgesic/anti- Not detected in WWTS effluent or surface waters
inflammatory
Fenoterol β2-sympathomometic Max. effluent 0.06µgl-1, in surface waters
0.061µgl-1.
Flurorquinolone Antibiotics Ubiquitous, led to resistance in pathogenic
carboxylic acids bacteria, strongly sorbs to soil.
Fluoxetine Antidepressant No studies
Fluvoxamine Antidepressant No studies

162
Section 6. Case Studies

Gemfibrozil Lipid regulator Removal efficiency 69%, max. effluent 1.5µgl-1, in


surface waters 0.51µgl-1.
Gentisic acid Metabolite of Efficiently removed by WWTS, max. effluent
acetylsalicylic acid 0.59µgl-1, in surface waters 1.2µgl-1.
o-hydroxyhippuric Metabolite of Efficiently removed by WWTS, not detected in
acid acetylsalicylic acid effluent or surface waters.
Ibuprofen Analgesic/anti- Removal efficiency 90%, max. effluent 3.4µgl-1, in
inflammatory surface waters 0.53µgl-1.
Ifosamide Antineoplastic Max. effluent 2.9µgl-1, not detected in surface
waters, hospital sewage 24ngl-1, totally refractory
to removal by WWTS.
Indomethacine Analgesic/anti- Removal efficiency 75%, max. effluent 0.60µgl-1,
inflammatory in surface waters 0.2µgl-1.
Iohexol X-ray contrast media Very low aquatic toxicity.
Iopamidol X-ray contrast media Max. effluent 15µgl-1, median 0.49µgl-1.
Iopromide X-ray contrast media Resistant to biodegradation, yields refractory,
unidentified metabolites, max. effluent 11µgl-1.
Iotrolan X-ray contrast media Very low aquatic toxicity.
Ketoprofen Analgesic/anti- Max. effluent 0.38µgl-1, in surface waters 0.12µgl-
inflammatory 1.
Meclofenamic acid Analgesic/anti- Not detected in WWTS effluent or surface waters.
inflammatory
Metoprolol betablocker Removal efficiency 83%, max. effluent 2.2µgl-1, in
surface waters 2.2µgl-1.
Nadolol Betablocker Max. effluent 0.06µgl-1, not detected in surface
waters.
Naproxen Analgesic/anti- Removal efficiency 66%, max. effluent 0.52µgl-1,
inflammatory in surface waters 0.39µgl-1.
Paroxetine antidepressant No studies
Phenazone Analgesic Removal efficiency 33%, max. effluent 0.41µgl-1,
in surface waters 0.95µgl-1.
Propranolol Betablocker Removal efficiency 96%, max. effluent 0.29µgl-1,
in surface waters 0.59µgl-1.
Propyphenazone Analgesic/anti- Prevalent in Berlin waters.
inflammatory
Salbutamol β2-sympathomometic Max. WWTS influent 0.17µgl-1, in surface waters
albuterol 0.035µgl-1.
Salicylic acid Metabolite of Up to 54µgl-1 in WWTS effluent but efficiently
acetylsalicylic acid removed in effluent, average in effluent 0.5µgl-1,
in surface waters 4.1µgl-1.
Sulfonamides Antibiotics Present inn landfill leachates
Terbutaline β2-sympathomometic Max. effluent 0.12µgl-1, not detected in surface
waters.
3,4,5,6-tetrabromo- Antiseptic, fungicide Found in influents and effluents in Germany
o-cresol <0.1µgl-1.
Timolol Betablocker Max. effluent 0.07µgl-1, in surface waters 0.01µgl-
1.
Tolfenamic acid Analgesic/anti- Not detected in WWTS effluent or surface waters.
inflammatory
Triclosan Antiseptic 0.05-0.15µgl-1 in water, very widely used.
Verapamil Cardiac drug No occurrence data

163
Section 6. Case Studies

Table d.6 summarises the occurrence of certain pharmaceuticals in the environment. It can
be seen that some pharmaceuticals, such as lipid regulators, X-ray contrast media,
antibiotics etc., are ubiquitous and extremely persistent in the environment, some are even
present in drinking water: clofibric acid for example has been found at concentrations up to
0.27 µg.l-1 in some German waters. This would breach EC regulations if the compounds
were classed as pesticides (ENDS, 2000). However only a fraction of the drugs on the
market, have been investigated regarding their occurrence in the environment.

The fate of pharmaceutical compounds

Pharmaceutical compounds enter the body and are then often metabolised in the liver
through oxidation, reduction, or hydrolysis to “phase I” metabolites, which tend to be more
toxic than the parent compound. Other reactions, such as conjugation, metabolise the
compounds into “phase II” metabolites, which tend to be inactive and more polar and water-
soluble. It has also been observed that phase II metabolites are often reactivated into the
parent compounds, either during treatment of wastewater and sewage sludge or in the
environment. For example, chloramphenicol glucoronide and N-4-acetylated sulphadimidine
(phase II metabolites of the antibiotics chloramphenicol and sulphadimidine, respectively),
are reactivated in liquid manure (Halling-Sorensen, 1998). This shows the importance of the
investigation of metabolites as well as parent compounds.

For example, 17β-oestradiol, is administered orally and mainly undergoes first-pass hepatic
metabolism, being transformed to oestrone and oestriol, which are less potent (Christensen,
1998). Other metabolites are also formed but to a lesser extent. Experiments using the
diluted slurry of activated sludge from a WWTS, were undertaken to investigate the
persistence of natural oestrogens and contraceptives under aerobic conditions (Ternes,
1999b). The natural oestrogen 17β-oestradiol, was oxidised to oestrone, which is then
linearly removed with time. Rapid elimination also occurred for16α-hydroxy-oestrone.
However, the contraceptive 17α-ethinyloestradiol was persistent and highly stable under
environmental conditions (Ternes, 1999b). Two glucuronides of 17β-oestradiol were cleaved
to their parent compounds and 17β-oestradiol was re-released in an activated form (Ternes,
1999b). This indicates that the microorganisms present have the ability to deconjugate
oestrogen glucuronides. It is interesting to note that glucuronide conjugates are the main
oestrogen metabolites excreted by humans, so during wastewater treatment, the
concentration of free oestrogen increases due to the cleavage of the glucuronide moieties
from the compounds. As a result, the predominant presence of oestrone in WWTS effluents
and rivers is due to; its high stability during treatment; the cleavage of glucuronide
conjugates from oestrone and 17β-oestradiol; and the oxidation of the latter to oestrone
(Ternes, 1999b).

Penicillin antibiotics are eliminated rapidly and have short half-lives in the body, usually 30-
60 minutes, and very high concentrations are excreted in urine: it has been determined that
up to 40% of penicillin V is excreted unchanged (Christensen, 1998).

Cyclophosphamide, an anti-cancer drug is administered intravenously or orally. It is not


active in itself but undergoes activation in the body when transformed to phosphoramide
mustard and acrolein. The parent compound is genotoxic. Some of it is excreted unchanged:
5-20% (Christensen, 1998).

Antibiotics are generally believed to leave humans unchanged by the body metabolism (see
Table d.7) (Hirsch, 1999) and it has been determined that up to 90% of the parent
compounds are excreted unchanged (ENDS, 2000). These active products can be excreted
either as unchanged compounds or as conjugates; 30-90% of administered antibiotics are
excreted via urine as active substances (Alcock et al., 1999). This introduces the problem at

164
Section 6. Case Studies

the WWTS of disruption of biological treatment processes, as pharmaceutical compounds,


particularly antibiotics, can potentially affect bacteria.

Table d.7: Human prescription amounts and excretion rates of antibiotics [Hirsch,
1999].

Antibiotic Amount prescribed Excretion (%)


(t/a) Unchanged Other
Metabolites
Amoxicillin 25.5-127.5 80-90 10-20
Ampicillin 1.8-3.6 30-60 20-30
Penicillin V 40 40 60
Penicillin G 1.8-3.6 50-70 30-50
Sulphamethoxasole 16.6-76 15
Trimethoprim 3.3-15 60
Erythromycin 3.9-19.8 >60
Roxithromycin 3.1-6.2 >60
Clarithromycin 1.3-2.6 >60
Minocycline 0.8-1.6 60 40
Doxycycline 8-16 >70

A study looking at the amounts of antibiotics in human faeces found trimethoprim and
doxycycline at concentrations between 3-40 mg.kg-1, and erythromycin at concentrations
around 200-300 mg.kg-1 (Hirsch, 1999). Elimination at treatment plants is usually incomplete,
ranging between 60-90% (Ternes, 1998b). Polar antibiotics are probably not removed
efficiently because elimination is mainly due to adsorption on activated sludge, which is
mediated through hydrophobic interactions (Hirsch, 1999). As a consequence, receiving
waters and other environmental media may become contaminated. Furthermore,
erythromycin and other drugs such as naproxen and sulphasalazine, have survived in the
environment for over a year (Zuccato, 2000). Clofibric acid was also found to survive for 21
years and although its use has been stopped, it is still detected in rivers and lakes in Italy
(Zuccato, 2000).

Many pharmaceutical compounds have the same physico-chemical characteristics as


organic compounds, such as persistence and lipophilicity; much less is known though about
their entry into the environment and their subsequent fate (Alcock et al., 1999). Over 30% of
all drugs produced between 1992 and 1995 were lipophilic, i.e. solubility less than 100 mg.l-1
(Halling-Sørensen, 1998). The fate of pharmaceutical substances may be divided into three
groups:

• Mineralisation to CO2 and water, for example aspirin.


• Retained in sludge, if the compound is lipophilic and not readily biodegradable.
• Emitted to receiving water due to transformation into a more hydrophilic form but still
persistent, for example clofibrate.

Richardson and Bowron (1985) investigated degradation of pharmaceuticals during


wastewater treatment and found that many common compounds are biodegradable,
although cortisteroid compounds and ethinyloestradiol, among others, were non-
biodegradable (Alcock et al., 1999).

In work by Kummerer (2000), two clinically important groups of antibiotics have been studied
with regards to their biodegradability. Chinolones and nitromidazoles possess different
chemical structures, actvity spectra and modes of action. The study found low rates of
biodegradation for ciprofloxacin, ofloxacin, and metronidazole; it also found that the
genotoxicity of these compounds remained unaffected during treatment (Kummerer, 2000).

165
Section 6. Case Studies

The different groups of antibiotics were active against bacteria present in wastewater
(Kummerer, 2000).

Only a few compounds have been studied regarding their behaviour in wastewater treatment
and the results are varied. Compounds such as the analgesics, ibuprofen and naxoproxen,
have been found to have removal efficiencies between 22-90% and 15-78% respectively
(ENDS, 2000). It has also been determined that 70-80% of the drugs administered in fish
farms, are transferred into the environment (Halling-Sorensen, 1998).

Table d.6 gives an overview of the present knowledge on the environmental fate of specific
pharmaceuticals. It can be seen that most hormones, such as oestrogen, are persistent in all
areas and that most of the antibiotics used for human treatment are not biodegradable. The
majority of other compounds used for human treatment are also non-biodegradable, with the
exception of the following: paracetamol, nicotinamide, ibuprofen, caffeine, and aspirin. The
compounds used in veterinary treatment tend to be more biodegradable than human
pharmaceuticals, although the speed of degradation will depend on environmental
conditions, such as pH, and temperature.

It has also been determined that iodinated X-ray contrast media are not degraded during
wastewater treatment, due to their high polarity (log K ow of iopromide = -2.33) (Ternes, 2000).
These compounds are designed to be highly stable to give optimum results during X-ray, so
are not readily biodegradable. Ninety percent of X-ray contrast media are excreted
unmetabolised (Ternes, 2000); hence, receiving waters will also tend to be contaminated.
Concentrations up to 0.49 µg.l-1 for iopamidol were detected in receiving rivers (Ternes,
2000). It appears that groundwater may also become contaminated, as concentrations of up
to 2.4 µg.l-1 were identified for iopamidol as a result of infiltration by polluted surface water
(Ternes, 2000). The concentration of X-ray contrast media in receiving water bodies is lower
than that detected in wastewater effluent; however, due to the high persistence of such
media in the environment, this reduction seems to be less important than for other
pharmaceutical compounds (Ternes, 2000). This shows that pharmaceutical compounds
have the ability to infiltrate aquifers and survive for many years. Pentobarbital, clofibric acid,
benzafibrate, diclofenac, and carbamezepine, have all been found in aquatic environments,
persisting there for up to 20 years (Ternes, 2000).

With the exception of Denmark, there is very little data available on the use and quantities of
pharmaceuticals, which renders the task of studying the fate of these compounds in
wastewater very difficult. The list of pharmaceutical substances could be exhaustive and
prioritisation is necessary.

Certain physical processes occur that may be used to degrade these contaminants: sorption
to solids, volatilisation, chemical degradation, and biodegradation. The effectiveness of
sorption and volatilisation can be determined using the octanol water partition coefficient
(Kow) and Henry's law constant (Hc) [Rogers, 1996]:

• if log Kow is less than 2.5, the compound has a low sorption potential (i.e. it will not
adsorb onto soil particles and will not be very lipophilic),
• if log Kow is between 2.5 and 4, the compound has a medium sorption potential,
• if log Kow is greater than 4, the compound has a high sorption potential and is very
lipophilic.
• if Hc is greater than 1x10-4 and Hc/Kow is greater than 1x10-9, the compound is thought
to have a high volatilisation potential,
• if Hc is less than1x10-4 and Hc/Kow is less than 1x10-9 the compound is thought to
have a low volatilisation potential.

166
Section 6. Case Studies

Several models, using Kow, Koc, and Hc, have been developed in order to take all these
characteristics into account in order to prioritise pollutants. This has enabled an assessment
to be made of the exposure risk to such pollutants, through consuming food derived from
sludge-amended soil. Two parameters are important when trying to determine movement of
contaminants through the food chain: persistence, and non-polarity. Easily metabolised or
polar compounds do not move through the food chain. As bioconcentration increases with
lipophilicity, compounds with high log Kow values will tend to accumulate in the food chain
(Duarte-Davidson, 1996).

Unfortunately, sewage sludge may contain a wide variety of pharmaceutical compounds,


and for many, information on their characteristics is not readily available. Therefore, it
becomes difficult to eliminate or prioritise pharmaceuticals using this screening process. In
addition, without proper information on the physico-chemical properties of these compounds,
it is not possible to predict their fate in the environment, or their concentrations in sewage
sludge (Alcock et al., 1999). In the absence of detailed knowledge, it can be presumed that
most pharmaceutical substances have the same properties as pesticides and other organic
pollutants (Halling-Sorensen, 1998). Also, as mentioned already, many of these compounds
have lipophilic characteristics, so they are likely to accumulate. Some pharmaceuticals may
even be metabolised during treatment or in the soil, to more readily available compounds,
increasing their potential for plant and animal uptake (Engwall et al., 2000).

The low concentration of individual pharmaceutical compounds, coupled with their metabolic
characteristics leads to incomplete removal in WWTS (Daughton, 1999). They tend to be
non-volatile, so transport and movement through the environment will occur via aquatic
media. In fact, their polarity and non-volatile characteristics will often prevent them from
leaving the aquatic environment (Daughton, 1999). As it has been seen earlier, metabolites
also tend to be cleaved to the parent compound during wastewater treatment and then
released afterwards.

Nutraceuticals/Herbal Remedies

During the last several years, the popularity of nutritional supplements was codified by the
creation of a new term for the subclass of highly bioactive food supplements called
nutraceuticals (Daughton and Ternes, 1999) also referred to as nutriceuticals.
Nutraceuticals are a rapidly growing commercial class of bioactive compounds, usually
botanicals, intended as supplements to the diet. Nutraceuticals and many herbal remedies
can have potent physiologic effects. These are a mainstay of alternative medicine and have
enjoyed explosive growth in use in the United States and Europe during the last decade.
Many are used as food supplements that have either proven or hypothesized biologic activity
but are not classified as drugs by the FDA, primarily because a given botanical usually has
not one but an array of distinct compounds whose assemblage elicits the putative effect and
because these arrays cannot be easily standardized. As such, they are not regulated and
are available over the counter (heavily promoted via the Internet). Even in those cases in
which the natural product is identical to a prescription pharmaceutical (e.g., the Chinese red-
yeast product Cholestin newly introduced to the United States contains lovastatin, an active
ingredient in the approved prescription drug Mevacor used to lower cholesterol levels), a
recent ruling (Borman , 1998; Zeissel, 1999). prevented the FDA from regulation.

The significance of dietary supplements in the United States led to the creation of the Office
of Dietary Supplements (ODS) via the DSHEA in 1995 under the National Institutes of
Health (NIH) (DSHEA, 1994). The ODS maintains a searchable database (International
Bibliographic Information on Dietary Supplements [IBIDS]) of published scientific literature
on dietary supplements (NIH Office of Dietary Supplements, 1999).

167
Section 6. Case Studies

Although these substances are readily available off the counter, not always in a
characterized/standardized forms, an effort is underway to patent various nutraceuticals by
standardizing the extracts and thereby making them available only by prescription. The
patenting of hundreds of multiple-molecule nutraceuticals for therapeutic purposes could
lead to more widespread use of these substances.

As an example, a recent addition to this class is a substance called huperzine A, an alkaloid


extracted from a Chinese moss, which has been documented to improve memory. It is
therefore experiencing strong demand for treating Alzheimer's disease and has captured the
attention of those who follow the nutraceutical market because of its true pharmaceutical
qualities. The significance of this particular compound is that it possesses acute biologic
activity as a cholinesterase inhibitor identical to that of organophosphorus and carbamate
insecticides. It is so effective that the medical community is concerned about its
abuse/misuse, especially since it is legal. While huperzine A, and alkaloids in general
(compounds with heterocyclic nitrogen, proton-accepting group, and strong bioactivity), are
naturally occurring compounds, their susceptibility to biodegradation in WWTS or in surface
waters is unknown. This is the case for almost all nutraceuticals, therefore more research is
needed.

Another example is Kava, which is prepared from the root of Piper methysticum, used of its
mild narcotic effect among other effects. The active ingredients in Kava are believed to be a
suite of lipophilic lactones comprising substituted -pyrones (methysticin, kavain, yangonin,
and others) (Shao, et.al.,1998). These compounds display a host of effects in humans, but
nothing is known about their effects on other organisms or fate in WWTS.

There are many nutraceuticals, both new and ‘traditional’, experiencing increased
consumption. These few examples illustrate the unknowns regarding whether these
compounds are being excreted, surviving WWT, and then having possible effects on aquatic
organisms. Nutraceuticals and herbal remedies would have the same potential fate in the
environment as pharmaceuticals, with the added dimension that their usage rates could be
much higher, as they are readily available and taken without the controls of prescription
medication. However, because these compounds are natural products, they would be
expected to biodegrade more easily .

Legislation and policy for risk assessment

At the beginning of the 1980s, environmental risk assessment was introduced for new
chemicals but it took a decade later for drugs to be included in the discussion. In Europe,
since the 1990's, there has been a distinction made between compounds for human use and
those used in veterinary practice. For several years legislation has been implemented for
veterinary medicines. The EU Directive 81/852/EEC, (Amended 1993), introduced the
requirement for a tiered environmental risk assessment of new veterinary products, and
attempts are being made to implement this for a review of existing substances (ENDS,
2000). Currently, environmental risk assessment consists of examining the likely
environmental sectors and if levels of pharmaceutical compounds exceed the trigger values
set, such as 100 µg.l-1 in manure, further data is required (ENDS, 2000). The technical
directive [Directive 81/852/EEC, amended 1993] concerning veterinary medical products
outlines the basic requirements for conducting an environmental risk assessment (Halling-
Sorensen, 1998). The technical directive [Directive 75/318/EEC, amended 1993] concerning
human medical products does not refer to any ecotoxicology or ecotoxicity tests and no
guidance is given on how to carry out an environmental risk assessment for drugs used by
humans. However, a draft directive for human pharmaceuticals is currently being devised,
proposing that risk assessment should be part of the approved procedure of new medical
substances (Halling-Sorensen, 1998). The EC is proposing a similar programme for human

168
Section 6. Case Studies

medicines: if drug concentrations in surface waters are predicted to exceed 0.01 µg.l-1,
toxicity testing is required to find the no effect level (NOEC) (ENDS, 2000). Although
environmental assessment of the potential impacts of newly developed drugs has been
expected in the EU since the 1st of January 1995 (Christensen, 1998), it is should be noted
that the end point of human exposure is not usually investigated. Also, assessment of
individual compounds is usually based on a limited number of tests but pharmaceuticals in
the environment may affect a large number of different organisms and species, so this ability
should be reflected in the tests carried out (Stuer-Laurisden, 2000). Pharmaceuticals may
not affect the standard test species and give rise to false negative results (Stuer-Laurisden,
2000).

A risk assessment study was carried out in Germany looking at salicylic acid, paracetamol,
clofibrinic acid, and methotrexate (Henschel, 1997). As seen previously in this Case Study,
these compounds were present in the environment and had toxic effects in at least one
standard ecotoxicological test. The most sensitive reaction however, was to a non-standard
test incorporating relevant end points for the pharmaceuticals (Henschel, 1977), so proving
the limitations of standard tests.

Risk assessment of pharmaceuticals

Risk assessment for pharmaceuticals in the environment has not usually been carried out
due to the lack of data and the need for more precise and sensitive measures in the
environmental sectors. Some high consumption compounds, such as antibiotics and clofibric
acid, are being released into the environment and have been found to be widely present in
aquatic environments, sediments and soils. Although the liver often metabolises
pharmaceutical compounds to more easily hydrolysed compounds, the metabolites can be
cleaved back to the more hydrophobic, active parent compounds by bacteria, which can
then persist and bioaccumulate.

There is a strong opinion that there are more pressing environmental problems than
pharmaceuticals and that these compounds do not pose a large risk because they are
present in such low concentrations (ng.l-1), with most effects only seen in the mg.l-1 range
(ENDS, 2000). As already stated though, disease resistance to pharmaceuticals is favoured
by low concentration exposure and compounds such as antineoplastic agents and hormones
have effects at very low levels. The effects of active compounds in the low, ng.l-1 range,
cannot be excluded, as experience with pesticides shows, impacts can be significant at low
levels (Stuer-Laurisden, 2000).

At the moment, most toxicity tests performed investigate acute impacts on specific species.
However, as most compounds in question are persistent and are discharged continuously
into the environment at low levels, it would appear to be more relevant to look at the chronic,
long-term impacts of exposure to low concentrations over all trophic levels. Some of the
long-term, chronic impacts that may be of concern are genotoxicity and reproduction
impairment. It has been found that Daphnia are tolerant to most antibiotics within the mg.l-1
range but that exposure to these levels over several weeks causes death, probably because
of toxic effects in the food organisms (ENDS, 2000). The effects of continuous exposure to
even low levels of pharmaceuticals in the environment are very complex and affect many
different organisms. More studies are necessary with regards to the long-term impacts and
the potential synergistic effects of exposure to a mixture of drugs.

Exposure route is very important in determining environmental loading, as the dose and
duration of exposure are important parameters in risk assessment. Drugs tend to be
released in low concentrations, although local discharges, such as those coming from
hospitals, may have higher concentrations (Jorgensen, 2000).

169
Section 6. Case Studies

A study carried out in Italy (Zuccato, 2000), found that most drugs were present in drinking
water, river water and sediments, but that human exposure would only be in the ng day-1
range, which is much lower that the concentration where effects are expected to be
observed. The study concluded that risk seems negligible but possible long-term exposures
and impacts still need investigation. The same was found with X-ray contrast media, which
were ubiquitous in the aquatic environment and highly persistent. No acute toxic effects
were observed, in Daphnia magna or in bacteria, algae, fish, and crustaceans (Ternes,
2000). Long-term exposure was not investigated.

Risk assessments were carried out on three pharmaceuticals, using the computer program
EUSES, which was developed as a support to the technical guidance document for risk
assessment on new and existing substances (Christensen, 1998). The three compounds
assessed were; the synthetic estrogen, 17α-ethinylestradiol; the antibiotic, penicillin V; and
the antineoplastic agent, cyclophosphamide. This program estimated environmental fate and
human exposure based on worst-case scenarios, using data on the physico-chemical
properties of the compounds and amounts consumed. The results indicated that for all three
there was negligible human risk. However, the author stressed the point that many
uncertainties are associated with this method and that the drugs, although seemingly
insignificant, still contribute to the total toxic load in the environment, and that interactions
may have ecotoxicological impacts.

Research in Denmark attempted to carry out a risk assessment for the 25 most highly used
drugs in the primary health sector in Denmark, including furosemide, paracetamol,
ibuprofen, and estradiol (Stuer-Laurisden et al., 2000). Different parameters are used to
calculate environmental exposure: biodegradation, bioaccumulation, and bioavailability are
three of the most important. Nevertheless, it has been seen that biodegradation of
pharmaceuticals does not happen very often. Bioaccumulation in the human body does not
happen for drugs, as they are metabolised to more polar compounds that can then easily be
excreted. The bioavailability of drugs is different if it is bound to solids, adsorbed, or
dissolved. However, as seen above, the octanol-water partition coefficient can be used to
determine bioaccumulation, and other parameters can be used to determine bioavailability.
However, this information on the properties of the compounds is not readily available. They
found that ecotoxicology data was available only for 6 of the 25 compounds, and
biodegradation data only for 5 (Tables d.9 and d.10) (Stuer-Laurisden et al., 2000).
Predicted environmental concentrations (PEC) should be determined for the system where it
is anticipated that the highest values would be found, i.e. aquatic ecosystems and sewage
sludge (Jorgensen, 2000). In order to do so, modelling could be a useful tool; however, not
many models have yet been developed and validated due to the lack of data in this area
(Jorgensen, 2000 and Halling-Sorensøn,1998). The predicted environmental concentrations
for the 6 compounds were calculated and all exceeded 0.001µg.l-1, which is the cut off value
in EU legislation for carrying out more investigations. The majority of the PECs are between
1-100ng.l-1, it is only for the top 5 compounds that these reach the µg.l-1 range (Stuer-
Laurisden, 2000). The predicted no effect concentration (PNEC) is based on
ecotoxicological data and the PEC/PNEC ratio was found to exceed one only for ibuprofen,
paracetamol, and acetylsalicylic acid and below one for estrogen, diazepam, and digoxin
(Stuer-Laurisden, 2000). This showed that data is only partially available, preventing
complete risk assessments. Nevertheless, it was concluded, with this data, that ibuprofen,
aspirin, and paracetamol may pose a risk; hence, contradicting other studied that had
concluded these were efficiently removed by treatment and did nor reach hazardous levels
in the environment (ENDS, 2000). The efforts are hampered by the fact that concentrations
measured in sludge and effluent vary extensively, and furthermore comparisons of predicted
concentrations in sludge based on Kow, sludge-water partition coefficients (Kd), or acid-base
constants (pKa) also reveal large variations (Stuer-Laurisden, 2000).

170
Section 6. Case Studies

The cost/benefit stage of risk assessment is extremely important: the indirect and direct
effects of the drug on the environment and the human body must be known in order to make
an informed decision (Jorgensen, 2000 and Halling-Sørenson,1998). This can allow
selection of a substitute drug that has the same benefits but fewer environmental impacts.
Hence, lack of data for toxicity but also environmental concentrations prevent calculation of
risks.

Examples of good environmental practice

In France, and the UK, there are procedures for returning prescribed but unused
pharmaceuticals. In France, these plans are encouraged by the ADEME "RETOUR" initiative
(ADEME, 1997a), which also encourages the distributor to include the costs of collection and
treatment into the product's selling price. This strategy is useful for reducing the amount of
polluted domestic and artisanal (laboratories, photographic shops etc) wastewater through
special collections for specific pollutants such as thermometers, medicines, and paint
leftovers. Most areas in France have implemented such programmes and they are
successful.

There are also possibilities of reformulating and substituting certain pharmaceutical


compounds with substances incurring fewer impacts. It has been found that
cyclophosphamide and ifosfamide, the very widely used antineoplastic drugs, act through an
active metabolite, which is highly unstable. German researchers have detected another
compound that has the same therapeutic activity but that is much more readily biodegraded
(ENDS, 200). However, in order to research more environmentally suitable drugs, the
characteristics of the existing ones must be known, and, as yet, there is still very little data
available.

If the assessment of a drug gives a high risk, the response may not have to be the phasing
out of the drug, but maybe just the collection and specific treatment of the faeces and urine
containing this compounds (Jorgensen, 2000). Environmental risk assessment should be
part of the development of all new drugs and could be used as a marketing tool, as public
concern for the environment is increasing (Jorgensen, 2000).

Analysis tools and their sensitivity must be improved for the determination of the very low
concentrations of drugs. A method obtaining detection limits within the ngl-1 range for
various pharmaceutical compounds, particularly neutral basic drugs such as betablockers,
has been developed, using advanced solid phase extraction, modified derivatisation
procedures and LC-electrospray-MS/MS detection (Ternes, 1998a). This allows detection
down to 10ng.l-1, in different aqueous matrices. In another study, determination limits down
to 5ng.l-1 were achieved for phenolic compounds and other acidic drugs, such as lipid
regulators and acetylsalicylic acid metabolites, using solid phase extraction and methylation
or acetylation of the carboxylic and phenolic hydroxyl groups, followed by detection by
GC/MS (Ternes, 1998b).

In Sweden, a pharmaceutical company, AstraB, was discharging very toxic effluents


containing a large amount of persistent organic pollutants and phosphorus, which had
caused operational problems at the WWTS (Rosen, 1998). There were large variations in
the composition of their effluent over time, as the drugs tend to be produced in discontinuous
batches. Hence, a broad and flexible treatment method had to be introduced to treat the
wastewater at source. The wastewater was investigated and it was found that the main
contribution came from the treatment of packages containing non-approved liquid
pharmaceutical preparations (Rosen,et.al. 1998). The washing water had a very high toxicity
and could not be treated biologically. This effluent was removed and incinerated and the
remaining effluent still too toxic for discharge into the UWWT system is now treated using a

171
Section 6. Case Studies

multi-stage biofilm process removing all organic matter and the toxicity is no longer
measurable (Rosen, et.al. 1998).

Conclusion and Recommendations

Pharmaceutical compounds must become priority substances in the same way as persistent
organic pollutants are. Judgements on the relative priorities are based on the knowledge at
the time and the priority list will obviously change over time as more studies are carried out
and more data is gathered. Pharmaceuticals are widely used and mainly disposed of
through the sewerage system, allowing their entry into the environment continually, as
removal rates can be compensated by replacement rates (Daughton and Ternes, 1999).
They are concerning because they are biologically active and are usually lipophilic and
potentially bioaccumulating. Many resist biodegradation, within the WWTS and in the
environment, and can end up in surface and ground waters, as well as sediment and soils
and are found to be highly stable under environmental conditions. Furthermore, metabolites
tend to be cleaved and transformed back to the parent compounds once in the environment,
increasing the concentrations and justifying the importance of metabolites. Many can have
unpredicted and unknown side effects particularly after long-term exposure to low
concentrations. Aquatic ecosystems are the most vulnerable, as this is the main
environmental compartment where pharmaceuticals are found ubiquitously.

Analytical methods must be improved to detect pharmaceuticals at very low levels and
sampling procedures must be of very high quality so as not to cause contamination. More
information on the physicochemical, ecotoxicity, and ecotoxicological characteristics, using
appropriate tests that better accommodate subtle end points, of drugs and their metabolites
should be obtained in order to allow environmental risk assessments to be carried out.
Furthermore, this may lead to the validation of modelling techniques that could speed up the
whole process. Furthermore, use patterns of drugs in all countries is still very limited and
should be determined, as it is essential for the elaboration of amounts released into the
environment.

Screening of high use drugs should be carried out and samples with high potential should
then be subject to more analyses (Daughton and Ternes, 1999). Furthermore, a more
precautionary view on the potential impacts of the drugs should be adopted and more
studies are required to elucidate these effects at the concentrations observed and also
investigating additive and synergistic effects of mixtures (Daughton and Ternes, 1999).

Risk assessment for pharmaceuticals should include an assessment of their biodegradability


and environmental fate and potential impact as occurs for other discharged substances,
such as detergent residues. Furthermore, the disposal of unwanted drugs into the
wastewater system from domestic sources should be discouraged by encouraging collection
of these wastes.

172
Section 6. Case Studies

(e) Personal Care Products, Fragrances in Urban Waste Water and Sewage Sludge

Personal care products are defined as chemicals marketed for direct use by the consumer
(excluding off the counter medication with documented physiologic effects) and having
intended end uses, primarily on the human body (products not intended for ingestion) or in
the household. In general, these chemicals alter odour, appearance, touch, or taste without
displaying significant biochemical activity (Daughton and Ternes, 1999). Most of these
chemicals are used as the active ingredients or preservatives in cosmetics, toiletries and
fragrances. They are not used for treatment of disease, but some may be intended to
prevent diseases (e.g., sunscreen agents). In contrast to drugs, almost no attention has
been given to the environmental fate or effects of personal care products, the focus has
traditionally been on the effects from intended use on human health.

Personal care products differ from pharmaceuticals in that large amounts can be directly
introduced to the environment and unlike medicinal compounds, there are rarely
recommended doses. These products can be released directly into recreational waters or
volatilised into the air. Because of this direct release they can bypass possible degradation
in UWWT. Also, in contrast to pharmaceuticals, less is known about the effects of this broad
and diverse class of chemicals on non-target organisms, such as aquatic organisms. Data
are also limited on the potential adverse effects on humans. For example, common
sunscreen ingredients, 2-phenylbenzimidazole-5-sulfonic acid and 2-phenylbenzimidazole,
can cause DNA breakage when exposed to UV-B (Stevenson and Davies, 1999).

The quantities of personal care products produced commercially can be very large. For
example, in Germany alone the annual output was estimated to be 559,000 tonnes for 1993
(Statistisches Bundesamt, 1993). A few examples are given below of common personal care
products that are ubiquitous pollutants, which may possess varying degrees of bioactivity.
Table e.1 Personal care and fragrances produced in Germany (1993)

Product category Tonnes


Bath additives 162 300
Shampoos, hair tonic 103 900
Skin care products 75 500
Hair sprays, hair dyes, setting lotions 71 000
Oral hygiene products 69 300
Soaps 62 600
Sun screens 7 900
Perfumes, aftershaves 6 600
TOTAL 559 100

• Preservatives

Parabens (alkyl-p-hydroxybenzoates) are one of the most widely and heavily used types of
antimicrobial preservatives in cosmetics (skin creams, tanning lotions, etc.), toiletries,
pharmaceuticals, and even foodstuffs (up to 0.1% wt/wt). Although the acute toxicity of these
compounds is very low, Routledge et al.[1998] report that these compounds (methyl through
butyl homologs), display weak oestrogenic activity. Although the risk from dermal application
in humans is unknown, the probable continual introduction of these benzoates into
wastewater treatment systems and directly to recreational waters from the skin, leads to the
question of risk to aquatic organisms. Butylparaben showed the most competitive binding to
the rat oestrogen receptor at concentrations one to two orders of magnitude higher than that
of nonylphenol and showed oestrogenic activity in a yeast oestrogen screen at 10-6 M .

173
Section 6. Case Studies

• Disinfectants/Antiseptics

Triclosan, a chlorinated diphenyl ether: 2,4,4´-trichloro-2´-hydroxydiphenyl ether, is an


antiseptic agent that has been widely used for almost 30 years in a vast array of consumer
products. Its use as a preservative and disinfectant continues to grow; for example, it is
incorporated at < 1% in Colgate's “Total” toothpaste, the first toothpaste approved by the
FDA to fight gingivitis. While triclosan is registered with the U.S. EPA as a pesticide, it is
freely available over the counter. Triclosan's use in commercial products includes footwear
(in hosiery and insoles of shoes called Odour-Eaters), hospital hand-soap, acne creams
(e.g., Clearasil), and rather recently as a slow-release product called Microban, which is
incorporated into a wide variety of plastic products from children's toys to kitchen utensils
such as cutting boards. Many of these uses can result in direct discharge of triclosan to
UWW collecting systems, and as such this compound can find its way into receiving waters
depending on its resistance to microbial degradation. Okumura and Nishikawa [1996] found
traces of triclosan ranging from 0.05 to 0.15 µg.l-1 in water. Although triclosan has long been
regarded as a biocide (a toxicant having a wide-ranging, nonspecific mechanism(s) of action
- in this case gross membrane disruption) McMurry et al. [1998] report that triclosan actually
acts as an antibacterial, having particular enzymatic targets (lipid synthesis). As such,
bacteria could develop resistance to triclosan. As with all antibiotics in the environment, this
could lead to development of resistance and change in microbial community structure
(diversity).

A wide range of disinfectants are used in large amounts, not just by hospitals but also by
households and livestock breeders. These compounds are often substituted phenolics as
well as other substances, such as triclosan. Biphenylol, 4-chlorocresol, chlorophene,
bromophene, 4-chloroxylenol, and tetrabromo-o-cresol [Ternes et al 1998] are some of the
active ingredients, at percentage volumes of < 1-20%. A survey of 49 WWTPs in Germany
[Ternes et al 1998] routinely found biphenylol and chlorophene in both influents, up to 2.6
µg/L for biphenylol and up to 0.71 µg.l-1 for chlorophene, and effluents. The removal of
chlorophene from the effluent was less extensive than for biphenylol, with surface waters
having concentrations similar to that of the effluents.

• Sunscreen Agents

The occurrence of sunscreen agents (UV filters) in the German lake Meerfelder Maar was
investigated by Nagtegaal et al. [1997]. The combined concentrations of six sunscreen
agents (SSAs) identified in perch (Perca fluviatilis) in the summer of 1991 were as high as
2.0 mg.kg-1 lipid and in roach (Rutilus rutilus L) in the summer of 1993, as high as 0.5 mg.kg-
1
lipid. Methylbenzylidene camphor (MBC) was detected in roach from three other German
lakes. These lipophilic SSAs seem to occur widely in fish from small lakes used for
recreational swimming. Both fish species had body burdens of SSA on par with PCBs and
DDT. The bioaccumulation factor, calculated as quotient of the MBC concentration in the
whole fish (21 µg.kg-1) versus that in the water (0.004 µg l-1), exceeded 5,200, indicating high
lipophilicity. The fact that SSAs (e.g., 2-hydroxy-4-methoxybenzophenone [oxybenzone] and
2-ethylhexyl-4-methoxycinnamate) can be detected in human breast milk (16 and 417 ng.g-1
lipid, respectively) [Hany et al 1995] shows the potential for dermal absorption and
bioconcentration in aquatic species. No data have been published on newer SSAs such as
avobenzene (1-[4-(1,1-dimethylethyl)phenyl]-3(4-methoxyphenyl)-1,3-propanedione).

• Perfume Ingredients
The raw ingredients in perfumes include essential oils, plant extracts and animal secretions,
and synthetic or semi synthetic (natural material that has undergone some chemical
modification) compounds. Thousands of these substances can be blended to create
perfumes. These can be used directly as perfumes or as scents in other products, for

174
Section 6. Case Studies

example in cosmetics, cleaning agents and air fresheners. Perfume ingredients may enter
the urban wastewater system directly from domestic sources, such as in the washing agents
or from being washed off skin in the case of perfumes and cosmetics.

The organic compounds found in perfumes that may be of environmental or health concern
include

- nitro-musk compound,
- polycyclic musk compound,
- solvents and fixatives
- other fragrances.

Details of the physical properties of these compounds are included in Appendix B. Health
and environmental effects of the compounds discussed are also briefly introduced within this
case study.

This case study will focus on musk compounds. Fragrances (musks) are ubiquitous,
persistent, bioaccumulative pollutants that are sometimes highly toxic; amino musk
transformation products are toxicologically significant.

Synthetic musks comprise a series of structurally similar chemicals (which emulate the odour
of the more expensive, natural product, from the Asian musk deer), used in a broad
spectrum of fragranced consumer items, both as fragrance and as fixative. Included are the
older, synthetic nitro musks (e.g., ambrette, musk ketone, musk xylene, and the lesser
known musks moskene and tibetene) and a variety of newer, synthetic polycyclic musks that
are best known by their individual trade names or acronyms.

The major musks used today are, the polycyclic musks (substituted indanes and tetralins),
which account for nearly two-thirds of worldwide production and the inexpensive nitro musks
(nitrated aromatics), accounting for about one-third of worldwide production. These
substances are used in nearly every commercial fragrance formulation (cosmetics,
detergents, toiletries) and most other personal care products with fragrance; they are also
used as food additives and in cigarettes and fish baits (Gatermann, et.al. 1998)

The nitro-musks are under scrutiny in a number of countries because of their persistence
and possible adverse environmental impacts and therefore are beginning to be phased out
in some countries. Musk xylene has proved carcinogenic in a rodent bioassay and is
significantly absorbed through human skin; from exposure to combined sources, a person
could absorb 240 µg/day [Bronaugh et al 1998]. The human lipid concentration of various
musks parallels that of other bioaccumulative pollutants, such as PCBs [Schmid 1996].
Worldwide production of synthetic musks in 1988 was 7000 tonnes [Gattermann et al 1998]
and worldwide production for nitro musks in 1993 was 1,000 tonnes, two-thirds of which
were musk xylene [Kfferlein 1998]

Synthetic musks first began to be identified in environmental samples almost 20 years ago
[Yamagishi 1981 and 1983]. By 1981, Yamagishi et al. had identified musk xylene and musk
ketone in gold fish (Carassius auratus langsdorfii) present in Japanese rivers and soon after
[Yamagishi et al 1983] in river water, wastewater, marine mussels (Mytilus edulis), and
oysters (Crassosterea gigas). This was followed by a number of studies in Europe, some of
which are summarised in table e.2.

175
Section 6. Case Studies

Table e.2 Concentrations of various musk compounds in environmental samples.


Location Tissue/Substance Product Concentration Reference
North Germany Freshwater Fish Musk Xylene 10-350µg.kg-1 Geyer et al, 1994
(Fillet) Musk Ketone 10-380µg.kg-1 Geyer et al, 1994
Ruhr River, Bream and Perch Galaxolide, Average Eschke et al 1998
Germany (Fatty tissue) Tonalide and concentrations
Celestolide between 2.5 and
4.6 mg.kg-1 (ppm)
Berlin, Germany Surface waters Galaxolide, Maximum Herberer et al
Tonalide and concentrations 1999
Celestolide above 10µ L-1
Elbe River, Particulate matter Musk ketone 4-22 ng/g Winkler et al. 1998
Germany from river samples Galaxolide 148-736 ng/g
Tonalide 194-770 ng/g
Italy Freshwater Fish Galaxolide, 4 ng.g-1 – Draisci et al 1998
(Fatty tissue) Tonalide 1054 ng.g-1

Musks are refractory to biodegradation (other than reduction of nitro musks to amino
derivatives), which explains why they have been detected in water bodies throughout the
world [Gattermann et al 1998]. They also are very lipophilic [octanol-water partition
coefficients are similar to those for DDT and hexachlorocyclohexane , Winkler et al, 1998]
and therefore can bioaccumulate, leading to very high concentrations being measured in
some studies.

The values for the three most prevalent musks in the Elbe river study (table e.2) were within
the same order of magnitude as those for 15 polycyclic aromatic hydrocarbons (PAHs) and
exceeded those for 14 common polychlorinated organic pollutants (only hexachlorobiphenyl
[HCB] and p,p´-DDT were of similar concentration). Also, all the 31 water samples contained
musk ketone (2-10 ng.l -1), Galaxolide (36-152 ng.l -1), and Tonalide (24-88 ng.l-1); Celestolide
was found only at 2-8 ng.l-1. These higher values exceeded those for all the polychlorinated
organics and the PAHs. The occurrences of individual musks are sometimes correlated as a
result of their use as mixtures in commercial products. In Germany, the nitro musks are
being replaced by the polycyclic musks, therefore resulting in lower concentrations for musk
ketone [Winkler et al, 1998].

Although the significance of the aquatic toxicity of the nitro and polycyclic musks is
debatable (genotoxicity from the polycyclics seems not to be a concern) [Kevekordes 1998],
the aminobenzene (reduced) versions of the nitro musks can be highly toxic. These reduced
derivatives are undoubtedly created under the anaerobic conditions of sewage sludge
digestion. Behecti et al. [1998] tested the acute toxicity of four reduced analogs of musk
xylene on Daphnia magna. The p-aminodinitro compound exhibited the greatest toxicity of
the four, with extremely low median effective concentration (EC50) values averaging 0.25
µg.l-1 (0.25 ppb).

Recently, the amino transformation products of nitro musks were identified in wastewater
treatment effluent and in the Elbe River, Germany. Gatermann et al. [1998] identified musk
xylene and musk ketone together with their amino derivatives 4- and 2-amino musk xylenes
and 2-amino musk ketone. In wastewater entering treatment plants, the concentrations of
musk xylene and musk ketone were 150 and 550 ng.l-1, respectively. In the effluent, their
concentrations dropped to 10 and 6 ng.l-1, respectively. In contrast, although the amino
derivatives could not be detected in the influent, their concentrations in the effluents
dramatically increased, showing extensive transformation of the parent nitro musks: 2-amino
musk xylene (10 ng.l-1), 4-amino musk xylene (34 ng.l-1), and 2-amino musk ketone (250
ng.l-1). It was concluded that the amino derivatives could be expected in wastewater effluent
at concentrations more than an order of magnitude higher than the parent nitro musks. In the

176
Section 6. Case Studies

Elbe, 4-amino musk xylene was found at higher concentrations (1-9 ng.l-1) than the parent
compound.

Amino nitro musk transformation products are


• more water soluble than the parent musks,
• still have significant octanol-water partition coefficients (high bioconcentration
potential),
• more toxic than the parent nitro musks,
therefore more attention should be focused on these compounds.

Because synthetic musks are ubiquitous; used in large quantities; introduced into the
environment almost exclusively via treated wastewater; and are persistent and
bioconcentratable, they are prime candidates for monitoring in both water and biota as
indicators for the presence of other personal care chemicals. Their analysis, especially in
biota, has been thoroughly discussed by Gatermann et al. [1998] and by Rimkus et al.
[1997].

It is thought that musk compounds can bioaccumulate in human tissue [spinnrad website
2000] and act as hormones, because they bind to the hormone receptors of the cells
[Gerhard, I umweltmedizin website 2000]. However, there is insufficient data for an adequate
toxicologically assessment for both the nitro- and the polycyclic musk scents [Antusch,
1999].

Emission Data

At the present time the quota of the polycyclic musk scents amounts to approximately 85 %
of total musk production worldwide, and the quota of nitro-musk scents is approximately 12
% [Rebmann et al., 1998].

Musk Compounds in Wastewater:


The use of musk compounds in cosmetic and detergent products, which are used primarily
in domestic situations or in buildings connected to the UWW collecting system, implies that
their presence in surface waters occurs via municipal wastewater treatment plants. The
mean concentrations found in biologically clarified wastewater from 25 German municipal
WWTP were,

o for musk-xylene: 0.12 µg.l-1 (concentration range: 0.03 – 0.31 µg.l-1) and
o for musk-ketone: 0.63 µg.l-1 (concentration range: 0.22 – 1.3 µg.l-1).

The mean emission levels in Germany were quantified as 20 µg/inhabitant/day for musk-
xylene and 90 µg/inhabitant/day for musk-ketone [Eschke et al., 1994].

In Vienna, Austria, extensive testing of wastewater was carried out at the pilot plant of the
city’s main WWTP, during 1999. Concentrations of musk compounds in WWTP influent and
effluent are shown in Table e.3.

177
Section 6. Case Studies

Table e.3: Musk compound concentrations in influent and effluent of the pilot WWTP
Simmering, Austria in 1999 [Hohenblum et al., 2000].n: number of samples analysed.
LOD: limit of detection
Compound Type of Sample Range Mean
(µg.l-1) sample number > (µg.l-1) Value
LOD (µg.l-1)
Musk-xylene Influent 4 0.023 - 0.037 0.031
(n=4) Effluent 0 - -
Musk-ambrette Influent 0 - -
(n=4) Effluent 0 - -
Musk-moskene Influent 0 - -
(n=4) Effluent 0 - -
Musk-tibetene Influent 0 - -
(n=4) Effluent 0 - -
Musk-ketone Influent 4 0.049 - 0.069 0.056
(n=4) Effluent 4 0.038 -0.053 0.049

Musk Compounds in Sewage Sludge:


The result of analyses into the presence of musk compounds in sewage sludge and the
sediment of UWW collecting systems in German commercial and residential areas, are
presented in Table e.4. In all samples noticeably high musk scent concentrations were
detected. Sediment samples from the UWW collecting system for the residential area had
slightly higher concentrations of the three polycyclic compounds ADBI (celestolide), HHCB
(galoxolide) and AHTN (tonalide). This is probably due to the more frequent use of perfumes
and detergents in domestic areas.
Table e.4: Concentration of different musk scents in sewage sludge and UWW
collecting system sediment in mg/kg DS, Germany [Antusch, 1999].
N = number of samples analysed. N>LOD number of samples over the limit of detection
Compound N> Sediment: Sediment: Sewage sludge
LOD
industrial area residential area
(n=17) (n=2) (n=2)
mean range mean range mean range
Musk-xylene 6 0.028 <0.005-0.20 0.095 0.066-0.134 <0.005 < 0.005
Musk-ketone 7 0.12 <0.01-1.78 0.25 0.15-0.36 0.03 <0.01-0.06
ADBI 12 0.051 <0.01-0.28 0.35 0.19-0.52 0.20 0.12-0.29
HHCB 17 1.43 0.08-5.2 15.5 9.1-21.8 8.87 4.3-13.4
AHTN 17 2.08 0.13 - 8.9 23.1 9.5 - 36.7 8.30 4.0 - 12.6

178
Section 6. Case Studies

Musk Compounds in Watercourses:

The pollution of the river Ruhr (Germany) with musk compounds was found to be relatively
low, with maximum concentrations of 0.08 µg.l-1 and 0.03 µg.l-1 for musk-ketone and musk-
xylene, respectively. Fish from the Ruhr contained residues of musk compounds in their
muscle flesh, at concentrations below 10 µg.kg-1 wet weight [Eschke et al., 1994].

The polycyclic musks, HHCB (galaxolide, abbalide) and AHTN (tonalide, fixolide) were found
in German receiving waters at concentrations up to the µg.l-1 level. In the Wuhle, a small
stream consisting almost totally of wastewater effluent, maximum concentrations were 12.5
µg.l-1 for HHCB and 6.8 µg.l-1 for AHTN. Additionally, the polycyclic musk ADBI (celestolide,
crysolide) and musk-ketone were detected at low concentrations in the majority of samples.
Two other nitro-musks, moskene and xylene, were only detected in a single surface water
sample [Heberer et al., 1999].

The concentration of the three compounds tonalide, celestolide and galaxolide, were
measured in different watercourses in Germany. The results of this study are shown in Table
e.5. The Elbe concentrations for musk-xylene were approximately 0.2 µg.l-1.

Table e.5: Concentration of nitro-musk compounds in different watercourses in the


länder Sachsen and Sachsen-Anhalt, Germany [Lagois, 1996].<LOD: below limit of
detection
Nitro-musk compounds

ADBI (celestolide) HHCB (galaxolide) AHTN (tonalide)


[µg.l-1] [µg.l-1] [µg.l-1]

Sample date 22.5.95 12.6.95 22.5.95 12.6.95 22.5.95 12.6.95


Elbe at Torgau <0.08 <LOD 0.057 0.092 0.062 0.116
Bank filtration, Torgau <LOD <LOD <LOD <0.03 <LOD <0.03
Pure water, Torgau-East <LOD <LOD <LOD <0.03 <LOD <0.03
Dam, Rappdode <LOD <LOD <0.03 <0.03 <0.03 <0.03
Pure water, Wienrode <LOD <LOD <LOD <0.03 <LOD <0.03
Ground water, Kossa <LOD <LOD <LOD <LOD <LOD <LOD
Pure water, Kossa <LOD <LOD <LOD. <LOD <LOD <LOD

Conclusions
There is very limited information on the health and environmental effects of personal care
products, such as the musk compounds found in perfumes. Many of these compounds have
the potential to bioaccumulate, which is why there is concern about their presence in
wastewater. Though these products may be used in large quantities there is insufficient data
though to establish whether the presence of these compounds in UWW could cause any
detrimental environmental or health effects.

179
Section 6. Case Studies

(f) Surfactants in Urban Wastewaters and Sewage Sludge

Introduction

Surfactants are the largest class of anthropogenic organic compounds present in raw
domestic wastewater. They are used in household and commercial laundry and cleaning
operations. Surfactants can be classified [Ullman’s Encyclopaedia of Industrial Chemistry,
2000] into:

• Anionic surfactants are anion-active, amphiphilic compounds in which the


hydrophobic residues carry anionic groups with small-sized counter-ions, such as
sodium, potassium or ammonium ions. These counter-ions have only a slight
influence on the surface active properties. Examples include soaps, alkylbenzene
sulphonates (ABS), alkylsulphates (AS), and alkylphosphates (AP).
• Non-ionic surfactants (NIS) – are amphiphilic compounds that are unable to
dissociate into ions in aqueous solutions, for example, alkyl- and alkylphenyl
polyethylene glycol ethers, alcohol ethoxylates (AE) and alkylphenol ethoxylates
(APE), fatty acid alkylolamides, sucrose fatty acid esters, alkylpolyglucosides,
trialkylamine oxides.
• Cationic surfactants, cation-active amphiphilic compounds in which the
hydrophobic groups exist as cations with counter-ions such as chloride, sulphate or
acetate. Examples include tetraalkyl ammonium chloride, N-alkylpyridinium chloride
and others.
• Amphoteric surfactants have zwitterionic* hydrophilic groups (*electrically neutral
ions with both positive and negative charges), such as aminocarboxylic acids,
betaines and sulphobetaines.

Uses and sources of surfactants in the environment

The largest proportion of surfactants is used in detergents and cleansing agents for
domestic and commercial use [Falbe, 1987]. Surfactants are also used in:

• fabric softeners (cationic),


• foam cleaning agents (sulphosuccinates, LAS, AE),
• general cleansing agents (LAS, alkylbenzenes, fatty alcohol ether sulphates),
• domestic washing up liquids (betaines, NPO, alkylpolyglucosides),
• industrial cleansing agents (alkylbenzene sulphonates, alkanesulphonates, fatty
alcohol ethoxylates, alkylphenol ethoxylates, fatty amine ethoxylates, ethoxylates,
propylene oxide adducts, and others),
• bodycare products (ethersulphates, ether carboxylates, betaines, sulphosuccinates
of fatty alcohol polyglycol ethers, isethionates, amineoxides, alkyl polyglucosides).

Textile manufacturers uses surfactants extensively as washing agents, also for cleaning,
lubricating, bleaching, de-sizing or shrinking (where the mutual adhesion of fibres is
reduced), mercerising (cotton treatment that requires wetting agents), and finishing. Wool
washing is done with NIS, while cotton is washed with anionic surfactants. The leather
industry uses non-ionic and cationic surfactants as wetting and cleansing agents, and also
for leather conditioning. Surfactants are also used as emulsifiers and dispersants, and also
as food additives (natural substances only, such as glycerides, fatty acid salts, etc.).
Pharmaceuticals manufacturing uses surfactants, and they are also used in agricultural
applications such as crop-protection and pest control agents. Metal working and machining,
petroleum extraction and processing, ore flotation and dressing, mineral oil industry, road
construction and maintenance work, cement industry, plastics production, pulp and paper
industry and printing, electroplating, adhesives manufacturing, all use surfactants for their
unique properties.

180
Section 6. Case Studies

Non-ionic surfactants are detergents which possess specific physicochemical properties,


including relative ionic insensitivity and sorptive behaviour [deVoogt et.al, 1997] which
makes them particularly suited for use wherever interfacial effects of detergents, foaming-
defoaming, de-emulsification, dispersion or solubilisation can enhance product or process
performance. The major part of the non ionic surfactants group consists of alcohol
ethoxylates (AE) and alkylphenol ethoxylates (APE) of which, nonylphenol ethoxylate (NPE)
is the main representative. Because of the formation of persistent metabolites in the
environment, OSPARCOM member states have decided to phase out the use of NPE and to
replace the APEs with AEs. The production of non-ionic surfactants in the USA and EU
amounts to about 750 000 t/a and includes some 300 000 t/a of APE [Holt et.al., 1992].

Ionic surfactant molecules contain both strongly hydrophobic and strongly hydrophilic
groups. They thus tend to concentrate at interfaces of the aqueous system including air, oily
material and particles. The hydrophobic group is generally a hydrocarbon radical (R) of 10 to
20 carbon atoms. The hydrophilic portion may ionise or it may not. Ionic surfactants may be
either anionic or cationic. Ionic surfactants constitute approximately two-thirds of the
surfactants used. Cationic surfactants constitute less than 10% of the ionics and are used for
fabric softening, disinfection and other specialized applications. The predominant class of
anionic surfactants is linear alkylbenzene sulphonates (LAS).

The concentrations of linear alkylbenzene sulphonates (LAS) in raw wastewater range from
3 mg.l -1 to 21 mg.l-1 (Brunner et al., 1988, De Henau et al., 1989, Ruiz Bevia et al., 1989).
Although LAS and other common surfactants have been reported to be readily
biodegradable by aerobic processes, much of the surfactant load into a treatment facility
(reportedly 20-50%) is associated with suspended solids and thus escapes aerobic
treatment processes, being directed via primary sedimentation into sludge management
processes. Because LAS is not biodegraded by anaerobic biological processes usually
employed in sludge stabilization (McEvoy and Giger, 1985; Swisher, 1987), it may be found
in the gram per kilogram range in anaerobic sludges. Given these concentrations and the
major effects of surfactants in particle surface modification, deflocculation, and surface
tension reduction, it seems clear that the performance of certain treatment processes as
thickening, conditioning, and dewatering may be strongly influenced by these materials.

Thus, surfactants may induce significant extra costs in sludge handling. Increased water
content in landfilled sludges represents an additional possible impact, adding to the difficulty
of proper landfill leachate control. Surfactants may also mobilise otherwise insoluble organic
pollutants within the landfill. Similar implications exist for land application of surfactant-laden
sludges.

Feijtel et al [1995] examined five WWTS across Europe and found the influent of LAS to
WWTS in the UK to be higher than in the other plants (see Table d.1).

181
Section 6. Case Studies

Table d.1 LAS in influent and effluent in the UK compared with other regions [Feijtel et
al 1995]

Country Influent mg/l Country Effluent mg/l


Mean (+/- 95% CIs) Mean (+/- 95% CIs)
UK 15.1 (2.3) UK 0.010 (0.002)
Germany 5.4 (6.1) Germany 0.067 (0.076)
Italy 4.6 (5.1) Italy 0.043 (0.065)
Netherlands 4.0 (4.0) Netherlands 0.009 (0.008)
Spain 9.6 (9.6) Spain 0.14 (0.14)

As it can be seen from this study, the UK plants had significantly higher influent
concentrations than in Germany, Italy and the Netherlands (Spain had a very small data set
and therefore there is uncertainty in these results, which is reflected in the large confidence
intervals, which overlap with those of the UK). Having a high influent of LAS was unrelated
to the concentration in the effluent and the UK samples had a lower concentration of LAS in
its effluent than Germany, Italy or Spain. The level of biodegradation of LAS during the
wastewater treatment process is high and also varied between the plants, with the UK
WWTS having the highest level of biodegradation breaking down greater than 99.9 percent
of the LAS.

The study above, used UK data from Holt et al [1995] in which the levels of LAS in the
influent corresponded to estimates of LAS usage in homes. However a subsequent study
[Holt et al 1996], based on usage data on the influent entering six WWTS in the Yorkshire
region, found much lower levels of LAS than expected. In no cases did the concentrations of
LAS reaching the plant approach the level predicted from consumer usage. The previous
study had been carried out in March while the second was carried out in a ‘warm dry
summer’. This study suggested there was significant biodegradation of LAS under certain
conditions in the UWW collecting systems. Even in the relatively short residence time in the
Yorkshire UWW collecting system, for a couple of hours, up to 60% of the LAS was removed
prior to the wastewater treatment plant. This was then followed by removal of between 70 to
99 percent of the remaining LAS in the treatment plants.

Given the right treatment conditions, LAS are biodegradable and more research is
necessary to compare risks associated with alternative chemicals used in detergents.

The impact of LAS in wastewater effluent has been studied on several UK and Dutch rivers
and steams sediment. In some cases (such as the small stream into which the Owlwood
WWTS discharges its effluent the LAS load in sediment upstream of the treatment plant was
higher than that downstream [Waters and Feijtel 1995] This was hypothesised to be
because that the LAS contribution upstream was due to unregulated discharges of untreated
wastewater to the aquatic environment while the input of the WWTS effluent actually served
to dilute the concentration of this pollutant downstream. A similar case was found in the
Netherlands when concentrations of LAS could be higher upstream of a WWTS due to direct
discharges from storm tanks. In other locations downstream sites were found to have very
slight elevations of LAS in sediment of between 0.49 and 3µg/g. A more careful policy of
discharges has to be followed across the EU.

A new study by NERI [NPE/DEHP in sewage sludge in Denmark,


http://www.dmu.dk/beretuk98/society.htm#c4] shows that only small amounts of NPEs and
DEHPs are discharged in the urban wastewater by the commercial sector and that they do
not accumulate in agricultural soils treated with sewage sludge in moderate amounts. Figure
d.1 shows the level of surfactants and plasticisers in soils with the depth of the soil.

182
Section 6. Case Studies

Fig. d.1 Vertical distribution of various nonylphenols and phthalates in agricultural


soils fertilized with large amounts of sewage sludge (17 tonnes dry matter per hectare
per year). [NERI, 2000]

Fate and effect of surfactants in the environment

Fate of surfactants during wastewater treatment:


LAS and other common surfactants have been considered to be readily biodegradable by
aerobic processes, based on laboratory studies (Swisher, 1970). Figure d.2 shows
schematically the fate of LAS in the environment (deWolf and Feijtel, 1998). LAS evidently
undergoes nearly complete biodegradation, with 97-99% removal rates found in some
wastewater treatment plants (Brunner et al., 1988; Bevia et al., 1989; De Henau et al.,
1989). However, the mass loadings indicated above suggest that even at these removal
rates, appreciable amounts are released to receiving waters. Ventura et al. (1989) identified
LAS and a variety of other anionic, cationic and nonionic surfactants in both surface and
drinking water extracts.

183
Section 6. Case Studies

Figure d.2 LAS fate in the environment (after deWolf and Feijtel, 1998)

Alkylphenol ethoxylates such as NPnEO are evidently less biodegradable than LAS with
laboratory results ranging from 0-20% based on oxygen uptake (e.g. Swisher, 1970; Steinle,
1964; Pitter, 1968) and a wider range of removals from 0-90% based on specific analyses
such as UV and IR spectroscopy (Swisher, 1970). This suggests that only partial
degradation occurs, such as conversion from polyethoxylates to nonylphenol diethoxylate
(NP2EO), nonylphenol monoethoxylate (NP1EO), and nonylphenol (NP). Mass balances
carried out on treatment plants in Switzerland (Brunner et al., 1988) support this.

The findings of Brunner et al. and other reserachers, also show that the nearly complete
removal of surfactants from treated waters is not entirely due to biodegradation. Brunner et
al. indicated that 19% of the surfactant load entering a treatment facility is associated with
suspended solids, and other studies report levels up to 27% (Rapaport and Eckhoff, 1990),
or even in excess of 50% (Bevia et al., 1989). The surfactant load linked to suspended solids
is directed into sludge treatment processes via primary sedimentation. Surfactants such as
LAS are not biodegraded by either mesophilic or thermophilic anaerobic digestion (McEvoy
and Giger, 1985; Swisher, 1987) so a large proportion of these materials simply escapes
treatment and becomes associated with sludge solids.

The resulting concentrations of surfactants in sewage sludges can be substantial. LAS


concentrations measured in sludges often make up between 0.5% and 1.5% of the dry solid
mass, particularly for anaerobically digested sludges (McEvoy and Giger 1986; De Henau et
al. 1989; Holt et al. 1989; Marcomini et al. 1989). Bevia et al. (1989) reported LAS between
2% and 4% of the sludge solids weight. In a study of 29 Swiss treatment plants, LAS
concentrations averaged 4.2 and 2.1 g kg-1 respectively in anaerobic and aerobic sludges.
NP exceeded 1 g kg -1 dry sludge and, in some instances NP1EO and NP2EO exceeded 0.1
g kg-1 dry sludge (Brunner et al. 1988).

184
Section 6. Case Studies

Effects of surfactants on wastewater treatment

As stated previously, given these surfactant concentrations and the considerable effect that
surfactants can have on the properties of suspensions such as sludges, the performance of
such processes as thickening, conditioning, and dewatering may be strongly influenced by
these materials. For example, Bierck and Dick (1988) have shown that surface tension of
sludge solids is directly related to the capillary pressure available for solids compression
during the latter stages of vacuum filtration:
Ps,s = v [1/R1 + 1/R2]

Where,
Ps,s = the pressure or effective stress producing solids shrinkage,
v = the surface tension,
R1 and R2 = principal radii of curvature of the solid surface.

Thus the effect of surfactants, in lowering the surface tension, is to decrease the
compressive dewatering by allowing gas penetration of the solids cake. Campbell et al.
(1984, 1986) showed that a detergent could decrease the dewaterability of a sludge even
before the compressive phase, as indicated by capillary suction time (CST) measurements.
Household detergent added to anaerobically digested sludge at 0.2 and 0.3% by volume
caused significant increases in the CST (poorer dewaterability) which could not be
compensated for even by doubling the addition of cationic polymer used as the sludge
conditioner.

The implications of surfactants' influence on dewatering should not be underestimated.


Costs for the sludge conditioning polymer are the greatest operating cost for dewatering at a
WWTS such as Wilmington, and sludge dewatering and disposal represent up to 50% of the
total cost of wastewater treatment (Evans, 1988).

The biodegradation mechanism of LAS was described by Balson and Felix(1995). The
mechanism of breakdown of LAS involves the degradation of the straight alkyl chain, the
sulphonate group and finally the benzene ring. The breakdown of the alkyl chain starts with
the oxidation of the terminal methyl group (w-oxidation) through the alcohol, aldehyde to the
carboxylic acid as follows (see Fig. d.3a). The reactions are enzyme catalysed by alkane
monooxygenase and two dehydrogenases. The carboxylic acid can then undergo b-
oxidation and the two carbon fragment enters the tricarboxylic acid cycle as acetylCo-A. It is
at this stage that problems arise with branched alkyl chains, a side chain methyl group or a
gem-dimethyl-branched chain cannot undergo b-oxidation by microorganisms and must be
degraded by loss of one carbon atom at a time (a-oxidation, Figure d.3b). (Scott and Jones,
2000).

185
Section 6. Case Studies

Figure d.3a w-Oxidation of LAS (after Scott and Jones, 2000)

The second stage in LAS breakdown is the loss of the sulphonate group. The loss of the
alkyl and the sulphonate group from LAS leaves either phenylacetic or benzoic acids.
Microbial oxidation of phenylacetic acid can result in fumaric and acetoacetic acids and
benzene can be converted to catechol .

Figure d.3b a- Oxidation of LAS ( after Scott and Jones, 2000).

186
Section 6. Case Studies

Effects of the surfactants on the wider environment:

The presence of surfactants in sewage sludge may have undesirable environmental effects
if land application is the chosen disposal method. The surfactant molecules may leach to
groundwater contributing to groundwater contamination. Federle and Pastwa (1988) studied
the percolation of anionic and nonionic surfactants through a soil column. Most of the
surfactant was mineralised, but this process was found to be highly dependent on the
number of organisms present in the soil. A number of reports (e.g. Bevia et al., 1989; Holt et
al., 1989) attribute observed decreases of LAS concentrations over time in sludge-amended
soils to biodegradation, without evaluating possible migration. Marcomini et al. (1989)
reported a fraction of LAS in sludge-amended soil to be resistant to biodegradation over long
time periods. Table d.2 contains data on fate and persistence of surfactants in sludge
amended soils.

Table d.2 Fate and persistence of surfactants in sludge amended soils

Application Country Surfactant/ Soil Monitoring Final Half Life Author


Form derivative Concentration period Soil (days)
post Conc.
application -1
-1 (mg.kg )
(mg.kg )

Sludge onto SP LAS 22.4 6 months 3.1 Not Prats et al


soil 12 months 0.7 reported
Sludge onto CH LAS 45 12 months 5 9 Marcomini et al
soil NP 4.7 0.5
Surfactant D LAS Not reported 2 months Not 5-25 Litz et al
onto soil 6 months reported summer
66-117
winter
Sludge onto D LAS 16 76 days 0.19 13 Figge and
soil 27 106 days 0.44 26 Schoberl
Surfactant USA LAS 0.05 40 days Not 1.1- Knaebel et al
onto soil LAE 0.05 reported 3.6
Sludge onto SP LAS 16 90 days 0.3 26 Berna et al
soil 53 170 days Not 33
reported
Sludge onto UK LAS 2.6-66.4 (*) 5-6 months <1 7-22 Water et al
soil Holt et al
Sludge onto UK LAB 0.3-9.5 (*) 55 days 0-0.38 15 Holt and
soil Bernstein
Composted AUS NPE 14 000 14 weeks 1200 Not Jones and
wool scour reported Westmoreland
sludge
(* estimated cumulative load)

Not only may surfactants migrate to groundwater, but they may also carry hydrophobic
organic pollutants with them. The degree of partitioning of hydrophobic organic pollutants to
particles depends on the hydrophobicity of the pollutant and the amount of organic matter
contained in the particle. Dissolved organic matter tends to decrease the potential for
sorption by providing an additional aqueous phase to which the pollutant can partition
(Enfield et al. 1989). Partitioning of surfactant to sludge particles in the sewage treatment
plant would be expected to enhance the partitioning of organic pollutants to sludge. When
applied to land, desorption of surfactant could lead to pollutants also being released. Kile
and Chiou (1989) studied the effect of anionic, cationic and nonionic surfactants on the
water solubility of DDT and trichlorobenzene. The results were extremely surprising. As
would be expected, the solubility was enhanced when the surfactant was present at

187
Section 6. Case Studies

concentrations greater than the critical micelle concentration. There was also a solubility
enhancement at surfactant concentrations less than the critical micelle concentration.

In addition to the effects of surfactants in sludge on pollution of groundwater, the surfactants


may effect soil texture and water retention through processes similar to those discussed with
respect to sludge dewatering. Holtzclaw and Sposito (1978) determined LAS content in a
sludge amended soil to be high enough (1% of the fulvic acid fraction) that soil fertility could
be affected.

The fate of surfactants in sludges disposed of in landfills is somewhat surprising.


Concentrations of LAS up to 1% by weight have been found in recently deposited material,
with some amounts above 1 g.kg-1 even after 15-30 years (Marcomini et al., 1989). Given
that landfills function in a similar manner to anaerobic digesters, the persistence of LAS is
evidently due to its poor degradability in such environments. The role of surfactants in
mobilizing less hydrophobic contaminants into landfill leachate is thus a relevant concern.

Behaviour of nonionic surfactants:

Recent studies have revealed that fish living downstream of wastewater treatment plants
show oestrogenic effects [Purdom et al. 1994] as a result of alkylphenol polyethoxylates
(APE) and nonylphenol (NP) present in the water. Male fish produce vitellogenin, a yolk
protein which is formed under the influence of oestradiol and therefore is typically produced
by females. Hermaphrodite fish species have been found as well. The decomposition
products of APE, are considered as a potential cause, since their decomposition products
formed in WWTS (Giger et al. 1984) show slightly oestrogenic effects (Soto et al. 1991,
Jobling and Sumpter 1993).

Alkylphenol polyethoxylates (APE) usually enter surface waters via WWTS, where they
are degraded - but not totally - by microorganisms. In a first rapid step the ethoxylate groups
are split off by hydrolysis, and the metabolites nonylphenol (NP), nonylphenol ethoxylate
(NP1EO) and nonylphenol diethoxylate (NP2EO) are formed. These metabolites are more
toxic than the original substances. Due to the hydrophobic properties of the aromatic group
the second step of biodegradation occurs much slower. The interim products can also be
biodegraded to alkylphenoxy ethoxylate carboxylic acids (APEC). The second, slower,
step of biodegradation, does not always occur, and the fact that the metabolites are more
lipophilic than the parent compounds can cause an accumulation of interim products in
sludge and sediment. Nonylphenol, for example, was determined in digested sludge in
concentrations between 0,45-2,53 g.kg-1 dry weight (Giger et al. 1984). Approximately 50 %
of the APE occurring in the wastewater are estimated to reach the sludge as NP (Brunner et
al. 1988). Before prohibition of APE in washing agents NP, NP1EO and NP2EO
concentrations between 36-202 µg/l were found in drain channels of WWTS in Switzerland.
Now NP concentrations in drain channels from WWTS, are found at concentrations between
1 and 15 µg.l-1 in Switzerland and Germany; other metabolites (NP1EO, NP2EO, NP1EC)
are normally determined to be between 1 and 40 µg.l-1 (Ahel et al. 1994a, Ahel et al. 1994b,
Giger 1990). Concentrations of 15 µg.l-1 in drain channels of WWTS were determined in the
USA. In highly polluted streams average nonylphenol concentrations are determined to be in
the range 0.3 to 3 µg.l-1 (Ahel et al. 1994a), polyphenoxy carboxylic acids products are
predominant, whereas in sediment NP was the dominating degradation product. Due to their
high octanol/water partition coefficient (log 4.0-4.6) nonylphenol, NP1EO and NP2EO show
a tendency towards bioaccumulation in organisms. This was confirmed by residue analyses
(Table d.3). The bioconcentration factor in fish is approx. 300, in one case, however it
amounts to 1300.

188
Section 6. Case Studies

Table d.3: Environmental concentrations of degradation products of nonionic


surfactants
Environmental Substance Concentration Reference
compartment
Sewage sludge NP 0,45 - 2,53 g kg-1* Giger et al., 1984
0,03 g kg-1* Giger and Alder, 1995
WWTS-drain NP, NP1EO, NP2EO 36 - 202 µg l-1 Stephanou and Giger,
NP 1 10 µg l-1 1990
NP1EO, NP2EO 1 - 40 µg l-1
Streams NP 0,3 - 45 (2-3) µg l-1 Ahel et al., 1994b
NP1EO, NP2EO < 3 - 69 µg l-1
NP1EC, NP2EC < 2 - 71 µg l-1
Stream sediment NP 0,5 - 13 mg kg-1* Ahel et al., 1994b
Fish NP, NP1EO, NP2EO 0,03 - 7,0 mg kg-1* Ahel et al., 1993
Algae NP, NP1EO, NP2EO 80 mg kg-1* Ahel et al., 1993
Waterfowl (ducks) NP, NP1EO, NP2EO 0,03 - 2,1 mg kg-1* Ahel et al., 1993
* dry weight

Health effects of surfactants:

Prats.et.al, 1993 show significant differences between distribution of LAS homologs in water
and solids (sludges, sediments, and soils), as compared to the original distribution in
detergent formulations, yielding a lower LAS average molecular weight in water samples.
The change observed in the homolog distribution of LAS implies a reduction in the toxicity to
Daphnia, because a lower average molecular weight of LAS is less toxic. The risk
assessment of LAS to terrestrial plants and animals reported by Mieure et al. (1990) also
concludes that there are adequate margins of safety in the use of wastewater for the
irrigation of plant species. Adverse effects on plant and animal species (earthworms Eisena
foetids and Lumbricus terrestris) were observed at LAS concentration of 10 mg.l -1 , however
LAS concentrations in wastewater effluents are in a range 0.09 mg l-1 to 0.9 mg l-1 . These
figures give a safety margin in a range 10 to 100. The effect of surfactant on plant growth
from the use of sewage sludge is difficult to assess because in general the sludge promotes
plant growth. Adverse effects on plant growth were observed at 392 µg g-1 but long term
monitoring at a range of 46 environmental sites gave LAS concentrations of less than 3µg.g-1
. These figures give a safety margin of 131. For terrestrial animals the limit of no adverse
effects was 235 µg.g-1 giving a safety margin of 78. However, in looking at ecotoxicity from
WWTS effluents the less toxic surfactant residues and surfactant catabolites must be
considered and this requires analytical tests for these entities (Scott and Jones, 2000;
Schoberl, 1997).

Amounting to 2-4 g.kg-1 the acute mammalian (mouse, rat) toxicity of APE is low. Dermal
toxicity, however, is higher (500 mg.kg-1), and eye irritation is the highest with 5-100 mg.kg-1.
NP can be metabolised to a glucoronide in the body and excreted via the kidney. Nonionic
surfactants are more toxic for aquatic organisms than for mammals. The toxicity of APE
increases with decreasing number of ethoxylate units and increasing hydrophobic chain
length. Accordingly, the toxicity of the original substances is lower than the toxicity of the
metabolites NP, NP1EO and NP2EO, whereas the carboxylic acids are less toxic than the
ethoxylates. For instance the LC50 (48 hours) of NP16EO is 110 mg.l-1 for fish (Oryzias
latipes) and decreases to 11,2 and 1,4 mg.l-1 for NP9EO and NP, respectively (Yoshima,
1986). The LD50 (96 hours) for algae (Skeletonema costatum) is 27 µg.l-1, and the value for
rainbow trouts 480 µg.l-1 (Nayler 1992). The no observed effect concentration (NOEC) for
reproduction for Daphnia is in the range of 24 µg.l-1. These data show that the acute toxicity
of NP is considerably high.

In vitro toxicity studies with fish hepatocytes indicate that several decomposition products of
APE cause weak oestrogenic effects (Jobling and Sumpter 1993, White et al. 1994). Studies

189
Section 6. Case Studies

based on the vitellogenin synthesis revealed that NP, NP1EO and NP1EC have the same
activity (half maximum activity: around 16 µM). The oestrogenic activity, however, is 10
times lower than that of oestradiol (Pelissero et al. 1993). Other in vitro studies give hints on
potential differences between fish and mammalia regarding the binding to the oestrogen
receptor (Thomas and Smith 1993). However, vitellogenin synthesis in fish hepatocytes is
also induced by well-known phyto-oestrogens. Studies in the UK indicate that downstream of
the drain channels of WWTS vitellogenin is formed in male fish. After 1 to 3 weeks exposure
of fish in 15 drain channels of WWTS, displayed a high increase of vitellogenin synthesis
(Purdom et al. 1994). It is supposed that the decomposition products of APE, especially NP,
are mainly responsible for this effect. The assumption is confirmed indirectly by the results of
the in vitro studies with fish hepatocytes. However, it cannot be excluded that synthetic
oestrogens are also responsible for this effect. On the one hand their concentrations are
lower than the usual concentrations of NP, but on the other hand their activity is some orders
of magnitude higher. Experimental exposure of fish to NP or metoxychlor over 7 days
induced vitellogenin synthesis in male fish (Nimrod and Benson 1995). The dose required to
induce the vitellogenin synthesis was 300 times (approx. 150 mg.kg-1) higher than the
necessary dose of oestradiol.

Further research in this field, especially the conduction of experimental in vivo studies, is
urgently required to allow for a more reliable assessment of the exposure of fish populations
to oestrogenic chemicals and their potential effects.

Field investigations indicate that downstream of the drain channels of WWTS oestrogenic
effects may be induced in fish. The in vitro studies with fish hepatocytes seem to indicate
that the oestrogenic activity of synthetic oestrogens is some orders of magnitude higher than
the activity of decomposition products of APE. On the other hand the oestrogenic potency of
NP, NP1EO, NP2EO and NP1EC is very similar. Consequently, all degradation products
have to be taken into consideration. It seems advisable to suppose that the above chemicals
have additive effects.

Best environmental practice examples


One of the main success stories regarding the use and fate of surfactants is linked with eco-
labelling. Eco-labelling has been developed for the products used in dishwashing, laundry
and cleaning detergents in Scandinavia, Germany, Austria and other European countries.
Products with the ‘Swan’ and ‘Good Environmental Choice’ label do not contain LAS and
Nonylphenol and have gained considerable market share. In Sweden, products with these
labels accounted for more than 95% of sales by 1997 while in Finland they reached 15%.
Norway and Denmark had lower sales (source, Danish Environment Agency 2000). More
research is needed for the potential environmental effects of the alternatives used in these
LAS-free and NPE-free surfactants.

This public awareness and consumer choice, lead to the use of LAS in Sweden falling from
6300 tonnes a year to 260 tonnes a year. The Danish Environment Agency launched a
public campaign against LAS in September 1999. Currently about 2500 tonnes a year of
LAS are used in Denmark.

During the development of the “Swan” mark, Stockholm water company identified the need
to have an alternative for taking care of hazardous waste in the household rather than
flushing it into the UWW collecting system. Environmental stations, or collection points were
established and an extensive public information campaign was carried out about the impacts
of household products on the aquatic environment [Ulmgren, 2000a, 2000b].

Detergents and cleaning agents containing alkylphenolethoxylates (APEO), such as NPE,


are being gradually phased-out under various initiatives and voluntary agreements in EU.
Distearyl-dimethylammonium chloride (DSDMAC), widely used in laundry softeners, was

190
Section 6. Case Studies

also substituted with more degradable substances during the 1990s in Germany [Greiner,
1996] and is currently under scrutiny in the rest of the EU.

The eco-labelling combined with a public awareness campaign could therefore influence
consumer choice and reduce contaminant discharges in the UWW from domestic products.

More research is necessary to experimentally determine the role of surfactants in sludge


treatment processes and following sludge disposal in the environment. Specific effects to be
investigated are

• impacts on sludge thickening, conditioning, and dewatering processes and


• transport and mobilization of hydrophobic organic contaminants when sludges are
landfilled or land-applied. Also anticipated is an improved fundamental understanding
of mechanisms by which surfactants are incorporated into sludge solids.

Some important research gaps and necessary research are summarised as follows:

Effects of endocrinally active chemicals have not yet been systematically investigated in
amphibian and reptiles. In this field nearly no knowledge is available.
• Chemical methods for the detection of traces of synthetic oestrogens and their
metabolites must be elaborated, since only very few data are available on
environmental concentrations, especially regarding concentrations in drain channels
of wastewater treatments plants. Furthermore, data material on NP concentrations in
drinking water and organisms including humans is insufficient.
• The ecotoxicological relevance of vitellogenin production in male animals has to be
elucidated. Which interrelations exist between the problem of vitellogenin production
and further estrogenic and ecotoxicological effects of NP and other chemicals? To
answer these questions in vivo experiments using histopathological, biochemical,
endocrinological and reproduction biological methods have to be conducted.
Furthermore, insufficient information is available about the bioaccumulation of these
chemicals. In a further step the problem should be investigated by more
comprehensive field studies.
• The mechanisms of chronic effects of alkylphenols (modes of action) must be studied
in more detail.
• Finally, in vitro assays should be elaborated to identify and estimate the oestrogenic
activity of existing new chemicals in fish and other organisms.

191
Section 6. Case Studies

(G) Use of Polyelectrolytes; The Acrylamide Monomer in Waste Water Treatment

Polyacrylamide (PAM) is a widely used flocculant in water treatment applications. Some


20,000 tonnes is used in the USA for this purpose each year. Concerns with its use are that
it can degrade to the acrylamide monomer which is known to affect the central and
peripheral nervous systems and is also believed to be carcinogenic. Safe levels for this
chemical are said to be 300 µg l-1 over a ten-day period and 2 µg l-1 over a seven year period
(EPA). PAM is used in other applications such as an aid in irrigation (Trout et al. 1995) and
in pulp and paper manufacture. The EPA also notes that it is used in formulating grouting for
tunnels and sewers. Effluents from a sewage works which used PAM as a flocculant in the
UK were reported to be 2.3 to 17.4 µg l-1. High levels of the monomers have been reported
in acrylamide manufacturing plant effluents. In this case the raw effluent contained 1100 µg l -
1
and the treated effluent 280 µgl-1 (EPA). Both PAM and its monomer are very soluble in
water and the presence of PAM in soil causes leaching of microorganisms by ground or
irrigation water.

PAM is shown to degrade by biological action and photolytic effects (Nakamiya 1995).
Experiments have shown that polyacrylamide solutions in a bottle covered with plastic film
and left outside can contain significant amounts of the monomer after two weeks exposure
(Smith et al. 1996). The polymer can also be degraded by turbulent shear stress in pumps
and pipes (Rho et al. 1996). Once the polymer degrades the monomer is also subjected to
more rapid degradation in which it is decomposed to acrylic acid and ammonia. These are
non toxic as acrylic acid degrades to CO2 and water in a day in soil (Staples et al. 2000) and
is thus not an ecological problem. The degradation of acrylamide under favourable
conditions by pseudomonas species immobilised in calcium aliginate took one day (Nawaz
et al. 1993). The EPA say that degradation of acrylamide in river water takes 4 to 12 days
and is more rapid in summer than winter. Due to its solubility adhesion of the monomer on
soil is unlikely, though it is reported that it is partially removed by secondary activated
sludge.

The general conclusion of the EPA paper is that the monomer is not an environmental
hazard when released in small quantities to the aqueous environment. Tests with fish would
indicate this. The monomer is relatively biodegradable within days compared to the time
span of years for substances such as PCB. There are two areas where there could be some
concern and these are control of effluents from acrylamide manufacturing and use in
drinking water treatment. The fact that the monomer is detected in water treatment plants
where the residence time is only a few hours suggests that the PAM flocculant could have
significant residual amounts of monomer.

There is a web site (www.fwr.org/waterg/dwi0084.htm) which quantifies some of the points


mentioned. Among the points noted are:

• Chlorination and the presence of potentially toxic elements can stop acrylamide
degradation by passifying the bacteria present.
• Degradation of the monomer is not pH dependant
• 50% of PAM is removed in aerated sludge and trickle bed filters.

A significant drop in the percentage of monomer present in the PAM used for flocculation
has eased the likelihood of serious contamination of water. The present level of monomer
present in grades of PAM used for water treatment is 0.3% and has dropped from 0.8%.
However PAM used in grouting has a much higher monomer content and the use of this
particular grade has caused the monomer to leak into grouted sewers.

To conclude it seems that whenever water is sent into the environment it would be safe to
use PAM as a coagulant. Problems may arise when it is used in a stream which is

192
Section 6. Case Studies

subsequently sterilised by chlorine or by another disinfectant. This removes the bacteria that
are needed to degrade the PAM and it would be a problem with using other organic
polymers as well. It might be concluded that a polymer grade containing just 0.3% of
monomer is very pure and improvements in purity might not be practically feasible.

Therefore in treating drinking water some intermediate step may be necessary to degrade
the monomer after flocculation and before adding the disinfection agent. This could involve a
holding lagoon or treatment using activated charcoal. In any case the case for or against the
use of PAM in flocculating drinking water lies in the conflicting aims of acrylamide
degradation and product sterilization. Its use in the treatment of drinking water needs
continuous monitoring and, if more stringent regulations are placed on the monomer
concentration in drinking water the issue will become a concern.

193
Section 6. Case Studies

(h) Landfill Leachate

Introduction

In the past treatment of leachates in WWTS were favoured but due to the effects of dilution
in the UWW system, there is little, if any information on the elimination of persistent
compounds (Alberts, 1991). In Germany, a recent requirement has been the proper
preliminary treatment of leachate before discharge either directly to surface waters or
indirectly to municipal WWTS.

With the introduction of redrafted legal conditions in Germany, strict demands have been
placed on the purification performances of leachate treatment plants. Thus, the treatment of
organic substances and nitrogen compounds using nitrification and denitrification, is required
prior to direct discharge to a receiving watercourse.

Wastewater and leachate quality requirements in Germany

Definitions of direct and indirect discharge of wastewater are as follows:

• Direct discharge: To discharge wastewater directly must conform to standards of


water quality in the receiving water.
• Indirect discharge: Discharging wastewater directly into a public WWTS requires that
the concentration of COD, BOD, NH4-N, AOX and potentially toxic elements must be
reduced to the same levels found in domestic wastewater.

Standard values for the composition and quality of non-domestic wastewater discharged to a
public WWTS are stated in guideline/directive ATV-A 115 (worksheet for indirect
dischargers). The standard concentrations for potentially toxic elements are shown in Table
h.1.

Table h.1: Standard concentrations for soluble and insoluble inorganic substances in
wastewater from non-domestic sources [ATV-A 115, 1994].

Potentially toxic Symbol Standard


element Concentrations
[mg/l]
Lead Pb 1
Cadmium Cd 0.5
Chromium Cr 1
Chromium (VI) Cr(VI) 0.2
Copper Cu 1
Nickel Ni 1
Mercury Hg 0.1
Zinc Zn 5
Regulation AbwV: “Requirements for discharging wastewater into watercourses”

The Wastewater Regulation (AbwV) places general requirements on the introduction of


wastewater into receiving watercourses. A permit for discharging wastewater into a
watercourse can only be granted, when the limit values for the pollution load at the point of
discharge are observed. Dilution of wastewaters in order to reach the required concentration
values is not permitted.

Requirements for wastewater from landfill sites are given special attention in annex 51 of the
regulation. It is a requirement that the quantity and pollution load of landfill leachate must be

194
Section 6. Case Studies

kept low by proper measures and operation at the landfill installation. The requirements
listed in Table h.2 relate to the discharge site of leachate into watercourses.

Table h.2: Requirements for wastewater quality at point of discharge (qualified sample
or 2 hour mixed sample) [AbwV, annex 51, 1999].

Parameter Unit Value


COD* mg/l 200
BOD mg/l 20
Ntotal** mg/l 70
Ptotal mg/l 3
Hydrocarbons, total*** mg/l 10
N02-N mg/l 2
Fish toxicity GF 2
* For wastewater with a COD value (before treatment) of more than 4000 mg/l, the COD
effluent value in the qualified sample or in the 2 hours mixed sample must be reduced by 95 %.
** Sum of ammonium-, nitrite- and nitrate-nitrogen (Ntotal) or total bound nitrogen (TNb). The
requirement applies to a wastewater temperature of 12 °C. A higher limit concentration of 100 mg/l is
permitted when the decrease of nitrogen load amounts to at least 75 %.
*** The requirement relates to the qualified sample.

The requirements listed in Table h.3 below relate to leachate before mixing with other
wastewaters.

Table h.3: Requirements on leachate before mixing (qualified sample or 2 hours mixed
sample) [AbwV, annex 51, 1999
Parameter Unit
[mg/l]
AOX* 0.5
Mercury 0.05
Cadmium 0.1
Chromium 0.5
Chromium VI* 0.1
Nickel 1
Lead 0.5
Copper 0.5
Zinc 2
Arsenic 0.1
Cyanide, easily released* 0.2
Sulphide* 1
* value for the qualified sample.

195
Section 6. Case Studies

Leachate can be mixed with other wastewater for common biological treatment only when:

• fish, indicator bacteria and Daphnia toxicity of a representative sample is not


exceeded (see Table h.3). It has to be stated that exceeding the GF value is not
caused by ammonia (NH3).
• a DOC elimination rate of 75 % is reached.
• leachate shows a COD concentration lower than 400 mg.l-1 before the common
biological treatment.

Table h.4: Fish, indicator bacteria and Daphnia toxicity [AbwV, annex 51, 1999]

Fish toxicity GF = 2
Daphnia toxicity GD = 4
Indicator bacteria toxicity GL = 4

Landfill Leachate

Formation:
A substantial proportion of pollutant emissions from landfill sites enters percolating through
the landfill. Rain water (and other sources of water) entering unsealed sections of the landfill
undergo chemical and biological transformation in the body of the landfill to form leachates.
Pollutants are taken up by solution processes or are carried in suspension. This loaded
water, the so called leachate, is collected at the base of the landfill in a drainage pipeline.

The quantity of leachate produced depends principally on rainfall and the state of the landfill.
At new, unsealed landfill sites, the total calculated rainfall collects as leachate. During the life
of the landfill leachate quantity reduces to 10 – 20 % of total rainfall, with an increase in
superficial sealing.

Composition:
Leachate is a heterogenezous mixture, often containing a high concentration of persistent
biological and toxic compounds. The type of material deposited in the landfill determines the
composition of the leachate. Leachate composition and pollutant concentration are also
influenced by the rate of biochemical processes in the body of the landfill. After an initial
intensive phase biological and chemical reactions in the landfill slowly subside. As the age of
a landfill increases, the quota of easily degradable compounds in and the COD/BOD5 ratio
rises (Leonhard, Wilderer, 1992).

Some of the main pollutants found in landfill leachates are organic compounds, such as alkyl
phenols, chlorinated phenols, polycyclic aromatic hydrocarbons (PAH), dioxins and furans.
Leachate from special waste landfills tends to have higher concentrations of inorganic
substances compared to leachate from household refuse landfills; chlorides, sulphates and
fluorides represent the main load.

Table h.5 gives an overview of the relevant pollutant concentration in landfill leachate.

196
Section 6. Case Studies

Table h.5: Mean composition of leachate from: industrial or special waste landfills,
and household refuse landfills, in Germany [Ehrig et al., 1988]

Parameter Units Industrial and special waste Household refuse landfill


landfill
Range Mean value Range Mean value
pH - 5.9 – 11.6 7.7 3.5 – 9 7.5
COD mg O2.l-1 50 – 35000 5746 500 - 60000 5000
BOD5 mg O2.l-1 41 – 15000 2754 100 - 45000 1500
Conductivity mS.cm-1 2110 – 183000 28217 - 10000
Chloride * mg.l-1 36 – 126300 13257 100 - 15000 2000
Sulphate mg.l-1 18 – 14968 2458 50 - 3000 300
Ammonium* mg.l-1 5 – 6036 921 20 - 3000 500
Nitrite* mg.l-1 0.02 - 131 7.3 - 0.5
Nitrate* mg.l-1 0.1 - 14775 606 0 - 50 3
Total-N* mg.l-1 1 - 3892 461 20 - 4000 600
Total-P* mg.l-1 0.03 - 52 7.9 0.01 - 10 1
Fluoride mg.l-1 0.1 - 50 13.3 - -
Total cyanide mg.l-1 0.007 - 15 1.3 - -
Easily released mg.l-1 0.008 - 1 0.2 - -
cyanide
Arsenic* mg.l-1 2 - 240 51 0.1 - 1000 20
Lead* mg.l-1 4.3 - 650 155 20 - 1000 50
Cadmium mg.l-1 0.2 - 2000 144 1 - 100 5
Copper* mg.l-1 1.3 - 8000 517 10 - 1000 50
Nickel* mg.l-1 14.2 - 30000 2096 20 - 2000 200
Mercury mg.l-1 0.17 - 50 5.5 - 10
Zinc mg.l-1 20 - 272442 2936 100 - 10000 1000
Chromium (total)* mg.l-1 0.009 - 300 18.1 0.02 - 15 0.2
Iron mg.l-1 0.38 - 2700 144 1 - 1000 50
Phenol index mg.l-1 0.01 - 350 26 - 0.006
Hydrocarbons mg.l-1 0.01 - 424 30 - -
AOX mg.l-1 44 - 292000 32000 320 - 3350 2000
*leachate substances not influenced by the biochemical state of the landfill matter.

Treatment Practices
Different methods can be used for treating leachate from landfills, consisting principally of
biological, physical and chemical processes. A specific process can only treat a particular
substance categories in wastewater. Because of the wide range of pollutants found,
leachate treatment has to be performed using a combination of suitable processes. The
choice of treatment processes depends closely on the leachate composition. A short
description of processes used in Germany for treating leachate follows below.

Biological Practices:
Biological process can be used to degrade leachate pollutants into mineral end products. To
enable degradation specialised microorganisms must be enriched in the bioreactors by
proper process conditions. Nitrogen elimination can also be obtained by nitrification and
denitrification. Biological processes, especially the aerobic ones, are efficient and cost-
effective in comparison with the chemical-physical processes (Rudolph et al., 1988). The
activated sludge process and the biofilm process are both use to biologically treat leachate
from landfills.

Activated sludge : In the activated sludge process micro-organisms aggregate in the form
of biological sludge flocs suspended in the wastewater flow, through the treatment plant. The
formation of settleable sludge is decisive for the efficient working of the activated sludge
process. Leachates though are often characterized by high salt concentrations and high

197
Section 6. Case Studies

concentrations of persistent organic compounds, forming a fine, dispersed sludge, which


does not settle readily. So the biomass passes through the activated sludge plant without
treatment. Under these conditions biological degradation of pollutants is not possible
(Albers, 1991, Wilderer et al., 1989).

Biofilms: Biofilm systems can be used to prevent the loss of biomass by washing-out, which
may be experienced in the activated sludge process. Biomass growth is encouraged by
attachment to support surfaces, in form of biofilm. SBBR, the so called sequencing batch
biofilm reactors, are also used for cleaning leachate with high salt concentrations and a high
percentage of persistent organic compounds. Advantages of the biofilm processes are the
small space requirement and the high flexibility in service (Wilderer et al, 1989).

Chemical-physical methods:
Flotation, precipitation and flocculation, adsorption, reverse osmosis and thermic techniques,
belong to the chemical-physical processes for treating leachate. Other chemical-physical
processes are chemical oxidation and membrane filters.

Flotation: Flotation is used for separating specific low density substances and suspended
solid constituents or liquid substances. In a leachate treatment plant they are normally the
first step of the treatment process.

Precipitation, flocculation and sedimentation: In leachate treatment iron and aluminum


salts are usually used to achieve precipitation and flocculation, which is then followed by
sedimentation of the settleable material. Using this process, potentially toxic elements in the
form of hydroxides and disperse organic substances, are separated with a removal
efficiency of 40 %.

Adsorption: At a leachate treatment plant, adsorption by activated carbon is always used in


combination with biological pretreatment or with a chemical-physical process. Any persistent
organic compounds not degraded in the pretreatment step and AOX compounds, can be
separated in the back-washed carbon filters. Through adsorption processes, an
agglomeration of the solute molecules takes place on the activated carbon interface.
Advantages of the adsorption process are; simplicity of the technology involved; relatively
low running costs; and possible thermic recycling of the exhausted carbon (Detter, 1998).
Regeneration of activated carbon is problematic and expensive though.

Chemical oxidation: In the oxidation stage of a leachate treatment plant non-biodegradable


and inhibitory organic substances can be oxidised or reduced. In ideal conditions, given a
sufficient supply of medium for oxidation, complete mineralisation can be achieved.
Substances such as potentially toxic elements and neutral salts remain in solution and are
not transformed (Döller, 1998). Hydrogen peroxide/UV or ozone/UV are the mainmedium
used for oxidation medium in leachate treatment. In practice, leachate is enriched with
ozone (O3) or hydrogen peroxide (H2O2) and afterwards conducted to the UV radiators.

Thermal treatment: In thermal treatment pollutants in leachate are separated from water
(stripping), concentrated (vapourising) and mineralized (combustion). Due to the different
volatilities of water, organic solvent and of dissolved and suspended substances, partition by
distillation can be achieved. Thus volatile hydrocarbons contained in the leachate can be
separated with a stripping step. With the vapourising process, inorganic and organic residual
substances are obtained separately in a chemically unchanged form. Then, the concentrated
organic phases must be made inert by combustion. Proper treatment of the exhaust gases
is necessary to meet air quality emission standards. During the vapourisation of critically
loaded leachate, single toxic halogen organic compounds such as polychlorinated biphenyls,
dibenzo-dioxins and dibenzo-furans can enter the distillate. In this case, post treatment with
activated carbon is essential (Leonhard, Wilderer,. 1992).

198
Section 6. Case Studies

Reverse Osmosis: In the treatment of leachate, reverse osmosis is only used for
desalination and concentration of the leachate to be treated. During operation, membrane
fouling caused by suspended and colloidal substances has to be prevented, which would
otherwise result in a regression of the treatment performance, due to reduction of the
permeate flow. At the end the accumulated concentrate must be subjected to additional
treatment. The principle advantage of reverse osmosis is the low energy cost.

Membrane filtration: The membrane technique has been successfully used for cleaning
leachates. A biological process tank is combined with post membrane filtration (nano and
ultrafiltration) for biomass retention. The activated sludge tank is in part operated by
overpressure in order to reach higher oxygen solubility and with this, a better oxygen supply
for the micro-organisms. The removal of treated water occurs continually over a cross-flow
membrane filtration plant. The membrane modules are especially capable of finely dispersed
sludge retention (Krauth,.1994).

Conclusions

In Germany, the discharge of wastewater into public WWTS and into receiving watercourses
is strictly regulated. Thus, leachate must also be treated before discharging and legal
regulations set high requirements on the performance of leachate treatment plants (ATV-
A115 1994 and AbwV 1999).

Prior to the discharge of non-domestic wastewater into a public WWTS, concentrations of


COD, BOD, NH4-N, AOX and potentially toxic elements must be reduced to at least
domestic wastewater standards. Purified leachate contributes only a relatively small
proportion of the pollutant load WWTS.

In ordinary analysis of treated and untreated leachate, only parameters such as COD, BOD
and AOX are determined. Additional quantification of high and low volatile hydrocarbons,
organic acids, phenols and single organic halogen compounds is necessary to adequately
describe the potentially hazardous impact of leachate.

In addition, it has to be taken into account that waste products loaded with pollutants
frequently arise from leachate treatment: toxic surplus sludge results from biological
treatment; charcoal is produced during adsorption processes; and polluted concentrates
form during vaporisation. To minimize the problematic emission of pollutants into the
environment, additional treatment of exhaust gases and proper disposal of the waste
residues are required.

199
Section 6. Case Studies

(i) Potentially Toxic Elements (PTE) transfers to sewage sludge

Sludges from conventional sewage treatment plants are derived from primary, secondary
and tertiary treatment processes. The polluting load in the raw waste water is transferred to
the sludge as settled solids at the primary stage and as settled biological sludge at the
secondary stage. Potentially toxic elements are also removed with the solids during the
primary and secondary sedimentation stages of conventional wastewater treatment. Metal
removal during primary sedimentation is a physical process, dependent on the settlement of
precipitated, insoluble metal or the association of metals with settleable particulate matter.
Minimal removal of dissolved metals occurs at this stage and the proportion of dissolved
metal to total metal in the effluent increases as a result. The efficiency of suspended solids
removal is the main process influencing the extent of metal removal during primary
wastewater treatment. However, the relative solubilities of different elements present in the
wastewater are also important (Table i.1). Thus, Ni shows the poorest removal (24 %) during
primary treatment whereas 40 % of the Cd and Cr in raw influent is transferred to the primary
sludge. Primary treatment typically removes more than 50 % of the Zn, Pb and Cu present in
raw sewage.

The removal of metals during secondary wastewater treatment is dependent upon the
uptake of metals by the microbial biomass and the separation of the biomass during
secondary sedimentation. Several mechanisms control metal removal during biological
secondary treatment including:

• physical trapping of precipitated metals in the sludge floc


• binding of soluble metal to bacterial extracellular polymers

In general the patterns in metal removal from settled sewage by secondary treatment are
similar to those recorded for primary sedimentation. However, the general survey of removal
efficiencies listed in Table i.1 suggests that secondary treatment (by the activated sludge
process) is more efficient at removing Cr than the primary stage. Operational experience
and metal removals measured by experimental pilot plant systems provide guidance on the
overall likely removal and transfers to sludge of potentially toxic elements from raw sewage
during conventional primary and secondary wastewater treatment. This shows that
approximately 70 – 75 % of the Zn, Cu, Cd, Cr, Hg, Se, As and Mo in raw sewage is
removed and transferred to the sludge (Blake, 1979) and concentrations of these elements
in the final effluent would be expected to decrease by the same amount compared with the
influent to the works. Lead may achieve a removal of 80 %, whereas the smallest overall
reductions are obtained for Ni and approximately 40 % of this metal may be transferred to
the sludge.

The majority of potentially toxic elements in raw sewage are partitioned during wastewater
treatment into the sewage sludge or the treated effluent. However, atmospheric volatilisation
of Hg as methylmercury, formed by aerobic methylation biotransformation processes, is also
suggested as a possible mechanism contributing to the removal of this element during
secondary wastewater treatment by the activated sludge system (Yamada et al., 1959).
Whilst it some of the Hg removal observed in activated sludge may be attributed to
bacterially mediated volatilisation, it is unlikely that this is a major route of Hg loss because
of the significant quantities of Hg recovered in surplus activated sludge (Lester, 1981).

200
Section 6. Case Studies

Table i.1 PTE removals and transfer to sewage sludge during conventional urban
wastewater treatment (Lester, 1981)

PTE Removal (%)


Primary(1) Secondary(2) Primary + Primary +
secondary secondary(3)
Zn 50 56 78 70
Cu 52 57 79 75
Ni 24 26 44 40
Cd 40 40 64 75
Pb 56 60 70 80
Cr 40 64 78 75
Hg 55 55 80 70
Se 70
As 70
Mo 70
(1)
Mean removal (n = 5) from raw sewage and transfer to sludge during primary sedimentation
(2)
Mean removal (n = 9) in activated sludge from settled sewage (3)Blake (1979)

201
Section 6. Case Studies

(J) Effect of chemical phosphate removal on potentially toxic element content in


sludge

The chemical treatment of wastewater to remove phosphorous is increasingly practised to


control P discharges and as a measure to reduce eutrophication of sensitive water courses.
This also has the advantage of increased BOD removal, reduction in polyelectrolyte
coagulant consumption for sludge thickening, elimination of hydrogen sulphide in sludge
digesters and reduced consumption of chemicals for exhaust gas scrubbing (Abendt, 1992).
High rates of P removal can be achieved from wastewater using common precipitants such
as aluminium sulphate (alum) and ferric chloride although this influences both the quality
and quantity of sludge produced (Yeoman et al., 1988). Chemical precipitation also
enhances the removal of potentially toxic elements from sewage effluent compared with
conventional treatment practices, increasing the transfer of metals to sewage sludge and the
content of metals in sludge. For example, Stones (1977) measured the reductions in metal
concentrations in sewage effluents obtained after an 18 h settling period with aluminium
sulphate (Al2(SO4)3) compared with sedimentation without Al salt. The removal of all the
elements examined was increased by the addition of aluminium sulphate compared to the
unamended control, except for Ni (Table j.1). The removal of Cu and Zn from the effluent
was raised by approximately 50 % by chemical treatment compared with removals achieved
by sedimentation without addition of Al. Lead removal increased by about 80 % and the
largest overall increase relative to the control was obtained for Cr. In the case of Cr,
precipitation with aluminium sulphate increased the recovery of this element in the sludge
almost by a factor of three.

Table j.1 Effect of chemical precipitation on metal removals (%) from raw sewage after
18 h sedimentation (Stone, 1977)

PTE Unamended Al2((SO4))3 Removal relative


control at 400 mg l-1 to control (%)
Zn 50 73 48
Cu 57 90 56
Ni 19 19 0
Pb 54 96 79
Cr 22 63 193

Iron-based precipitants are marketed for use in wastewater treatment may be derived from
industrial by-products of titanium oxide production. Such by-products may contain significant
concentrations of potentially toxic elements (PTEs) with potentially undesirable effects on
the metal content of sludge (Thiel, 1992).
An example of the effects of Fe dosing with industrial by-product on the maximum potential
increase in the PTE content of activated sludge is shown in Table j.2. The typical dosing
rates of FeSO 4 are typically in the range is 15 – 30 mg Fe salt l-1, but may increase up to 50
mg Fe salt l-1, to comply with the discharge requirements for P in the Urban Waste Water
Treatment Directive (CEC, 1991). The calculations suggest that dosing with FeSO4 may
potentially increase the Cd content of activated sludge by approximately 300 % to 6 mg kg-1
ds from a typical background value of 1.5 mg Cd kg-1 ds, assuming the maximum likely dose
rate of 50 mg Fe salt l-1 and that secondary sludge production is equivalent to 250 mg l-1 of
total solids (UKWIR, 1997). The Ni content in activated sludge may theoretically increase by
130 % compared to sludge without Fe addition, whereas Pb and Zn concentrations may
increase by about 10 % with Fe dosing. These increases in sludge content remain well
within the current quality standards for agricultural use (CEC, 1986). However, the revision
of the Directive on land application (CEC, 2000b) will introduce more stringent limit values
for PTEs and the use of Fe salts from industrial processes could potentially penalise the
acceptability of sludge for use in agriculture under the new regulatory regime. Furthermore,

202
Section 6. Case Studies

the potential increase in the metal content of sewage sludge, resulting from the use of
industrial-grade chemical precipitants, could also be considered as unsatisfactory because it
erodes the beneficial reductions in metal inputs that have been achieved through the
successful control of trade effluent discharges.

The quality and metal content of low-grade chemical precipitants for use in wastewater
treatment should be examined to ensure that they do not significantly increase the metal
content of sludge. In Germany, for example, composition standards are recommended for
Fe and Al-based coagulants used for sewage treatment and sewage sludge conditioning
(Schumann and Friedrich, 1997). The use of potable water grade Fe salts should be
considered for sewage treatment (Thiel, 1992) to avoid potential problems associated with
contamination with potentially toxic elements. In practice, there are few published data on
the effects of chemical precipitants on sludge metal contents and Fe and Al dosing. One
example from the literature (Yeoman et al., 1993) showed no consistent effects of chemical
treatment with Al or Fe salts on potentially toxic elements in sewage sludge from Beckton
WWTS in the UK (Table j.3). However, the significance of the direct metal inputs in chemical
precipitants will increase as industrial discharges are effectively controlled and as diffuse
inputs from domestic sources and run-off become the predominant sources of potentially
toxic elements entering the wastewater collection system.

Table j.2 Metal concentrations (mg kg-1) in Fe precipitants and activated sewage
sludge (UKWIR, 1997)

PTE FeSO4 Increase in FeCl2 salt Increase in Activated


salt activated activated sludge
sludge due sludge due without Fe
to FeSO4 to FeCl2
Zn 348 70 26 5.2 600
Cu 5 1.0 51 10 400
Ni 160 32 120 24 25
Cd 22 4.4 3.0 0.6 1.5
Pb 64 13 22 4.4 110
Cr 32 6.4 236 47 -

Table j.3 Effect of chemical P removal on the PTE content of sludge digested sewage
sludge(1) (adapted from Yeoman et al., 1993)

Sludge type Salt addition Concentration (mg kg-1) ds


Cd Cu Ni Pb Zn
Digested None 5.4 159 24 137 231
Digested + Al Raw sludge 5.4 142 19 62 148
Digested + Al Activated sludge 4.5 254 22 168 184
Mean 4.9 198 20 115 166
Digested + Fe Raw sludge 8.5 195 40 253 300
Digested + Fe Activated sludge 4.8 95 18 155 121
Mean 6.6 145 29 204 211
(1)
Sludge was collected from Beckton WWTS, sludges were digested in laboratory scale digesters (75
% raw sludge, 25 % activated sludge)

Waste products from water treatment and industrial processes, incinerator ash and acid
mine drainage have potential for re-use as P precipitants in wastewater treatment processes
(Fowlie and Shannon, 1973). For example, Oostelbos et al. (1993) treated Fe-enriched
sludge from water treatment with hydrochloric acid to convert ferric hydroxide to ferric
chloride for use in sewage treatment for phosphate removal, and as a dewatering agent in

203
Section 6. Case Studies

sludge conditioning. Verberne (1992) considered that the use of water treatment sludges as
chemical precipitants for P removal was technically feasible and would depend on the
agreement and acceptance of the approach by water and sewage treatment authorities. The
recovery of Fe and Al from acid mine drainage is another source of chemical precipitants
that can be used for P removal during sewage treatment (Bouchard et al., 1996). The re-use
of secondary resources for precipitating P during wastewater treatment is intuitively
attractive and also alleviates the environmental problems and impacts associated with
disposal of those wastes. However, some product types derived from waste materials are
potentially contaminated with potentially toxic elements that accumulate in the sludge
(Fowlie and Shannon, 1973). Therefore, the metal content of waste derived products should
be established, and the potential consequences for sludge quality determined, before a
particular product is accepted for use as a chemical precipitant in wastewater treatment.

204
Section 7. Report Synopsis, Discussions and Conclusions

7. REPORT SYNOPSIS, DISCUSSION AND CONCLUSIONS


7.1 Report Synopsis

7.1.1 Scope of the study

The European Union is introducing an integrated policy to promote sustainable water use
through the Water Framework Directive-2000/60/EC (WFD) based on a long-term
protection of water resources. A strategic aspect of this is the progressive decrease in
contaminant discharges to the aquatic environment. Allied to this water policy is the
amended proposal by the European Commission (COM/2001/17) listing 32 priority
substances to be phased out and 11 hazardous substances that will be subject to
emission controls and quality standards in accordance with Article 16 of the WFD.
Furthermore, Directive 86/278EEC concerning the use of sewage sludge in agriculture
(USSA) is undergoing major revision of the quality standards for potentially toxic
elements and organic contaminants in sludge and metal concentrations in sludge-treated
soil. The urban wastewater (UWW) collection system is one of the main facilities used for
the disposal of many types of commercial and domestic wastes that contain potentially
toxic elements and organic pollutants. It also receives unintentional diffuse inputs of
contaminants in storm run-off from paved surfaces. However, wastewater treatment
processes are effective in mitigating the discharge of many substances to surface waters
with the treated effluent. This is achieved principally through aerobic biological
transformations or because a significant proportion of the contaminant load is transferred
to the sewage sludge. Centralised collection and treatment of urban wastewater and
sewage sludge is therefore a pivotal link in defining the pathways and fate of
contaminant releases to the environment.

A major review of scientific, operational and regulatory information and literature from
published sources, research institutions, industrial operators and environmental agencies
has pooled current knowledge and developed a data-base of the sources and pathways
of pollutants in the wastewater treatment system (WWTS) within the European context.

The main objectives of this study were to determine the multiple sources of potentially
toxic elements and organic pollutants entering UWW, to determine quantitatively the
amounts of pollutants passing into the influent of wastewater treatment plant (WWTP),
and to assess the effects of treatment processes on the fate of both inorganic and
organic pollutants in sewage sludge and treated effluents. This information was to be
used to identify problems, to make recommendations and enable optimum reduction of
pollutant inputs, and to identify areas where data are lacking and where further research
is required. The significance of the inputs and types of contaminants from different
sectors connected to the wastewater collection system and potential opportunities and
practical measures to reduce the extent of contaminant discharges to sewer are
discussed. Potentially toxic elements are routinely measured in wastewater and sludge
and an extensive data-base of information has accumulated on the concentrations and
fate of these elements in environmental media. Several important groups of organic
contaminant have also received considerable attention (eg PAHs, PCBs, PCDD/Fs), but,
in general, the amount of published information on organics is limited compared with
potentially toxic elements due to the high cost of analysis, and need for specialist
analytical facilities and the absence of standardised methodologies.

More information has been identified for potentially toxic elements, which have been
subject to more detailed monitoring, as they are relatively easy to analyse using routine
and inexpensive tests and environmental or food chain impacts are much easier to
quantify where high soil loadings have occurred. Much less information is available on

Pollutants in Urban Waste Water and Sewage Sludge 205


Section 7. Report Synopsis, Discussions and Conclusions

organic pollutants where some six thousand or more compounds have been identified.
Many of these cannot be routinely determined in the majority of laboratories due to lack
of appropriate instrumentation, the absence of a unified methodology and expense.

The type of pollutants and the magnitude of loadings to the WWTS system are a
complex function of:

• Size and type of conurbation (commercial, residential, mixed);


• Plumbing and heating systems;
• Domestic and commercial product formulation and use patterns;
• Dietary sources and faeces;
• Atmospheric quality, deposition and run-off;
• Presence and type of industrial activities;
• Use of metals, and other materials in construction;
• Urban land use;
• Traffic type and density;
• Urban street cleaning;
• Maintenance practices, for collecting systems and stormwater controls;
• Accidental releases.

Quantitative information on both metal and organic pollutants in urban runoff arising from
anthropogenic activities is difficult to evaluate, due to the lack of information on
background levels of these substances in the environment. Background concentrations
relate to natural geochemical sources and biological sources, and include amounts in
soils, dusts and waters derived from historical pollution.

The specific potentially toxic elements (PTEs) and organic contaminants considered in
this report are listed in Table 7.1.

Table 7.1 Potentially toxic elements and organic contaminants examined in the
review of pollutants in urban waste water and sewage sludge

Potentially toxic elements Organic contaminants


Zinc (Zn) Linear alkylbenzene sulphonates (LAS)
Copper (Cu) Nonylphenolethoxylates (NPE)
Nickel (Ni) Di-(2-ethylhexyl)phthalate (DEHP)
Cadmium (Cd) Polycyclic aromatic hydrocarbons (PAHs)
Lead (Pb) Polychlorinated biphenyls (PCBs)
Chromium (Cr) III and VI Polychlorinated dibenzo-p-dioxins (PCDDs)
Mercury (Hg) Polychlorinated dibenzo-p-furans (PCDFs)
Platinum group metals (PGMs) Nitro musks (chloronitrobenzenes)

Other PTEs* Pharmaceuticals


Oestrogenic compounds:
Endogenous forms: 17β-oestradiol, oestrone
synthetic steroids: ethinyloestradiol
Polyelectrolytes (polyacrylamide)

Other organics**
*- such as Arsenic, Silver, Molybdenum and Selenium
**- such as Adsorbable organo halogens (AOX) and chlorinated paraffins

Pollutants in Urban Waste Water and Sewage Sludge 206


Section 7. Report Synopsis, Discussions and Conclusions

Specific case studies on the following key issues are included in greater detail in Section
6

• Platinum group metals (PGMs),


• Sustainable urban drainage,
• Artisanal activities,
• Pharmaceuticals,
• Body care products and fragrances,
• Surfactants,
• Polyelectrolytes in sludge treatment and dewatering,
• Influence of chemical phosphorus removal on potentially toxic element content in
sewage sludge.

The review has emphasised that an assessment of the contaminants entering UWW and
sludge cannot be divorced from an understanding of their potential impacts on the
environment, and particularly in relation to the use of sewage sludge in agriculture, as
this provides the context for defining the significance of UWW and sludge contamination.

Finally, areas where there is a deficit of information concerning particular sources or


contaminant groups, or their behaviour in the WWTS are identified and
recommendations for further investigations to inform decisions about the direction of
future research requirements have been formulated.

7.1.2 Potentially toxic elements

Sources of potentially toxic elements entering the WWTS

The sources of potentially toxic element contamination in the wastewater system have
been classified into three main categories:

• Domestic;
• Commercial;
• Urban runoff.

The information that was collected identified domestic inputs as the largest overall
sources of Cu, Zn and Pb entering the UWW system, whereas commercial sources
represent the major inputs of Hg and Cr (Table 7.2). Commercial discharges contribute
moderately larger inputs of Cd (30 – 60 %) compared with domestic sources (20 – 40
%). Estimates of Ni loadings from domestic sources are highly variable and this
contribution may be similar to, or greater than, the commercial input. The size of the run-
off contribution depends on climate and traffic intensity, and can be a significant
proportion (>20 %) of the total metal load for Cd and Pb, but it is a relatively minor
source of Cu and Hg. However, storm discharge was identified as an important source of
Hg in a survey of metal inputs to the river Rhine (French region), contributing 15 % of the
total load of this element to the river. Chromium, Ni and Zn represent an intermediate
group and run-off typically contributes <20 % of the total input of these elements to
UWW.

There is a degree of uncertainty in the mass balance, however, and a significant


proportion of the load is from unidentified sources, which represent ≥50 % of the total
input of Cr, Ni and Zn. Unclassified inputs of Cu, Hg and Pb represent 20-40% of the
total loading of these elements, whereas >80 % of the Cd is from identified sources.
Nevertheless, the relative magnitude of the domestic and commercial inputs of metals to
UWW is highly consistent with the estimated total loadings from these sources to major
river systems in Europe (Table 7.3). Strategies to reduce discharges of metals to sewer

Pollutants in Urban Waste Water and Sewage Sludge 207


Section 7. Report Synopsis, Discussions and Conclusions

can only focus on those sources that can be identified and quantified. Therefore, given
the extent of the uncertainty in establishing the sources and inputs of certain elements, a
priority area for research would be to determine these contributions and to develop a
complete mass balance for potentially toxic elements entering to the UWW system in
different European countries.

Cadmium and Hg have been proposed as priority hazardous substances by the


European Commission and will be subject to the controls required by the WFD to end all
releases of these elements to the water environment within a 20-year period. The status
of Pb as a priority substance is currently under review. Nickel is not designated
hazardous, but is classified as a dangerous substance and emission controls and quality
standards will also apply to this element as required by the WFD.

Table 7.2 Provisional potentially toxic element load from different sources entering
UWW in EU countries (% of total input)

PTE Domestic Commercial Urban Runoff


Wastewater Wastewater
Zn 30-50 5-35 10-20
Cu 30-75 3-20 4-6
Ni 10-50 30 10-20
Cd 20-40 30-60 3-40
Pb 30-80 2-20 30
Cr 2-20 35-60 2-20
Hg 4-5 50-60 1-5

The ranges in Table 7.2 are estimates from various sources in this study and may not
add up to 100%. Quite a high proportion of the Zn, Ni and Cr are not identified and
attributed to certain sources, and more research is needed in calculating the mass
balances of these PTEs in the urban environment.

Table 7.3 Diffuse and point sources of potentially toxic elements entering the river
Rhine reported in 1999 (% of total input)

PTE Point sources(1) Total diffuse sources(2)


Domestic Industry
Zn 30 10 60
Cu 20 15 65
Ni 20 20 60
Cd 10 10 80
Pb 15 10 75
Cr 15 25 60
Hg 20 20 60
(1)
Points sources include discharges through the UWW system
(2)
Diffuse inputs enter surface water directly

Despite uncertainties in identifying all the metal inputs there is ample evidence
demonstrating the significant reduction in metal discharges to the WWTS, principally due
to implementation of effective trade effluent controls, more efficient processes and
change in industrial base. This is reflected in the declining concentrations of metals
present in sewage sludge and in influent wastewaters (Section 2.1) and was reported in
all countries where data could be abstracted on temporal trends (The Netherlands,
France, UK and Sweden). Examples of the general declining trends in metal
concentrations in sludge over the past 20 years in European countries are shown in
Figure 7.1 for Zn and Cd for a major WWTP in the UK. In Sweden, Cd inputs declined by
60 % during the period 1992 – 1998 and Cr, Hg and Pb were reduced by 40 – 50 %. Zn

Pollutants in Urban Waste Water and Sewage Sludge 208


Section 7. Report Synopsis, Discussions and Conclusions

and Ni declined by 10 % during the same period, and there was no change in Cu
generally reflecting the importance of the domestic contribution of these elements in
UWW. Metal concentrations in rivers receiving treated UWW have also shown a marked
decline. For example, concentrations in the river Thames have declined on average by
50 % in the period 1986 – 1995.

(a) Zinc (b) Cadmium


2000 2
1.8
1800

Total Cd (Log mg kg-1 ds)


Total Zn (mg kg-1 ds)

1.6
1600
1.4
1400 1.2
1200 1

1000 0.8
0.6
800
0.4
600 0.2
400 0
1978 1983 1988 1993 1998 1978 1983 1988 1993 1998

Year
Figure 7.1 Reduction in (a) zinc and (b) cadmium concentrations (untransformed
and log 10 transformed data, respectively) in sewage sludge from Nottingham STW,
UK during the period 1978 – 1999

Measures to reduce metals discharges from domestic sources

Faeces comprise a significant proportion (>20 %) of the load of Cd, Cu, Zn and Ni
(equivalent to 60-70 % of the total amount of these elements in domestic contribution to
wastewater). Faeces typically contain 250 mg Zn kg -1, 70 mg Cu kg-1, 5 mg Ni kg-1, 2 mg
Cd kg-1 and 11 mg Pb kg -1 dry solids. The residual sewage sludge from WWTS generally
has significantly larger concentrations of metals than those present in human faeces
because of the contributions from other sources.

For Cd, however, which is the most labile zootoxic element in UWW and sludge and its
release is of particular concern in the environment, the weighted average content in
sludge is comparable to the concentration in human faeces. Whilst other sources of this
important element can be identified, solids inputs and secondary sludge production
during WWT may have a significant dilution effect on the mass input and transfer to the
sewage sludge. Consequently, a critical balance between input concentration in
wastewater and dilution processes may control the final Cd content in sludge to within
the normal range for faeces, which represents the minimum potential background
concentration value. The precise nature of these mechanisms could be identified to
better understand the behaviour of Cd in WWTS and in relation to effects of measures to
reduce Cd inputs on sludge quality. Whilst the opportunities for further reducing Cd
inputs would generally appear to be limited, removing phosphate from detergent
formulations has successfully reduced Cd discharges from domestic sources in The
Netherlands and Sweden (Section 2.1.2).

Pollutants in Urban Waste Water and Sewage Sludge 209


Section 7. Report Synopsis, Discussions and Conclusions

However, the principal sources of metals in domestic wastewater are body care
products, pharmaceuticals, cleaning products and liquid wastes (eg paint). Plumbing is
the main source of Cu in hard water areas, contributing >50 % of the Cu load. It may
also be a principal source of Pb where this was used historically as a means of drinking
water conveyance, accounting for 25 % of the input to WWTS. Lead solder in copper
pipes may also be an important source.

One approach to reducing the domestic input of contaminants is for homeowners to be


advised on the proper disposal of household wastes, for example the ‘bag it and bin it’
campaign run by some UK water companies . This will require co-operation between the
wastewater collector and regional authority responsible for municipal waste disposal to
establish and publicise schemes and accessible facilities for the disposal of liquid wastes
by homeowners. Metals (eg Zn) are also important active ingredients in other commonly
used household products, but it may be impracticable to eliminate these although
manufacturers minimise their excessive use, for example in packaging. An assessment
and survey of the practical implementation of voluntary collection schemes for liquid
waste and a programme of pilot studies is recommended to assess attitudes and the
extent of homeowner participation.

Commercial sources and inputs of potentially toxic elements to UWW


Regional studies of metal emissions from commercial premises indicate that further
reductions in discharges of most elements of concern could be potentially achieved from
this sector (Section 2.1.2). The main sources that may be the focus of further
investigation include health establishments, manufacturing industry and hotel/catering.
Approximately 30 % of medical establishments and 20 % of the other activities may be
discharging significant amounts of potentially toxic elements in wastewater. In particular,
Hg in UWW and sludge is largely attributable to dental and medical practices. Dental
amalgam separators are effective at reducing Hg emissions where their use is
compulsory and there is evidence, for example following the Danish ban, that
alternatives to Hg used in thermometers and other products can reduce discharges to
the WWTS.

Large industrial installations are required to treat wastewater to an appropriate standard


before discharging to the WWTS and are subject to rigorous trade effluent control
standards. However, small commercial, artisanal enterprises that are connected to
WWTS may also be a potentially significant source of contaminants. One of the largest
agglomerations of artisanal activities in Italy was investigated in Case Study (c) . This
Case Study identified vehicle repair shops, metal processing and jewellery
manufacturers as principal artisanal activities potentially responsible for discharging
significant amounts of PTEs to the UWW system (table 7.4). However, many small
enterprises pretreat wastewater before discharge and this was found to markedly reduce
the extent of actual metal discharges to sewer. In the Vicenza Case Study, for example,
pretreatment reduced the input of Zn, Cu and Pb from artisanal activities to <10 % of the
total load entering the WWTS and Cr and Ni inputs were reduced to <2 and 0.5 % of the
total input. Cadmium achieved the smallest overall reduction and approximately 40 % of
the total load of this element to the WWTS, was identified as coming from artisanal and
commercial activities, principally goldsmiths and car repairers. Further detailed
assessment of wastewater management by these types of small enterprises is
necessary in other European countries to determine the extent and effectiveness of
wastewater treatment prior to discharge and whether specific measures and
requirements are necessary and warranted to reduce potentially toxic element
contamination from these sources.

Incomplete information regarding these sources could account for a major proportion of
the unidentified inputs of metals to UWW (Table 7.2). The identification and control of

Pollutants in Urban Waste Water and Sewage Sludge 210


Section 7. Report Synopsis, Discussions and Conclusions

these inputs is practiced in a number of regions in France by operating registration


schemes and inventories of all discharging business premises/activities connected to the
WWTS within specific catchment areas. Premises are inspected and the necessary
levels of remedial action are agreed with the owner. Small business enterprises may be
an important source of potentially toxic elements and the extent of these inputs to UWW,
and the level of process wastewater treatment or segregation, should be examined in
other European countries to assess the effectiveness and practicability of targeting
artisanal activities for specific remedial action.

Other investigations in Sweden and Norway confirm the importance of motor industries,
vehicle workshops and washing facilities (particularly heavy goods vehicles) as major
sources of potentially toxic elements in UWW. Oil separating devices may be fitted as a
measure to reduce wastewater contamination from these activities. However, the
formation of stable emulsions in the wastewater by detergent microemulsion formulations
used for vehicle washing tend to limit the effectiveness of these systems at reducing
pollutant emissions.

Pollutants in Urban Waste Water and Sewage Sludge 211


Section 7. Report Synopsis, Discussions and Conclusions

Table 7.4 Total metal loads (mean values) from artisanal activities (in discharged and segregated wastewater) in Northern Italy

Activity Zn Cu Ni Cd Pb Cr(III)(4)
(number of % total load to % total load to % total load to % total load to % total load to % total load to
enterprises(1)) WWTS (mean) WWTS (mean) WWTS (mean) WWTS (mean) WWTS (mean) WWTS (mean)
Food (52) 0.28 0.09 <LOD <LOD <LOD <LOD
Car repair (174) 6.4 8.5 0.3 6.3 34.0 1.0
Ceramic (24) 0.01 0.001 <LOD 0.14 3.1 1.1
Galvanic (17) 0.07 0.84 0.67 0.39 1.5 0.15
Printing (141) 0.24 2.0 < LOD 2.8 0.59 0.6
Wood (92) 0.29 0.46 <LOD <LOD 5.5 0.76
Metallurgist (155) 8.7 5.3 15.6 2.3 25.7 4.7
Dental (88) 0.16 0.02 <LOD 0.25 <LOD 0.05
Gold (253) 2.1 7.6 <LOD 32.2 <LOD 0.14
Hairdressing (316) 0.99 0.69 <LOD <LOD <LOD <LOD
Laundry (88) 0.49 0.09 0.04 2.3 0.45 <LOD
Total(2) 19.9 25.5 16.6 46.6 71.1 8.9
Total(3) 8.8 9.5 0.46 36.9 7.9 1.8
(1) (2)
Total number = 1579 enterprises Calculated on basis of no pre-treatment and discharge directly to UWW system.
(3)
Based on discharge of pre-treated wastewater to the UWW system (car repair, ceramic, galvanic, printing, wood processor and metallurgy enterprises
usually segregate and pre-treat process water to comply with the standards for discharge of industrial wastewater in Italy).
(4)
Cr VI was discharged in the effluent from galvinising shops, but was not detected any other sample or in the influent to the WWTS. Cr VI is rapidly
transformed to Cr III on contact with organic matter in sewage and sludge. Therefore the Cr VI input from galvanising shops was calculated as a proportion of
the total Cr load to the UWWS (as Cr III). Loadings >5 % of the total input to the UWWS system are highlighted in bold and <LOD=below limit of detection

Pollutants in Urban Waste Water and Sewage Sludge 212


Section 7. Report Synopsis, Discussions and Conclusions

Urban run-off
Metal inputs to WWTS in urban run-off are highly variable and depend on traffic,
surface and roofing materials and age, and environmental factors (Section 2.1.3).
The principal sources of PTEs in urban run-off include:

• Wet and dry atmospheric deposition;


• Degradation of roofing materials;
• Construction;
• Road and vehicle related pollution;
• Litter, vegetation and associated human activities;
• Soil erosion.

Urban run-off is potentially a significant source of Cd and Pb, contributing up to 40 %


of the total load of these elements entering the WWTS (Table 7.2). The removal of
Pb from fuel additives has significantly reduced runoff inputs of this element.
Precipitation represents a comparatively small proportion of the total bulk input of
metals in urban run-off. Rainfall contributes approximately 10 % of the Cd, Pb and Cu
and only about 1 % of the Zn load in run-off. The majority of elemental inputs are
derived from dry deposition onto paved surfaces, surface degradation processes as
well as from vehicle emissions.

Roads and vehicles have been investigated as potential sources of PTEs entering
WWTS. Lead, Cu, Cd and Zn are present in high concentrations in brake linings and
amounts of Cd and Zn are also significant in tyre rubber. Tyre abrasion and brake-
lining wear appear to be more important as sources of Cd and Zn transfer to runoff
water. Whilst these metals may be released during brake-lining wear, the amounts of
Pb and Cu entering the drainage system in runoff is relatively small. Run-off is a
minor source of Cu entering the UWW compared with the domestic load from
plumbing. Nickel is the main element released from the abrasion of road surfaces.
Roofing materials influence concentrations in runoff and Zn is significantly increased
by galvanised surfaces. Lead in window frames and roof sheeting and also Pb
painted surfaces can contribute significant amounts of this element to runoff water.
Interestingly, the concentrations of Cd, Cu, Pb and Zn in roof runoff may be
comparable to, or greater than, those in road run-off suggesting that atmospheric
deposition onto paved surfaces may be more important as a source of metals in run-
off than vehicle or road related inputs. Concrete structural materials transfer
negligible amounts of potentially toxic elements to run-off. The relative size of the
inputs of different potentially toxic elements to UWW in run-off can be ranked in
increasing order as: Cd<<Ni<Cu<Pb<<Zn. Although there is more Zn in urban run-off
than any other metal, this represents a relatively minor input to the WWTS (<20 %)
compared with domestic (50 %) and commercial (<35 %) discharges of Zn to sewer
(Table 7.2).

The available mass balance information suggests that the overall contribution of
urban run-off to the metal flux in UWW is generally comparatively small, and
intermittent depending on rainfall, relative to other sources (Table 7.2). However, the
variable nature and uncertainty about the extent of these inputs could partly explain
the apparent discrepancy between the identified sources of PTEs and the actual load
entering the WWTS. The significance of potentially toxic elements in urban run-off
could be quantitatively examined by relating rainfall frequency, duration and intensity
with temporal trends in the metal content of sewage sludge sampled from WWTS
serving different catchments types (industrial, domestic, mixed). There are a number
of possible measures that can potentially reduce contaminant entry into UWW from
run-off. For industrial and other paved areas, for example, where it is practicable,
interception systems to remove contaminants bound to suspended solids by

Pollutants in Urban Waste Water and Sewage Sludge 214


Section 7. Report Synopsis, Discussions and Conclusions

sedimentation or filtration can reduce inputs to the WWTS. However, these are only
moderately effective because the smallest particles containing the largest
concentrations of metals do not settle efficiently. The design and management of
these systems are described in Case Study (b). In general, however, it is difficult to
practically control or minimise run-off contamination due to the diffuse nature of the
sources of metals, although targeting Pb painted surfaces for source preventive
action would further curtail inputs of this element into the environment.

Metal transfers to sewage sludge during WWT


The majority of the polluting load in UWW, including potentially toxic elements, is
transferred to the sewage sludge during WWT and a relatively small soluble or
suspended fraction may be discharged to the environment in the treated effluent.

Empirical and mechanistic models of metal transfer (TOXCHEM) have been


developed. Both modelling approaches can be used to predict the metal
concentration in wastewater on the basis of the content in sludge. Metal removal
during primary sedimentation is a physico-chemical process, dependent on the
settlement of precipitated, insoluble metal or the association of metals with settleable
particulate matter. The removal of metals during secondary wastewater treatment is
dependent upon the uptake of metals by the microbial biomass and the separation of
the biomass during secondary sedimentation. Approximately 60 – 80 % of most
elements in raw sewage are removed and transferred to the sludge. Nickel is the
most soluble element and removals of 40 % are more typical for this element. The
arithmetic mean metal concentrations in sewage sludge in European countries are
listed in Table 7.5.

Mass balance of metals in the WWTS must take into account metal contents and
their fates in sewage sludge. Detailed environmental, toxicological and
ecotoxicological assessments of metals provide assurance that the concentrations of
Cd, Cu, Ni, Cr, Hg and Pb in sewage sludge are well below values that constitute a
potential risk to soils and the environment when sludge is applied to agricultural land.
Zinc, on the other hand, presents the principal potential risk to crop yields from
phytotoxicity to affecting soil microbial processes. However, it is also an important
trace element and the environment can be protected from the potentially toxic effects
of Zn in sludge by technically based, but precautionary soil limits.

Table 7.5 Arithmetic mean metal content in sludge and maximum permissible
limits in soil and sludge (mg kg-1ds) in the EU(1)
Element Mean 86/278/EEC Proposed EU 86/278/EEC Proposed
maximum in maximum in maximum in EU
sludge sludge soil (range) maximum in
(range) soil (pH 6-7)
(2)
Zn 863 2500-4000 2500 150-300 150
Cu 337 1000-1750 1000 50-140 50
Ni 37 300-400 300 30-75 50
Cd 2.2(3) 20-40 10 1-3 1
Pb 124 750-1200 750 50-300 70
(4)
Cr 79 1000 60
Hg 2.2 16-25 10 1-1.5 0.5
(1)
Data are reported for 13 countries: Austria, Denmark, Finland, France, Germany,
Greece (Athens), Ireland, Luxembourg, Norway, Poland, Sweden, The Netherlands and UK.
(2)
Excludes Poland and Greece (represented by Athens WWTS); the mean Zn content in
Polish sludge and sludge from Athens WWTP is 3641 and 2752 mg kg-1 ds, respectively. The
-1
mean European value including Poland and Greece is 1222 mg Zn kg .

Pollutants in Urban Waste Water and Sewage Sludge 215


Section 7. Report Synopsis, Discussions and Conclusions

(3)
Excludes Poland; the mean Cd content in Polish sludge is 9.9 mg kg-1 value. The mean
European value including Poland is 2.8 mg Cd kg-1 ds.
(4)
Excludes Greece; the mean Cr content in sludge from Athens WWTP is 886 mg kg-1. The
mean European value including Greece is 141 mg Cr kg-1.

Variations in metal concentrations in sewage sludges observed between different


countries are difficult to reconcile because all European governments, local
environmental agencies, water utilities and municipal authorities actively enforce
trade effluent control. Metal concentration data are most widely reported for sludge
that is used in agriculture and lower values may be apparent where national
regulations enforce stringent metal limits for sludge, although this approach tends to
diminish the opportunities for utilising sludge on agricultural land. These data are
therefore specific to particular sludge sources and do not provide an overall
assessment of sludge contamination with potentially toxic elements disposed of by
alternative routes such as incineration. However, certain countries report lower metal
contents in sludge than in other states, even when sludge limit values do not appear
to be generally restrictive of sludge recycling to land.

A possible explanation may be related to the statistical characteristics of metal


concentrations and whether data are reported as arithmetic or weighted averages.
The data are usually skewed and the median values are usually lower than the
means. This would give rise to large discrepancies in amalgamated data from
different member states. Variations could also be related to the efficiency of different
analytical methods at extracting metals from the sludge matrix. The size of WWTP
may also be important since sludges from large works contain more metals than from
smaller works. This could be interpreted as the result of higher industrial inputs of
metals to large works, although it may also be explained by the greater interception
of atmospheric deposition of metals by paved areas in urban centres served by the
largest sewage treatment works. A more detailed assessment and examination of the
sludge qualities and quantities from different types of treatment centre in relation to
disposal outlet in European Member States is necessary, and a consistent statistical
format should be developed, for the comparative analysis of concentration data from
different countries.

Enhancing metal partitioning between treated wastewater and sewage sludge


The chemical treatment of wastewater to remove phosphorus is increasingly
practiced to control P discharges in the treated effluent as a measure to reduce
eutrophication of sensitive water courses. Chemical precipitation with Al or Fe salts
can also enhance the efficiency of metal removal and transfer to the sewage sludge,
thus potentially increasing the metal content of the sludge (Case Study (i)). For
example, Cu and Zn removal from UWW can be raised by 50 % compared to
conventional sedimentation without chemical enhancement; Pb removal may
increase by 80 % and a 3-fold increase in Cr (III) removal by chemical precipitation
has been reported. However, potentially the most important effect of chemical
precipitants on metal concentrations in sewage sludge is associated with the actual
quality and metal content of commercially available precipitant formulations
themselves. For example, Fe-based precipitants marketed for use in wastewater
treatment can be industrial by-products from titanium oxide production and may
contain significant amounts of potentially toxic elements.

Theoretical calculations (Case Study (i)) suggest that typical dosing rates of FeSO4
salt may increase the Cd content of sludge by 4.5 mg kg-1. The Ni concentration in
sludge may increase by 130 % compared with national weighted average values and
Zn and Pb contents may be typically raised by 10 %. Indeed, the use of low-grade
precipitants could erode the significant progress that has been achieved in reducing

Pollutants in Urban Waste Water and Sewage Sludge 216


Section 7. Report Synopsis, Discussions and Conclusions

metal emissions to sewer through controlling trade effluent discharge. In response to


these concerns, certain European countries (e.g. Germany) have introduced controls
on the composition of Fe and Al-based coagulants used for UWW treatment and
potable water grade Fe salts are recommended to avoid potential problems
associated with potentially toxic elements. However, relatively pure sources of Fe
and Al salts can be recovered from other types of waste, such as acid mine drainage,
and are also effective P precipitants. The use of secondary resources for P
precipitation during UWW treatment is intuitively attractive and also alleviates other
potential environmental problems associated with the disposal of those wastes.
However, the metal content of waste-derived products should be established, and the
potential consequences of their use on sludge quality determined, before a particular
product is accepted for use as a chemical precipitant in UWW treatment.

Significance of Platinum Group Metals in UWW

The platinum group metals (PGMs) are a group of rare elements including platinum
(Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir) and osmium (Os) and
the current status of the sources and knowledge of the fate and environmental
consequences of PGMs are described in Case Study (a). The commercial use of Pt
and Pd in particular has expanded significantly in recent years in the manufacture of
catalytic converters to reduce atmospheric emissions of carbon monoxide,
hydrocarbons and nitrous oxide from internal combustion engines. The discharge of
Pt from excreted anti-neoplastic drugs used in the treatment of cancers is another
identified source entering the WWTS. However, reliable quantitative estimates of
major Pt and Pd sources are available and show that hospitals contribute a relatively
minor input, equivalent to 6 – 12 % of Pt discharged to sewer, compared with vehicle
exhaust catalysts. Glass, electronics and jewelery manufacturing are other potential
sources of PGMs and can represent important local inputs of these elements
entering particular WWTS. The rate of removal of PGMs from UWW by sewage
treatment processes is generally within the range of most other potentially toxic
element species and approximately 70 % of the Pt in wastewater is transferred to the
sewage sludge. Reported concentrations of Pt in sludge from 2 WWTP in Munich
were in the range 86 – 266 µg kg-1 ds.

Platinum group metals emitted as autocatalyst particles behave inertly and have
limited mobility in soil so there would appear to be negligible risk to health,
groundwater and the environment. However, it is possible for transformations to
soluble, bioactive forms to occur and as the commercial use of PGMs continues to
rise, there is a case for a limited investigation of their environmental significance.
These studies should focus on the factors controlling the solubility and bioavailability
of PGMs and on the behaviour of PGMs in surface waters receiving treated sewage
effluents. Information is also needed on the uptake of PGMs by crops from the
agricultural use of sludge and direct deposition onto urban garden soils to quantify
the potential transfer by multiple exposure routes to the human foodchain.

7.1.3 Organic compounds

General
Compared with the small number of PTEs of concern in wastewater and sludge
which are routinely monitored and controlled, the range of organic contaminants
present in these media, with the potential to exert a health or environmental hazard,
are significantly more diverse. For example, approximately 140 organic compounds
have been identified in UWW in Sweden and more than 330 organic substances
have been determined in German sewage sludge. Forty two organic compounds are
regularly detected in sludge.

Pollutants in Urban Waste Water and Sewage Sludge 217


Section 7. Report Synopsis, Discussions and Conclusions

Persistent organic contaminants


Source and emission controls on persistent organic contaminants were introduced
between 1980-90 to curb the extent of environmental releases as concern increased
about the extent of their occurrence and potential toxicity. This legislation has been
relatively effective and there are several reliable examples in the literature illustrating
significant reductions in the primary sources of PAHs, PCBs and PCDD/Fs and this
has lowered inputs to the UWW system and reduced concentrations in sewage
sludge (Table 7.6). For example, discharges of PCBs to UWW declined by >99 % in
the Rhine region of France between 1985 to 1996 due to stricter industrial source
control and PAHs were also reduced by >90 % over the same time period. The
principal inputs of these contaminants to UWW are from atmospheric deposition onto
paved surfaces and run-off.

Controls on combustion and incineration emissions and the production of certain


potentially contaminated chlorinated pesticides have also markedly reduced the
release of PCDD/Fs to the environment. A review of PCDD emissions in Austria in
1998 show small consumers including household, trade and administration activities
are the principal sources of release contributing almost 60 % of the total
contemporary load to the environment (Figure 7.2). In the UK, incineration of
municipal waste is the largest emitter of PCDD/Fs representing about 40 % of total
emissions to the environment. The emission controls have had a positive effect on
the quality of sewage and PCDD/F concentrations have declined significantly. For
example, the average PCDD/F concentration in sludge sampled from Spanish
WWTS declined from an average value of 620 ng kg-1 TEQ reported for the period
1979 – 1987 to 55 ng kg-1 TEQ in 1999. In the case of sludge from a major London
WWTS (Figure 7.3), PCDD/F concentrations decreased by >97 % in the past 40
years from 166 ng kg-1 TEQ in 1960 to 4.2 ng kg-1 TEQ in 1998. Typical PCDD/F
concentrations reported in sewage sludge are significantly below the highly
precautionary standard for agricultural utilisation (100 ng kg-1 TEQ) proposed by the
EU (Table 7.6). Indeed the numerical limit is unlikely to restrict land application yet
the cost of PCDD/F analysis is high and routine monitoring of sludge for its PCDD/F
content is impractical. The implementation of quality standards for PCDD/Fs in
sewage sludge should be reviewed in terms of environmental effects, analysis
frequency and cost.

Historic pollution levels are important for organic pollutants as well as potentially toxic
elements. For example PCBs, which are no longer used, largely result from
volatilisation from soil and are found in similar concentrations in all the WWTS. This
suggests either that sources are diffuse and spread evenly or that this is due to
general background concentrations. Soil is an effective scavenger and sorptive
medium for organic pollutants and acts as a long-term and major repository, although
biodegradation also takes place. Contemporary remobilisation by volatilisation from
soil and redeposition onto surfaces and consequential collection by UWW systems is
a major source of these compounds entering sewage sludge.

Controls on the use and emissions of persistent organic contaminants have


significantly reduced industrial inputs of these substances to sewer. Therefore, the
concentrations present in sludge principally reflect:

• Background inputs to the sewer from normal dietary sources ;


• Background inputs by atmospheric deposition due to contemporary
remobilisation/volatilisation from soil and cycling in the environment (eg
PCBs, PCDD/Fs and PAHs);
• Atmospheric deposition from waste incineration (eg PCDD/Fs);

Pollutants in Urban Waste Water and Sewage Sludge 218


Section 7. Report Synopsis, Discussions and Conclusions

• Atmospheric deposition from domestic combustion of coal;


• The extent of biodegradation of organic contaminants during sludge
treatment, which is limited for most of these compound types;
• The extent of volatile solids destruction during sludge treatment, which
increases the concentration of conservative persistent organic compounds in
sludge.

Polycyclic aromatic hydrocarbons are proposed as priority hazardous substances


(COM(2001) 17 final) within the European Water Framework Directive and the aim
will be to achieve cessation of emissions, discharges and losses of these compounds
by 2020. However, curbing the emissions of PAHs and PCDD/Fs from domestic coal
burning would be technically difficult and incinerators are already subject to stringent
air quality emission standards. Consequently, there is probably little opportunity to
further reduce the inputs and concentrations of PAHs, PCDD/Fs as well as PCBs in
UWW and sewage sludge. Furthermore, the compounds are effectively removed by
wastewater treatment processes because they strongly bind to the sludge solids
minimising the discharge in treated effluent. The increasing amount of scientific
investigation also shows there are no significant environmental consequences from
PAHs, PCBs or PCDD/Fs when sludge is used on farmland as a fertiliser. In the light
of such developments and their physico-chemical behaviour, it may be argued that
the importance of these substances as major pollutants of UWW and sludge has
been significantly diminished. Soil is a major repository for persistent organic
contaminants and further investigations are necessary to improve understanding of
the remobilisation and cycling processes in the environment that control diffuse
inputs of these organic compounds to UWW.

Table 7.6 Concentrations and proposed limit values of selected organic


contaminants in sewage sludge (mg kg-1 ds)

Organic compounds Mean content Proposed EU


mg kg-1 ds maximum in
sludge
mg kg-1 ds
Halogenated organics (AOX) 200(1) 500
Linear alkylbenzene sulphonates (LAS) 6500 2600
Di(2-ethylhexyl)phthalate (DEHP) 20 – 60 100
Nonylphenol and ethoxylates (NPE) 26 (UK: 330 – 640) 50
Total polycyclic aromatic hydrocarbons 0.5 – 27.8 6
(PAH)
Total polychlorinated biphenyls (PCB) 0.09 0.8
Polychlorinated dibenzo-dioxins 36(2) 100(2)
and –furans (PCDD/Fs)
(1) (2) -1
German sludge only Units ng kg TEQ

Pollutants in Urban Waste Water and Sewage Sludge 219


Section 7. Report Synopsis, Discussions and Conclusions

(a) Austria (b) United Kingdom


Municipal waste
incineration
Small consumer Industrial

Industry - combustion Domestic

Clinical waste
Industry - processes incineration
Volatilisation from
Waste and landfills chlorophenol
Vehicle

Figure 7.2 Sources of dioxin emissions (% of total emitted) in (a) Austria in


1998 and (b) UK in 1991

450
Dioxin concentration (ng TEQ kg ds)

400
350 US EPA proposed
limit
300
250
200
150 German
100 limit
50
0
1944 1949 1953 1956 1958 1960 1998

Year
Figure 7.3 Dioxin content of archived samples of sewage sludge from a WWTS
in West London, UK

Other organic contaminants

Emissions of other organic contaminants and entry to the WWTS are associated with
direct or indirect discharges resulting from their use in commercial and domestic
activities. For example, the principal emissions of DEHP occur from the use of
finished products and major domestic inputs to UWW are floor and wall coverings
and textiles with PVC prints. In Sweden, for example the domestic contribution was
equivalent to approximately 70 % of the total load of phthalates to Gothenburg
WWTS. Numerically, detergent surfactants and residues (LAS and NPE) are the
most significant contaminants in sewage sludge and the LAS content is typically
more than twice the proposed European limit for this pollutant in sludge (Table 7.6).
Unless action is taken to reduce the use of the surfactant LAS in detergent
formulations, the proposed standard will prevent use of sludge on agricultural land.
The UK also appears to have a particular problem with NP and NPEs as
concentrations of these compounds in UK sludge are an order of magnitude larger
than those reported in average sludges in other European countries Non-

Pollutants in Urban Waste Water and Sewage Sludge 220


Section 7. Report Synopsis, Discussions and Conclusions

Governmental organisations in Sweden and Denmark have been successful in


independently introducing eco-labelling schemes persuading consumers against
detergents containing LAS or NPE.

Linear alkylbenzene sulphonate and NPE can be substituted in detergent


formulations and alternatives may also need to be sought for DEHP in plastics
manufacture if emissions of this substance to water are to be controlled. Nonylphenol
is a proposed priority hazardous substance within the Water Framework Directive
and the use of NPEs in detergents is therefore likely to end with the implementation
of European legislation to phase out discharges, losses and emissions of
alkylphenolic compounds to the aquatic environment. A comprehensive independent
review, also involving the detergent and plastics manufacturers, regarding the fate,
behaviour, degradability, toxicity and environmental consequences of these and the
alternatives compounds would provide information on the advantages and
disadvantages of product substitution in detergent formulations and plastics
manufacture.

A group of emerging compounds of potential significance in UWW were identified by


the review due to their persistence during sewage or sludge treatment, persistence in
soil or toxicity in the environment:

1. Little is known about the fate and behaviour in UWW of the large number (>200) of
commercial chlorinated paraffin formulations in use as plasticisers in PVC and
other plastics, extreme pressure additives, flame retardants, sealants and paints.

2. The brominated diphenyl ethers (PBDEs) are a group of compounds used for
flame retardation in furnishings, textiles and electrical insulation and their use has
expanded due to fire regulation requirements and the increased use of plastic
material and synthetic fibres. A survey in Sweden indicated concentrations of PBDE
congeners in sludge were between 15 and 19 µg kg-1, respectively. PBDEs are on
the list of proposed priority hazardous substances.

3. Polychlorinated naphthalenes (PCNs) are released into the environment by


waste incineration and landfill disposal of items containing PCNs. Concentrations in
sewage sludge may be in a similar range to individual PCB congeners. A survey of
Swedish sludges indicated that PCN concentrations were in the range 1.6 mg kg-1
ds. Some PCN congeners have dioxin like activity and have been assigned TCDD
toxic equivalent values similar to those for coplanar PCBs and so have toxicological
interest.

4. A small amount of Quintozene (pentachloronitrobenzene) is produced in the EU


(21.5 t y-1) and it is registered for use in the UK, Spain, Greece and Cyprus. It has
low water solubility and half-lives in soil are reported to be in the range 5 – 10
months.

5. Polydimethylsiloxanes (PDMS) are nonvolatile silicone polymers used in


industrial and consumer products including lubricants, electrical insulators and
antifoams. They are hydrophobic and partition onto the sludge solids and
concentrations in N American sludge reported to be in the range 290 – 5155 mg kg-1.
However, PDMS do not bioconcentrate or exhibit significant environmental toxicity,
but they are relatively persistent in soil and can take months to years to degrade.

6. Nitro musks (chloronitrobenzenes) are a group of synthetic dinitro- trinitro-


substituted benzene derivatives used as substitutes for natural musk in perfumed
products (Case Study (e)). In Europe, current consumption is estimated to be 124 t y-

Pollutants in Urban Waste Water and Sewage Sludge 221


Section 7. Report Synopsis, Discussions and Conclusions

1
for musk ketone and 75 t y-1 for musk xylene and the release of these compounds
to the environment is dominated by domestic discharges to WWTS.

Further studies on the biodegradation and transformations of these compounds


during secondary wastewater and sludge treatment are required as a preliminary
stage in understanding whether the release of musk compounds to the environment
is significant from WWT.

7. Endogenous oestrogens (17b-oestradiol and oestrone) and synthetic steroids


such as ethinyloestradiol, which is the active oestrogenic component in oral
contraceptives, are discharged in trace amounts in the effluent from WWTS and are
primarily a concern due to the possible impact on the aquatic ecosystem. These
compounds also partition onto particulates and may be associated with sewage
sludge, but this is unlikely to have significant environmental implications for use of
sludge in agriculture. Recent investigations show that approximately 90 % of
potential oestrogenic activity (based on 17b-oestradiol equivalency) in UWW is
reduced by sewage treatment and that <3 % may be transferred to the sewage
sludge.

8. Pharmaceutical compounds, designed for specific biological effects in medical


and veterinary practice, can enter the wastewater system by excretion or residues
and metabolites in urine and from intentional disposal (Case Study (d)). Disposal into
the UWW system is common practice, although the rationale for justifying this on the
grounds of the dilution received within the sewer system should be reviewed in
context of subsequent environmental fate and behaviour of individual compounds.
Significant amounts of administered drugs are excreted from the body and 30 – 90 %
of antibiotic doses to humans and animals enter UWW in active forms in the urine.
The potential toxicological and ecotoxicological activities of these substances in the
wider environment are generally unknown, but, because of their biological function,
they are generally designed to be rapidly metabolised and degraded, although they
are often lipophilic and potentially bioaccumulate. Removal efficiencies during WWT
of >60 % are typical for most types of drug, although a wide range of removal rates is
reported (7 – 96 %) and drug compounds are routinely found in treated effluents and
surface waters. Many commonly used analgesic drugs are rapidly biodegraded
during sewage treatment including aspirin, ibuprofen and paracetamol. Most of these
are soluble and exist primarily in the aqueous phase and transfer to sewage sludge is
probably of only minor concern, although it is not possible to predict partitioning and
fate during sewage treatment due to the absence of physico-chemical data for many
of the compounds. The occurrence of drugs in soil is widespread from veterinary
administration to livestock. A risk assessment on the fate and biodegradation of drug
compounds could form an integrated part of the approval procedure for
pharmaceutical products. This would improve understanding of their behaviour and
fate to balance the benefits to health with the potential consequences of their release
into the environment. Collection systems for unwanted drugs should be encouraged
to reduce disposal into the wastewater system.

Polyelectrolytes and sludge treatment


Polyelectrolytes based on polyacrylamide and cationic copolymers are used
extensively in sludge treatment to aid dewatering, see Case Study (g). The
polyelectrolyte concentration in mechanically dewatered cakes is relatively large
typically in the range 2500 – 5000 mg kg-1 ds and they only degrade relatively slowly
by abiotic processes in cultivated soil at a rate of 10 % per year. Acrylamide is a
common monomer associated with polyelectrolytes and is potentially toxic to humans
and is a reported carcinogen. Concern that residual monomers in polyelectrolytes
used in drinking water treatment may have implications for human health has

Pollutants in Urban Waste Water and Sewage Sludge 222


Section 7. Report Synopsis, Discussions and Conclusions

resulted in their withdrawal from this application in Japan and Sweden, and stringent
controls on their use are also in place in Germany and France. These factors have
drawn attention to the possible environmental implications of sludge dewatering
practices with polyelectrolytes and long-term accumulation in sludge-treated soil.

Attenuation and transformations during wastewater and sludge treatment


Sewage sludge is treated to reduce its fermentability, nuisance and vector attraction
and to aid its management and acceptability for use on agricultural land. These
processes include physical, chemical and microbiological treatment of the sludge that
may influence the loss, or potential formation, of organic contaminants (Section 3.2).
Loss mechanisms include:

• Volatilisation;
• Biological degradation;
• Abiotic/chemical degradation (e.g. hydrolysis);
• Extraction with excess liquors;
• Sorption onto solid surfaces and association with fats and oils.

The sorption of organic contaminants onto the sludge solids is determined by


physico-chemical processes and can be predicted for individual compounds by the
octanol-water partition coefficient (Kow). During primary sedimentation, hydrophobic
contaminants may partition onto settled primary sludge solids and compounds can be
grouped according to their sorption behaviour based on the Kow value as follows:

Log Kow < 2.5 low sorption potential


Log Kow > 2.5 and < 4.0 medium sorption potential
Log Kow > 4.0 high sorption potential

Many sludge organics are lipophilic compounds that adsorb to the sludge matrix and
this mechanism limits the potential losses in the aqueous phase in the final effluent.
A proportion of the volatile organics in raw sludge, including benzene, toluene and
the dichlorobenzenes, may be lost by volatilisation during wastewater and sludge
treatment at thickening, particularly if the sludge is aerated or agitated, and by
dewatering. As a general guide, compounds with a Henry’s Law constant >10-3 atm
(mol-1 m -9) can be removed by volatilisation. The significance of volatilisation losses
of specific organic compounds during sewage treatment can be predicted based on
Henry’s constant (Hc) and Kow:

Hc > 1 x 10-4 and Hc/Kow > 1 x 10-9 high volatilisation potential


Hc < 1 x 10-4 and Hc/Kow < 1 x 10-9 low volatilisation potential

Biodegradation may be more important than air-stripping in removing volatile organic


contaminants during secondary biological WWT.

Mesophilic anaerobic digestion is the principal sludge stabilisation process adopted


in most European countries and many organic contaminants are biodegraded under
anaerobic conditions and this is enhanced by increasing retention time and digestion
temperature. Biodegradation during anaerobic digestion may eliminate certain
organic contaminants from sewage sludge, but in general the destruction achieved is
typically in the range of 15 – 35 %. Aromatic surfactants including LAS and 4-
nonylphenol polyethoxylate (NP nEO) are not fully degraded during sewage treatment
and there is significant accumulation in digested sludge. For example, mass balance
calculations suggest that approximately 80 % of LAS is biodegraded during the
activated sludge process and 15-20 % is transferred to the raw sludge, although near
complete biodegradation (97-99 %) is also reported in some cases. Approximately 20

Pollutants in Urban Waste Water and Sewage Sludge 223


Section 7. Report Synopsis, Discussions and Conclusions

% of LAS in raw sludge may be destroyed by mesophilic anaerobic digestion. The


compounds, nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate
(NP2EO) are formed during sewage treatment from the microbial degradation of
NPnEO. These metabolites are relatively lipophilic and accumulate in sludge and are
also discharged in the treated effluent from WWT. Approximately 50 % of the NPnEO
in raw sewage is transformed to NP by sludge digestion.

Lower molecular weight phthalate esters and butyl benzyl phthalate are completely
degraded in 7 days by anaerobic digestion at 35°C and should be removed by most
municipal anaerobic digesters. The extent and rate of biodegradation of organic
compounds during anaerobic digestion is apparently related to the size of alkyl side
chains and compounds with larger C-8 groups are much more resistant to microbial
attack. Therefore, di-n-octyl and DEHP are more persistent and are not removed by
conventional anaerobic treatment of sludge. Phthalate esters are rapidly destroyed
under aerobic conditions, however, and biological WWT (eg activated sludge
process) can usually achieve >90% removal in 24 h. In soil, the reported half-life of
DEHP is <50 d.

Composting is a thermophilic aerobic stabilisation process and has the potential to


biodegrade relatively persistent organic compounds in sludge. Thermophilic aerobic
digestion processes and sludge storage for three months can achieve similar overall
removal rates for organic contaminants as those obtained with mesophilic anaerobic
digestion. Thermal hydrolysis conditioning of sludge prior to conventional anaerobic
stabilisation may have a significant influence on the removal of organic contaminants
from sludge, but this is a comparatively new enhanced treatment process and effects
on the destruction of organic contaminants have yet to be investigated.

Pollutants in Urban Waste Water and Sewage Sludge 224


Section 7. Report Synopsis, Discussions and Conclusions

Table 7.7 Assessment of the significance of PTEs entering UWW and SS


(1) (2) (3)
PTE Trade Priority Environmental Significance of input sources (L, Low; Moderate, M; High, H)
(4)
effluent hazardous significance in Commercial Run-off Domestic
(5) (6)
control substance (Yes, sludge-treated Relative Opportunity Relative Opportunit Relative Opportunit
(Yes, Y; Y; soil (short importance to reduce importance y to reduce importanc y to reduce
No, N) No, N) –term) e
(Yes, Y; No, N)
Zn Y N N* M M L-M L H M
Cu Y N N L-M M L L H L
Ni Y N N M M L–M L M L
(7) (8)
Cd Y Y N M-H M L–M L M L
Pb Y (Y) N L–M M M L H L-M
Cr Y N N M-H M L–M L L L
Hg Y Y N H H L L L L
Pt N N N M L H L L L
Pd N N N M L H L L L
(1)
Proposed priority hazardous substance in COM(2001) 17 final: Amended proposal for a Decision of the European Parliament and of the Council
establishing the list of priority substances in the field of water policy. Lead is in parentheses as a proposed priority substance under review.
(2)
Reported environmental effects at current maximum permissible limit concentrations in sludge-treated agricultural soil (86/278/EEC) for Zn, Cu, Ni, Cd, Pb,
Hg; There are no reported environmental effects of Cr, Pt or Pd in sludge-treated soil. *Long-term potential for Zn, to soil microbial community at maximum
limit.
(3)
Relative to total identified inputs according to the following approximate ranges: L = <10 %, M = 10 – 50 %; H > 50 %.
(4)
Medical activities, manufacturing industries and small artisanal enterprises including: car repair, galvanising, metal work and goldsmiths are identified as
sources of metals discharging to sewer, where further reductions may be achieved.
(5)
Run-off is difficult to mitigate in practice; sedimentation ponds capturing run-off from paved areas of known deposition risk (eg industrial sites) can reduce
pollutant inputs bound to suspended solids.
(6)
Mainly voluntarily through product ecolabelling and education concerning appropriate use and disposal of liquid wastes, body care products, cleaning
agents and detergents by homeowners. A reduction in Pb may be possible in the long-term by replacing historical leaded pipework used for water
conveyancing.
(7)
Discharges may be indirect as Cd is an impurity associated with P (eg used in detergent formulations) and Zn used in industrial processes and roofing
materials.
(8)
Human faeces are the main domestic source of Cd representing the background concentration in UWW and sewage sludge.

Pollutants in Urban Waste Water and Sewage Sludge 225


Section 7. Report Synopsis, Discussions and Conclusions

Table 7.8 Assessment of the significance of organic contaminants entering urban wastewater and sewage sludge
(1) (2) (3) (4)
Contaminant Content in Priority Destruction in treatment Accumulation Background Overall
WW/sludge hazardous (Yes, Y; No, N) inputs significance
substance (Yes, Y; No, N)
(5)
Wastewater Sludge Biological Soil (Yes, Y; No, N) Wastewater Sludge
LAS H N H L Anaerobic N N N H L
H Aerobic
NPE M-H Y M L Anaerobic N N N H L
H Aerobic
DEHP M (Y) M L Anaerobic N N N H L
M Aerobic
PAHs L-M Y L L Y Y Y L L
PCBs L N L L Y Y Y L L
PCDD/Fs L N L L Y Y Y L L
Pharmaceuticals L N M M N N N M L
Oestrogenic:
Endogenous L N M-H M-H Y N Y H L
Synthetic L N L-M L-M Y N N H L
(1)Concentration ranges for sludge: L< 1 mg kg-1 ds; M<100; H >100 mg kg-1 ds. Concentrations in wastewater are small (mg l-1) and highly
variable, but will follow a similar general pattern to sewage sludge; published values are listed in Table 3.14 in the Main Report.
(2)European Commission Amended Proposal for a European Parliament and Council Decision establishing the list of priority substances in the field of
water policy (COM(2001)17 final of 16 January 2001).
(3)Approximate indicative ranges: L < 20 %; M = 20 – 60 %; H > 60 %
(4)Significance rating: Low, L; Moderate, M; High, H
LAS Linear alkylbenzene sulphonates
NPE Nonylphenolethoxylates
DEHP Di-(2-ethylhexyl)phthalate
PAHs Polycyclic aromatic hydrocarbons
PCBs Polychlorinated biphenyls
PCDDs Polychlorinated dibenzo-p-dioxins
PCDFs Polychlorinated dibenzo-p-furans

Pollutants in Urban Waste Water and Sewage Sludge 226


Section 7. Report Synopsis, Discussions and Conclusions

Table 7.9 Sources and control of organic contaminants entering urban waste water and sewage sludge

Contaminant Commercial Run-off Domestic


Relative Opportunity Relative Opportunity Relative Opportunity
importance to reduce importance to reduce importance to reduce
LAS H M L L H M
NPE H M L L H L
DEHP H M L L M M
PAHs L L H L L L
PCBs L L H L L L
PCDD/Fs L L H L L L
Pharmaceutical H M L L H M
LAS Linear alkylbenzene sulphonates
NPE Nonylphenolethoxylates
DEHP Di-(2-ethylhexyl)phthalate
PAHs Polycyclic aromatic hydrocarbons
PCBs Polychlorinated biphenyls
PCDDs Polychlorinated dibenzo-p-dioxins
PCDFs Polychlorinated dibenzo-p-furans

Pollutants in Urban Waste Water and Sewage Sludge 227


Section 7 - Discussion and Conclusions

7.2 COMMENTS, CHALLENGES AND STRATEGIES FOR THE NEXT 5 TO 10 YEARS

The significance of the identified sources of metals entering the UWW system has been
reviewed and opportunities for further reducing metal inputs are considered. This may be
possible through, for example, controlling discharges from a number of specified commercial
sectors and the introduction of remedial measures to reduce inputs from certain domestic
and diffuse sources. Therefore, a feasibility study of the most effective approaches to further
reducing metal inputs is recommended so that appropriate remedial strategies can be
implemented.

The contributions by the three major sources of pollutants to UWW is predicted to change.
Commercial sources are expected to become less important as the regulatory control is
more widely implemented and tightened, while the percentage contribution from domestic
sources is expected to increase. This is important as it is less easy to regulate domestic
discharges to UWW. However this can be achieved to some extent by controlling the
products used in homes; for example cadmium emissions from households could be
reduced by a ban on the use of phosphates in washing powders. Increasing consumer
awareness of pollution in UWW, for example through eco labelling schemes, can lead to
reductions in load to UWW from some sources such as the domestic use of LAS, however
this requires much wider adoption by manufacturers of eco labelling schemes. Industry and
stakeholder involvement need to be encouraged. Mechanisms to provide an incentive for
reductions in pollution and alternative product development should be developed.

There is probably little scope for further reductions in the inputs and concentrations of
persistent organic contaminant types in sewage sludge. For example, it is unlikely that much
can be done to curb emissions of PAHs and PCDD/Fs from domestic coal burning, where
this is widely practiced, and incinerators are already subjected to stringent air quality
emission standards. Losses of PCBs from electrical transformers is rapidly declining as
these are phased out of use. However, the importance of soil as a repository for persistent
organic contaminants is emphasised and the focus of further investigations to minimise
inputs to sludge could be directed towards better understanding of the remobilisation and
cycling of these substances in the environment.

Due to the variability of existing data on potentially toxic elements and organic pollutants,
common methodologies and standards of chemical and statistical analysis are necessary
and should be implemented at a European level as soon as feasible.

Feasibility of reuse of treated wastewater for non-household purposes, such as for irrigation
of agricultural crops, parkland, and golf courses needs to be considered but must involve
assessment of risks to human , environmental and economic strategic issues. Reuse of
domestic grey waters in the EU needs to be re-evaluated. Development of common
standards are necessary.

Return of unused pharmaceuticals to dispensaries/hospitals needs to be encouraged and


made more widespread throughout Europe. Hospitals and medical centres effluents should
be monitored closely for discharge to the urban wastewater network. Possible segregation
and pre-treatment of hospital, medical centre and laboratory effluents, for the reduction of
PGMs, pharmaceuticals and potentially toxic elements is recommended.

Sustainable urban drainage, discussed in detail, Case Study (b), may have great potential in
terms of reduction of urban runoff pollution. However it is recommended that each case
should be assessed individually, and an incremental approach containing both high tech and
low-tech solutions is the most likely development scenario (Butler and Parkinson, 1997).

Financial incentives/grants to encourage and facilitate removal of lead piping from


households would reduce lead emissions to UWW and should initially target areas with soft
water.

Pollutants in Urban Waste Water and Sewage Sludge 228


Section 7 - Discussion and Conclusions

There are some areas where restrictions need to be tailored to specific uses: for example,
the urban use of pesticides may need separate guidelines, than those applicable to
agriculture. Urban use of pesticides and herbicides in gardens and allotments is often
indiscriminate and can result in major uncontrolled inputs to the UWWS.

For mercury, dentists are important sources and improved dental practices may reduce this
source, but other sources, such as chloralkali processes, can in some instances emit more.
The use of thermo-reactive liquids in thermometers has been introduced in some regions as
a replacement for mercury. Mercury recycling schemes have also been a success in many
regions and could be extended to other potential pollutants used in domestic and
commercial settings.

Adjusting the pH of tap water may be useful in reducing corrosion, for example, from
domestic and commercial heating systems, but may be limited by practical and economic
factors and it can still be a problem in drinking water in some regions. For example, lead
passing into drinking water supplies from old lead piping and then into the sewage system
can be controlled by adjusting the pH and hardness of the water supply.

This report benefits from the presentation of several specific case histories, which provide
detailed information in support of the above conclusions. Some specific potential problem
areas have been reviewed. For example, the differences in cadmium concentrations
reported in sewage sludge in the United Kingdom and Germany have been shown to be due
to different approaches to data treatment and presentation rather than real variations in
composition. (see Section 2.3)

In the WWTS the fate of compounds often differs, for example, Ni is removed less well from
treated wastewater than other metals. This means that more Ni will pass out in the effluent
from the WWTS and less will be concentrated in the SS. The behaviour of compounds
should be borne into consideration when considering acceptable levels in the influent.

It is also important to note that some of the metals in this study, for example zinc and
copper, are essential trace elements to plants and animals in low concentrations. It is
important that levels in treated UWW and SS are not set so low by regulation that mineral
deficiency could arise due to removal of these sources where UWW and SS might have
been used, for example, on nutrient deficient land.

Domestic and industrial product formulation can have an important role in determining the
nature and amount of pollutants that are likely to enter the WWTS. Risk assessment of
domestic products should be based on their input of pollutants to the urban wastewater and
the biodegradability of the pollutants. Health and environmental effects should be considered
in the risk assessment process. Efforts to remove phosphate in detergents have had a knock
on effect in lowering the cadmium input to the WWTS. NPE bans and regional LAS
reduction through eco-labelling schemes have also been proven effective. It would also be
possible to pre-treat high LAS concentration in UWW from commercial sources, which would
then reduce levels reaching the WWTP.

Advice on household refurbishment (e.g. for old lead paint, piping) and advice on disposal of
potential pollutants (e.g. down sinks) and eco-labels and public education should be
provided and extended where possible to raise awareness of ecological impacts of various
processes and products in urban wastewater.

The inclusion of Cu, Zn and LAS on the proposed list of priority substances is recommended
because they are the most limiting substances to utilising sludge in agriculture within the
limits proposed in the revision of Directive 86/278/EEC and they are ubiquitous in
wastewater. Therefore, these substances should also be the focus of measures to reduce

Pollutants in Urban Waste Water and Sewage Sludge 229


Section 7 - Discussion and Conclusions

discharges and emissions to further improve sludge quality and support the recycling route
for sewage sludge.

In order to reduce inputs to UWW, it is important to target the sources contributing most to
the system, especially the diffuse sources. Trade effluent discharge controls have been
successful in lowering emissions but are still necessary for certain industries. Reductions of
many pollutants including lead and dioxins have been seen in sewage sludge since the
1960s. Increasing control on emissions, not only to water but also to air and land, are likely
to continue this reduction. This study concludes that small users, hospitals, garages and car
washes, dental and medical practices need a close monitoring and control for connection to
the urban wastewater systems.

Pollutants in Urban Waste Water and Sewage Sludge 230


Section 7 - Discussion and Conclusions

7.3 INFORMATION GAPS AND RESEARCH RECOMMENDATIONS

Relatively few regional surveys of the sources and significance of potentially toxic element
(PTE) inputs to UWW (Section 2.1) have been reported and recently published work, in
some cases, quote data from considerably earlier studies. There is a general lack of recent,
quantitative information regarding the sources and inputs of PTEs to UWW for the EU and
this is identified as a priority area for further data gathering.

There are very few studies available on the mass balance of potentially toxic elements and
organic pollutants through WWTS. More work is needed to understand the partitioning and
speciation of pollutants, particularly for compounds, such as NPE, which may become more
toxic through wastewater treatment. Some pollutant sources still need further identification.
In fact there are also many instances where the majority of pollutants sources remain
unidentified, for example the ADEME study in France estimated that over 50% of some of
the metals came from unidentified sources.

Identification and monitoring of trace organics is still sparse and more detailed work, though
costly, is urgently required. Better source inventory data is essential. In some cases
specific industrial sources are difficult to locate. For example, platinum uses and losses from
industry into the wastewater system are subject to the protection of commercial interests.

Information on organic pollutants comes mainly from France, the United Kingdom, Benelux,
Scandinavia and Germany but is very limited from the other EU countries. More research is
needed for estimates and quantification of diffuse sources of organic pollutants especially in
Iberia, Italy and Greece. Some data especially from Iberia is not readily available and an
integrated data collection system is needed across the EU 15 for PTEs and organic
pollutants.

Information is still needed in order to asses health and environmental effects. UWW effluent
and sewage sludge use on land usually involves exposure to very small quantities of mixed
pollutants over a prolonged period of time, and there is little health data about chronic
exposure, particularly to organic pollutants. A particular area of current concern is the
possible impact of cocktail effects where several contaminants are present at the same time.
Interactions between metals, organics, and metals and organics may be synergistic or
antagonistic, are complex and far from clearly understood.

Another area where knowledge is lacking is that concerning the effects of both potentially
toxic elements and trace organics on components of the ecosystem, both in soils and in
surface and subsurface waters. The prime effects to be considered are those on sensitive
receptors, including micro-organisms, invertebrates and plants. At present there is a lack of
base line information in this area. Ecotoxocity tests that are applied are undertaken in
laboratory conditions assuming 100% bioavailability of the pollutant, and are not appropriate
for field conditions. Research into the transfer of organic pollutants through uptake into
pasture plants and into crops and thus into the food chain is limited and should be
considered.

Pollutants in Urban Waste Water and Sewage Sludge 231


Appendix A

APPENDIX A
URBAN WASTEWATER TREATMENT SYSTEMS (WWTS) AND SEWAGE SLUDGE TREATMENT (SST)-
REGIONAL ASPECTS

Figure A.1 Water and pollutant sources and pathways in urban catchments
[after Ellis, 1986, note that this figure could be extended to include sludge output from the WWTS and
also other potential inputs such as from urban use of pesticides
* a gully pot (also known as catchbasin) is a chamber or well, usually built at the kerb side, for the
admission of surface water to a sewer or sub-drain. It has a sediment sump at its base to trap grit and
detritus below the point of overflow.]

Pollutants in Urban Waste Water and Sewage Sludge 232


Appendix A

TREATMENT PROCESS OUTLINE:

Urban wastewater and sewage treatment is comprised of unit operations to separate,


modify, remove and destroy objectionable, hazardous and pathogenic substances carried by
wastewater in solution or suspension in order to render water fit and safe for discharge and
intended uses. Stringent water quality and effluent standards have been developed that
require reduction in suspended solids, biochemical oxygen demand (BOD, related to
biodegradable organic compounds), COD (chemical oxygen demand) and to some extent
coliform organisms (indicators of faecal pollution), control of pH as well as the
concentrations of certain organic compounds, together with some potentially toxic elements
and non-metals.

Sewage sludge consists of residues originating from mechanical, biological, chemical and
physical treatment of wastewater in sewage plants. The quantity and nature of the arising
sewage sludge are subjected to strong fluctuations depending on the wastewater
composition, the kind of wastewater purification process and the purification degree. Two
different sewage sludge types can mainly be distinguished:

• Primary sludge: becomes physically or chemically separated from wastewater in


primary treatment
• Secondary sludge: arises from the biological step (surplus activated sludge, sewage
sludge from trickling filters) and tertiary treatment (often nutrient removal).

Primary and secondary sludges are usually combined to create a composite sludge, which
often goes for further treatment in sludge digestion and dewatering. Residues resulting from
screening in preliminary treatment are not considered as sludge, consisting mainly of coarse
solid particles, grits, sands and grease [Magoarou, 1998].

Although the ‘nitrate’ and ‘phosphate’ ions in sewage are beyond the realm of this project, it
has to be noted that pollutants such as potentially toxic elements, organics, sulphides and
residuals, can form insoluble phosphates in the course of treatment processes. These have
great propensity for sedimentation in all stages of the sewage treatment process, thus
becoming part of the sewage sludge that has to be managed.
Figure A.2 shows the schematics of urban wastewater and sewage sludge treatment.
Prel

Prim

Adv
Secondary Treatment
Trea

Trea

Trea
imintmen

ance
arytmen

Secon

men
ary t

d t
Nutrie
Sceen

Physic

Activa

Settle

Colou
Girt&

Liquid

Basin

dary
t Separ
ing,

nt Remo
ment
al/Che

ted Sludge
Remo
Greasval

r Remo
and
ation
mical
e Trap

Solid

val,
val
SECO

TERT
PRIM
RESIDUES

SLUD

SLUD
SLUD

IARY
NDAR
ARY

GE Y

GE
GE

SludAnaer
geMesop
Sludg

Dewatering Land Application


Dige
Condi

Comp
obic/A
e tioning

Stabil
hilic/T
stion
Advan
osting
erobic
isation
hermo
ced ponds

Figure A.2 Schematic Urban Wastewater and Sewage Sludge Treatment


Treatm
philic ents

Pollutants in Urban Waste Water and Sewage Sludge 233


Appendix A

REGIONAL ASPECTS:

Protection of the receiving waters from pollution by harmful effluent is the primary goal for
the treatment of urban wastewaters at WWTS. Urban wastewater is defined by the Council
Directive 91/271/EEC of 21 May 1991 concerning urban wastewater treatment (and as
amended by Commission Directive 98/15/EC of 27 February 1998) as, domestic wastewater
or the mixture of domestic wastewater with industrial wastewater and/or run-off rainwater.
The figures for water supply, consumption and treated wastewater are very variable across
the European Union. The water supply (litres/inhabitant/day) fluctuates greatly accross the
European urban areas (EUROSTAT data,1998-2000, Ginés, 1997). Not all collected
wastewater is treated; the percentage of urban wastewater not receiving treatment ranges
from 3% in Germany, up to 77% in Greece. This may include unplanned wastewater
collection, such as septic systems or leakage of UWW collection systems. Cities such as
Milan and Brussels do not yet have a centralised WWTS.

Table A.1 Population and household access to sewerage and wastewater treatment
facilities
Country Population Percentage of population with access to sewerage and public WWT
(1998) facilities
thousands Access to No treatment P P+S P+S+ Year
sewerage T
(%) (%) (%) (%) (%)
Austria 8,075 76 1 1 39 35 1995
Belgium 10,192 78 37 1997
Denmark 5,295 87 18 1996
Finland 5,147 78 0 7 71 1997
France 58,727 81 4 0 0 77 1994
Germany 82,057 92 >31 >47 1995
Greece 10,511 70 16 0 0 54 1996
Ireland 3,694 68 32 23 12 1 1995
Italy 57,563 84 16 3 38 26 1996
Luxembourg 424 88 0 19 57 11 1995
Netherlands 15,654 98 2 0 68 28 1994
Portugal 9,957 55 34 9 11 0 1990
Spain 39,348 62 13 11 34 3 1995
Sweden 8,848 86 0 0 5 81 1995
UK 59,090 96 9 9 64 14 1996
- England & - 96 10 0 0 86 1995
Wales
-N. Ireland - 83 1996
-Scotland - 94 1996
TOTAL EU 374,582 84 - - - 48 -

[after OECD Report, 1999, EUROSTAT, 1998-2000] P=primary, S= secondary, T=tertiary


treatment

Table A.1 shows the data in EU15 for the total population, population access to UWW
collecting systems and to urban wastewater treatment facilities. The EU15 average shows
that 84 % of the households have access to UWW collecting systems, whereas only 48 % of
the urban wastewater is treated in primary + secondary + tertiary treatment facilities.

According to the European Waste Water Group (1997) report on urban wastewater
treatment in the EU and accession countries, there are marked differences between various
European regions in terms of primary, secondary and tertiary treatment as shown in Figure
A.3. The four represented groups of countries are: EU10 (all EU countries minus Austria,
Belgium, Denmark, Ireland and Sweden), EU south (France, Greece, Italy, Portugal, Spain),
EU north (Germany, Finland, Netherlands, Luxembourg and United Kingdom) and AC10
(accession countries, Bulgaria, Czech Republic, Estonia, Hungary, Lithuania, Latvia, Poland,
Romania, Slovenia, Slovakia).

Pollutants in Urban Waste Water and Sewage Sludge 234


Appendix A

The percentage of population not connected to the UWW collecting systems (considered
"rural") increases in the order:
EU north (4%) < EU south (18%) < AC10 (40%)

The percentage of untreated urban wastewater increases in the order:

EU north (7%) < AC10 (18%) <EU south (18%)

In terms of primary, secondary and nutrient removal treatment the order is:

EU north (57%) > EU south (3%) > AC10 (2%)

These differences show a north-south and an west-east divide and point towards the need
for greater investment in the urban wastewater treatment in the southern region and the
accession countries.

Figure A.3 Urban wastewater treatment in EU and accession countries (minus Cyprus)
[after EEA, 1999, chapter 3.5 Water Stress]

Pollutants in Urban Waste Water and Sewage Sludge 235


Appendix A

Northern region (Sweden, Denmark, Finland and Norway):


Environmental awareness in this region is high compared to many other countries in Europe
(Germany and the Netherlands being the major exceptions to this). This is in part due to the
environmental damage experienced in the past decades in this region from trans-boundary
acid deposition due to the burning of high sulphur fossil fuels. A number of national pollution
events, such as mercury poisoning of fish due to discharges from chloralkali plants also
increased awareness of the damage emissions can cause.

This led to increased recognition of the need for national and international agreements to
limit local and global environmental perturbations and has led Sweden and Norway in
particular to be among the most pro-active nations in terms of setting environmental
standards and education amongst the general population.

Finland, Norway and Sweden have low population densities and there are similarities in the
commercial activities in these regions, for example the oil production, metals and
engineering and paper manufacturing industries. Denmark has a higher population density
than other countries in the Northern region and therefore more of an urban environment but
also has a high level of environmental concern about water pollution, although all the
drinking water in this region is from groundwater sources. This compares with the UK, for
example, where approximately one third of potable drinking water is abstracted from surface
water sources that receive effluent from wastewater treatment.

The Central Region (Germany, Austria and CEE countries):

In addition to Germany and Austria, data are gathered where available for Switzerland and
for Central and Eastern European countries (Bulgaria, Czech Republic, Estonia, Hungary,
Latvia, Lithuania, Poland, Slovakia, Slovenia), all associated EU countries. Environmental
awareness in the Central Region is high in Germany, Austria and Switzerland whereas the
CEE countries experience a high level of environmental damage due to the long years of
neglect while part of the Soviet bloc. Transboundary pollution issues are very important in
the accession CEE countries and their neighbours. Very little data is available for the CEE
countries regarding the pollutants in UWW and SS. An inventory of organic pollutants in the
environment in the CEE countries was done by a team at Brno University, the Czech
Republic. (Persistent, Bioaccumulative and Toxic Chemicals in Central and Eastern
European Countries - State-of-the-art Report-TOCOEN REPORT No. 150, 1999). The main
organic pollutants investigated are the PAHs, PCBs, PCDD/PCDFs and their ocurrence in
the urban environments in the CEE countries. Most data available is from the Czech
Republic, Poland, Slovakia and Hungary.

The Southern Region (Greece, Italy, Portugal and Spain):

The environmental awareness in the region is on the increase in the recent years. Water
resources are limited in the Southern Region and therefore recycling of treated waste water
and pollution reduction at source are important issues. Data regarding sources of pollutants
is less abundant in the 'Southern Region' especially regarding specific organic pollutants.
The region has among the lowest percentage of population access to UWW collecting
systems in the EU (70% for Greece, 84% for Italy, 55% for Portugal and 62% for Spain). The
percentage of non-treated wastewater is among the highest in the EU (16% for Greece and
Italy, 34% for Portugal and 13% for Spain) [after OECD Report, 1999, EUROSTAT, 1998-
2000].

Typically, the metal content of sewage sludge in Italy is low, according to the literature
[Garcia-Delgado et al., 1994; Lang et al., 1988] suggesting that the sludge is mainly of
domestic origin, with negligible contribution from urban and industrial wastewater. Data for
Southern Italy were gathered in a two years pilot campaign [Braguglia et al., 2000; Marani et
al., 1998; Mininni et al., 1999].

Pollutants in Urban Waste Water and Sewage Sludge 236


Appendix A

Metal Concentration range


Southern Italy Literature
As 1.1-1.8 0.3-20
Cd 3-23 1-50
Co 1-4 5-30
Cr 227-535 40-1500
Cu 258-373 160-1600
Hg 1.1-3.1 1-12
Mn 80-109 240-600
Ni 34-57 20-240
Pb 95-137 80-850
Zn 1650-4213 900-4200
Table A.2. Metal concentrations in sewage sludge (mg/kg of DS)

Wastewater treatment systems in Italy may treat 'non domestic' wastewater if the following
requirements are fulfilled:
- the plant has a residual capacity of treatment;
- wastewater meets the limits for discharge in UWW collecting systems;
- wastewater derives from the same territorial area;
- the same treatment tariff valid for the UWW discharge is applied.

In Spain, which is organised in 17 comunidades autonomas (autonomous communities)


there are more than 300,000 point sources of water discharges (both to superficial and to
groundwater) out of which 240,000 are to UWW collecting systems [Ministerio de Medio
Ambiente, 1997]. However, the quantification of the pollutants discharged is very limited.
Routine controls are generally limited to those established in Royal Decree 509/1996 and
which must be published every two years: BOD5, COD, suspended solids, total phosphorus
and total nitrogen in the case of treatment plants located in sensitive areas. However, these
controls are usually employed only for the discharges (not for the wastewater coming into
the treatment plant). As the discharges into the UWW collecting systems are under the
control of the local governments (municipalities), the limited information on levels of
pollutants in wastewater that exists comes from the enforcement inspection controls and is
not publicly available nor published in any form [Palerm and Singer, 2000].

There is almost no information on sources of pollutants and levels of pollutants in urban


wastewater and sewage sludge in Iberia [Palerm and Singer, 2000]. Water management in
Spain is completely de-centralised and the discharges into the UWW collecting system are
under the competence of the municipal authorities, which must meet the established
parameters for discharge into the public waterways.

There is very little information sources of pollutants and levels of pollutants in urban
wastewater and sewage sludge in Portugal [Palerm and Singer, 2000]. Most of the
information that exists was obtained prior to designing the wastewater treatment plants, but
this information was gathered at a local level and is not publicly available.

Data are available in Greece for sewage sludge content of potentially toxic elements, and
more limited for pollutants in urban wastewater. The Hellenic Ministry for Environment,
Physical Planning and Public works co-ordinates the data management in terms of
pollutants load in urban areas. The research studies tend to centre on the cities of
Thessaloniki or Athens.

Pollutants in Urban Waste Water and Sewage Sludge 237


Appendix A

The Western Region (UK, Ireland, France and the Benelux countries, Belgium Netherlands
and Luxembourg):

In this region, wastewater treatment is among the most advanced in the EU. France has
over 160,000 km of sewers and 11,300 treatment plants. The WWTS are operated by public
or private bodies. The ownership of WWTS and sewers are always public, owned by
municipalities or associations of municipalities. France is divided into six Water Agencies,
mainly around hydrographic areas, Adour-Garonne, Artois-Picardie, Loire-Bretagne, Rhin-
Meuse, Rhone-Méditéranée-Corse and Seine-Normandie. The municipalities operate the
sewer systems and often, private companies run the plants [EWWG, 1997].

In the Netherlands, the municipalities are responsible for collection of sewage and disposal
of sludge from sewers. The treatment of wastewater and disposal of effluent and sludge is
the responsibility of 27 waterboards. Sludge disposal is partially privatised. In Belgium, the
municipalities are responsible for the sewerage systems in both Vlanderen and Wallonie.
Similarly, in Luxembourg, the 118 municipalities are responsible for the collection and
treatment of urban wastewater and sludge. The management of sludge is partially shared
with operators of solid waste [EWWG, 1997].

In UK there are over 300,000 km sewers and 7,600 WWTS. The collection of sewage, its
treatment and disposal of effluent and sludge are the responsibility of privately-financed
water service companies in England and Wales (10), public water and sewerage authorities
in Scotland (3), and the Water Service of the Department of Environment in Northern Ireland
[EWWG, 1997]. In the Republic of Ireland, the urban wastewater collection and treatment is
the responsibility of local councils. Private-Public Partnerships (PPP) schemes are in place
for modernising and upgrading the WWTS [Dept. of Environment and Local Govt, Ireland,
1999]

Pollutants in Urban Waste Water and Sewage Sludge 238


Appendix B

APPENDIX B Physical and chemical properties of selected pollutants

In order to understand the behaviour of organic pollutants in the urban environment the
knowledge of their physical and chemical properties is very important. Vapour pressure,
boiling-point, water solubility and distribution coefficients describe the distribution between
solid, liquid and gaseous phase. The adsorption coefficient KOC is important for transitions
between soil or sewage sludge particles and water. The transition water/air is governed by
the Henry coefficient KAW. The distribution coefficient octane/water KOW is a measure for the
lipophilic or lipophobic qualities of a chemical compound. For substances with similar
physical properties, their water solubility is a crucial factor for the liquid phase transport.

Anionic and Non-ionic Surfactants

A1. Linear Alkylbenzenesulphonate

Linear alkylbenzenesulphonate (LAS) is a synthetic compound utilized as surfactant in


detergents, washing-up liquids and cleaning agents. The most important LAS qualities are
represented in Table II.22 Figure B.1 shows the LAS structure formula.

Table B.1 LAS properties [Bürgermann 1988].


Abbreviation Molecular Molar mass Colour Solubility Vapor Density
formula pressure at 20°C
[g/mol] [g/l] [g/cm3]
LAS C18H30O3S ca. 326 colourles 1.1 extremely low 1
s

CH3-CH2-CH-(CH2)8-CH3

SO3-Na+
Figure B.1: LAS structure formula.

A2. NPEs or nonylphenol polyethoxylates and APEs alkylphenol ethoxylates

Polyethoxylated nonylphenols are important surfactants used comercially and in some


household products for many years, also as emulsifiers and solubilisers in industrial
processing, as well as household cleaning products. They have the general formula:

R-C6H4-(OCH2-CH2)nOH, where R=C9H19 and n=6-18.

B. Polychlorinated Dibenzo-p-dioxins and Dibenzofurans (PCDD/PCDF)

PCCDs and PCDFs are tricyclic, aromatic, almost planar built ethers with comparable
physical, chemical and biological qualities. They differ from each other in the position and
number of chlorine atoms and the symmetry of the basic structure. Figure B.2 shows the
structure formulas of the polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo
furans (PCDD/F).

239
Appendix B

9 1

8 2

7 3

Clx Cly
6 4

PCDD
9 1

8 2

7 3

Clx Cly
6 4

PCDF
Figure B.2 PCDD/F structure formulas.
PCDD/F are extremely heavy-volatile components (high melting and boiling-points). The
vapour pressure drops with chlorine substitution, so that low-chlorinated dioxins and furans
are quite volatile. Highly-chlorinated compounds are found in solid state adsorbed on
particles. The greatest mobility