ScorePP D5.5 Production, Treatment and Disposal of PP Contaminated Sludge, 2010-03-23 PDF

Production, treatment and disposal of
priority pollutant contaminated sludge.

Deliverable No: D5.5, Date: 23rd March, 2010
Dissemination level: PU
Erica Donner1, Kemi Seriki2, Mike Revitt1.

1
2
Urban Pollution Research Centre, Middlesex University, UK.

Anjou Recherche, Veolia Environnement, France
Source Control Options for Reducing Emissions of Priority Pollutants (ScorePP)

Sixth Framework Programme, Sub-Priority 1.1.6.3, Global Change and Ecosystems
Project no. 037036,
www.scorepp.eu,
Duration: 1 October 2006 31 March 2010
D5.5 Production, treatment and disposal of PP contaminated sludge

Date submitted: 2010-03-31
Deliverable number:
D5.5
Deliverable title:
Production, treatment and disposal of priority pollutant

contaminated sludge
Authors:
Erica Donner, Kemi Seriki, Mike Revitt
Review and assessment
Luis Castillo, Anjou Recherche
Date submitted to project coordinator:
2010-03-23
Approved by Work package leader:
2010-03-23
Approved by Project Coordinator:
2010-03-31
Abstract
This report is based on a literature review of published data and describes the sources of priority
pollutant (PP) contaminated sludge materials together with a discussion of potential treatment and
reuse/disposal pathways. Published data showing the presence of PPs in European sewage sludge is
summarised in this document along with data collected in Work Package 2 of this project during a
sludge monitoring campaign in four European case study cities. In addition to municipal sewage
sludge, the production and management of industrial process sludge and industrial wastewater
treatment sludge, greywater treatment sludge and stormwater treatment sludge is also discussed.
Conventional sludge treatment techniques have been designed primarily in order to reduce sludge
volume, odour and pathogen content and the specific removal of micropollutants has generally been of
relatively minor concern. Nowadays, with sludge disposal pathways increasingly subject to more
stringent regulation, and guideline limits for popular disposal pathways such as agricultural reuse
increasingly referring to substances such as metals, polycyclic aromatic hydrocarbons, nonylphenols
and DEHP (i.e. PPs) the presence and treatment of micropollutants in sludge is of growing relevance.
Revised European regulations pertaining to the agricultural reuse of sludge products is currently under
discussion and the revised regulations can be expected to include guideline limits for key PPs referred
to in this report. Meanwhile, experience with the dredging and disposal of stormwater sediments
remains somewhat limited but is a growing issue as relevant facilities reach the point where sediment
related maintenance is required. Overall, it is clear that current EU regulations encourage the
reuse/recycling and valorisation of the various forms of sludge waste but care must be taken to ensure
that such practices are sustainable in the long-term.
Acknowledgement
The presented results have been obtained within the framework of the project ScorePP - Source
Control Options for Reducing Emissions of Priority Pollutants, contract no. 037036, a project
coordinated by Department of Environmental Engineering, Technical University of Denmark within
the Energy, Environment and Sustainable Development section of the European Communitys Sixth
Framework Programme for Research, Technological Development and Demonstration.
Page ii
Table of Contents
Overview and general introduction
5
Section A Municipal wastewater treatment sludge
6
1. Introduction
6
2. The production of municipal sewage sludge
6
3. Sludge treatment and disposal options
7
3.1 Overview of sludge treatment and disposal options

3.2 Treatment and disposal of sludge in ScorePP case cities
4. Priority pollutants in European sewage sludge
7
11
13
4.1 Literature data
13
4.2 Case city monitoring data
23
5. Treatment of PP contaminated sewage sludge
24
6. Conclusion
33
Section B: Industrial Sludge Production and Treatment
34
1.Introduction
34
2.Sludge production and management in key European industrial sectors
35
2.1 Cement and Lime Manufacturing Industries
35
2.2 Ceramic Manufacturing Industry
37
2.3 Chlor-alkali manufacturing industry
39
2.4 Industrial cooling systems
43
2.5 Ferrous Metals Processing Industry
44
2.6 Non-ferrous metals industry
48
2.7 Food, drink and milk industries
51
2.8 Storage activities
55
2.9 Glass manufacturing industry
57
2.10 Intensive rearing of poultry and pigs
58
2.11 Large combustion plants
60
2.12 Pulp and paper industry
63
2.13 The tanning of hides and skins
67
2.14 The production of polymers
69
2.15 Surface treatment using organic solvents
70
2.16 Surface treatment of metals and plastics
71
2.17 Waste incineration
74
2.18 Large volume organic chemical industry
78
2.19 Large Volume Inorganic Chemicals - Ammonia, Acids and Fertilisers Industries
81
iii
2.20 Manufacture of organic fine chemicals
82
2.21 Manufacture of large volume inorganic chemicals solids and other industry
86
2.22 Production of specialty inorganic chemicals.
88
2.23 Management of tailings and waste-rock in mining activities
90
2.24 Mineral oil and gas refineries
92
2.25 Textiles industry
95
2.26 Slaughterhouses and animal by-products industries
97
3.Conclusions
100
Section C Greywater treatment sludge
107
1. Greywater treatment systems as sources of PP contaminated sludge and sediments and implications
of sludge disposal methods for PP fate
107
Section D Stormwater sludge and treatment
110
1.Stormwater Best Management Practices as sources of PP contaminated sludge and sediments

110
2.Treatment and/or disposal of stormwater sludge/sediments
112
General Conclusions
115
References
116
iv
Overview and general introduction

The research presented in this report was conducted as part of the European Union (EU) Framework 6
funded project Source Control Options for Reducing Emissions of Priority Pollutants (ScorePP). The
overall objective of the ScorePP project is to develop comprehensive and appropriate source control
strategies that authorities, cities, water utilities and chemical industries can use to reduce the emissions
of priority pollutants (PPs) to urban environments in order to help meet the stringent environmental
objectives of the European Water Framework Directive (WFD) (EC, 2000; Directive 2000/60/EC) and
Environmental Quality Standards (EQS) Directive (EC, 2008; Directive 2008/105/EC).
The ScorePP project focuses specifically on the priority substances (PS) and priority hazardous
substances (PHS) listed under the WFD and is organized into a set of 10 different work packages
covering areas such as PP source characteristics, treatment options, modelling and monitoring
strategies etc. Further details can be found at www.scorepp.eu. Each work package (WP) is divided
into a number of different tasks that are relevant to the overall objectives of that WP. WP5 focuses on
the use and applicability of potential treatment options for removing PPs from stormwater, household
greywater, industrial wastewater, and combined municipal wastewater. Task 5.5, as reported in this
document, addresses the treatment and disposal of PP in contaminated sludges. As such, the report is
divided into four separate sections:
Section B Industrial process sludge and industrial wastewater treatment sludge
Section D Stormwater treatment sludge
For each of these sections information from a wide variety of reference sources has been reviewed in
order to identify:
the likelihood of PP contaminated sludges being produced
the compositional characteristics of such sludges and extent of PP contamination
potential sludge treatment and disposal/reuse options
the applicability of such options.

1. Introduction
The first section of this report focuses on the sludge produced during the treatment of municipal
wastewater. End-of-pipe treatment of combined municipal wastewater is a conventional practice
throughout Europe. Combined wastewaters entering such systems typically include domestic and
commercial wastewater as well as industrial wastewater. In some cases, particularly in older cities,
combined sewers are encountered, in which case stormwater is also fed to the municipal wastewater
treatment plant. In separate sewer systems, stormwater is not included and is either released directly to
surface waters or diverted to structural stormwater treatment systems prior to release. In any case, it is
clear that the wastewater reaching municipal treatment plants is sourced from a vast array of smaller
sources located throughout the sewer network and the characteristics of such waters can therefore be
expected to vary considerably. With this wide array of sources, it is expected that if PPs are present in
the urban water cycle they will be likely to pass, at least to some degree, through this pathway of
municipal wastewater treatment, and if recalcitrant or non-degradable during treatment these
substances are also likely to be present in the resulting wastewater treatment sludge.
In the following sections a summary is given of the formation and characteristics of municipal sewage
sludge. This is followed by a description of sludge treatment and disposal methods including those
used in the European case cities that were studied in detail as part of the ScorePP project (i.e. WP2).
Literature data showing the concentrations of PPs measured in municipal sludge in the EU Member
States is then presented followed by a review of reported PP treatment efficiencies of different sludge
treatment options. Disposal/reuse options are also discussed.
2. The production of municipal sewage sludge

Wastewater is basically a mixture of liquid and suspended solid wastes from a variety of different
sources. As such it also includes a range of different pollutants with varying physico-chemical
characteristics and associated risks. Not only inorganic pollutants (e.g. metals) but also organic
pollutants and microorganisms are of potential concern during the treatment of wastewater. Hence,
techniques are designed to remove these constituents from the aqueous stream in order to improve the
quality of the discharged effluent water and ensure that it is fit for release to surface waters. Treatment
processes involving the removal of solids and dissolved compounds from the water phase typically
produce sludge. Indeed, conventional wastewater treatment systems incorporating unit processes such
as chemically assisted coagulation and settling and activated sludge processes generate large volumes
of sludge, and as EU effluent quality standards continue to become increasingly stringent ever greater
quantities of wastewater treatment sludge are produced.
The quantity, consistency and pollutant content of sludge depend on the characteristics of the influent
wastewater and applied treatment techniques. In general however, wastewater sludge has a high water
content, with even after thickening, the solids content ranging between 0.25 and 12 % of the total
volume.
Treatment steps such as sedimentation (or clarification) which involve the separation of suspended
particles and floating material by gravitational settling lead to the formation of a sludge layer at the
bottom of the settling tank. When the suspended solids cannot be removed effectively by gravitational
settling alone, chemical flocculants such as alum, ferric chloride, or lime are added to induce
coagulation, flocculation and settling. Other treatment processes leading to the production of sludge
include air flotation and filtration, and precipitation. Precipitation is typically used deliberately to aid
the removal of hazardous substances such as metals (e.g. by the addition of lime, sodium hydroxide,
sodium sulphide etc.). In such cases it can be expected that the sludge produced may contain high
concentrations of metals which could result in the sludge being classified as hazardous waste and
which may thereby limit the disposal/reuse options for that particular sludge. As indicated earlier,
biological treatment processes such as activated sludge treatment also generate significant quantities of
waste sludge and recalcitrant substances are also expected to be present in these materials.
Wastewater treatment methods will not be covered in further detail here but it is worth noting that
wastewater treatment sludge differs in composition and pollutant content depending on the stage of
treatment from which it was generated. For example, it is common to differentiate between primary
and secondary wastewater treatment sludge, with primary sludge coming from the primary processing
of wastewater, where sedimentation is typically the primary mechanism of treatment. Secondary
treatment of wastewater typically refers to biological wastewater treatment where microorganisms
(e.g. activated sludge) are used to degrade and/or remove the pollutant compounds still present in the
wastewater. Primary sludge typically differs from secondary sludge in that the primary sludge has a
higher pathogen content and is more easily dewatered than secondary sludge. Further details regarding
the conventional process of activated sludge treatment (the most common wastewater treatment
system used throughout Europe) can be found in ScorePP Deliverable 5.4.
3. Sludge treatment and disposal options

3.1 Overview of sludge treatment and disposal options
If sludge is not recycled within the treatment plant (such as the return activated sludge used to
maintain the treatment process) it needs to be disposed of. Further sludge treatment and processing
may potentially be carried out on-site or may take place externally at dedicated facilities. In some
cases sludge may be disposed of directly without further treatment (as was previously the practice for
sea disposal) but this is becoming increasingly unusual as regulations become progressively more
stringent. Indeed, over the past 30 years new regulations have increasingly promoted the (safe) reuse
and recycling of sewage sludge and/or environmentally responsible disposal options. Current EU
legislation encourages EU Member States to re-use and recycle sludge wherever possible, however,
major reuse options such as agricultural reuse and land application can only be practiced if the sludge
meets quality criteria which are sometimes difficult to achieve (e.g. guideline limits for metals may be
difficult to meet in areas with high industrial activity). Further sludge treatment and/or greater
attention to source control is often necessary to facilitate the sustainable reuse/recycling of sewage
sludge.
Conventional treatment of sludge prior to disposal focuses largely on lowering the pathogen content of
the sludge to acceptable levels to prevent the spread of disease and other negative impacts on human
and environmental health. Another key objective is to reduce the volume of sludge requiring disposal,
largely in order to lower the transport and disposal costs. Although sludge treatment and disposal is
highly variable and site specific a common order of treatment may consist of pretreatment (e.g. grit
removal, grinding, mixing etc.), following by thickening, stabilisation and conditioning, dewatering
and drying. Frequently the treatment consists of fewer steps than this but these can generally be
considered as the main categories of treatment.
It is common for sludge thickening to be used as a pretreatment to facilitate easier handling of the
sludge during subsequent treatment stages and/or disposal. Methods for sludge thickening are well
developed, with common techniques including:
gravity thickening or sedimentation using a settling tank

centrifugal thickening, with the centrifuge operated either as a solid bowl centrifuge or
imperforate basket centrifuge
flotation thickening (i.e. using Dissolved Air Flotation (DAF))
gravity belt thickening where conditioned sludge is fed to a gravity belt moving over rollers
and the sludge is ridged and furrowed by a series of plough blades, allowing the released
water to pass through the belt
rotary drum thickening, where polymer and thin sludge are mixed to flocculate and the
sludge is then separated from the water phase using rotating cylindrical screen drums
As explained earlier further treatment typically involves some form of stabilisation or conditioning
followed by additional thickening/dewatering. Common stabilisation techniques include:
chemical stabilisation, generally using lime (this may be done either before or after
dewatering), the objective being to raise the pH above 12 in order to inactivate pathogens
thermal stabilisation, where the sludge is heated in a pressure vessel at temperatures up to

260 C and pressures up to 2.8 MPa for approximately 30 minutes (this is also used as a
conditioning technique)
aerobic digestion, which is similar to an extended aerobic activated-sludge process (using

either air or oxygen) and can result in a 75 to 80 % reduction of the activated sludge volume
anaerobic digestion, which is carried out in a closed tank either in the mesophilic (30 to 38
C) or thermophilic (49 to 57 C) range and which produces a combustible gas mixture
(biogas)
dual sludge stabilisation, where upstream aerobic thermophilic digestion and downstream
anaerobic mesophilic digestion are used in combination.
In addition to lowering the pathogen content of the sludge and associated risks, these stabilisation
methods help to reduce/eliminate sludge odour, reduce the content of biodegradable sludge solids, and
also facilitate improved dewatering. Sludge conditioning techniques may also be used to improve the
conditions for subsequent thickening/dewatering, with common techniques including:
chemical conditioning using coagulants and flocculants (e.g. ferric chloride, lime, alum and
organic polymers
thermal conditioning, whereby the sludge is heated in a pressure vessel.
It should be noted that with the exception of polymer conditioning, chemical stabilisation and
conditioning can result in a considerable increase in the solids content requiring disposal. Following
stabilisation and/or conditioning the sludge is typically dewatered to lower the volume requiring
transport for disposal/reuse. Common dewatering practices include:
centrifugal dewatering
belt filter press dewatering, where the conditioned sludge passes a vacuum assisted gravity
drainage section and is then squeezed between opposing porous belts at low pressure to
release additional water
filter press dewatering, where the sludge is forced through a series of filter cloths at high
pressure to induce solid/liquid separation
Finally the sludge may be dried prior to the final disposal/reuse stage. Drying options include:
rotary drying
spray drying
flash drying
evaporation, and
multiple hearth drying
The above thermal sludge reduction methods are all heat drying techniques whereby the water content
of the sludge is reduced through vaporisation. Drying processes are frequently used prior to sludge
disposal and in the case of incineration, the water content may be reduced to the point where sludge
becomes autocombustible. Despite this, auxiliary fuels are frequently required to facilitate the efficient
combustion of sewage sludge.
Thermal sludge oxidation methods (or incineration) may also be used to reduce sludge volume by
mineralising the organic content, converting it into oxidised products (i.e. CO2 and water) that can be
discharged as gas and leaving a primarily inorganic solid fraction. Sludges treated by oxidation
methods are generally unstabilised raw sludges that have undergone dewatering. Incineration is
increasingly commonly practiced throughout Europe with subsequent disposal of the solid residue
(ash) often to landfill or for reuse in the production of building products. Techniques commonly used
for thermal sludge oxidation include:
fluidised-bed incineration (auxiliary fuel is not required after start-up if the process is
operated continuously or with shutdowns of short duration)
wet air oxidation used for untreated sludge
deep-shaft oxidation
co-incineration with other waste (costs can be reduced by using the same facility and using
the heat from waste incineration for evaporation of the sludge water content).
A summary of the main sludge treatment techniques applied throughout Europe is provided in Table
A1. Note that the availability (or non-availability) of a particular sludge disposal route can be a strong
driver influencing both the choice of wastewater treatment system and sludge treatment methods in
any given location. More detailed information regarding the treatment and disposal of sewage sludge
can be found in Spinosa and Vesilind (2001) and Tchobanoglous et al (2003).
Table A1: Sludge treatment applied in Europe (Fytili, 2008; Hosseti, 2006)
Process
Description
Sludge pasteurisation
Sludge is heated at a temperature exceeding 70C for 20 min or at 55C for

4 hours. The sludge is then sent for mesophilic anaerobic digestion.
Mesophilic anaerobic
digestion
The sludge is retained for 12 to 24 days in a digester at 35C or 25C. The

sludge is then retained for a period of 14 days before disposal.
Thermophilic aerobic
digestion
Sludge is retained for a period of 7 days at 55C.
Composting
Sludge is composted at 55C for 4 hours and stored at 40C for 5 days
followed by maturation.
Lime Stabilization of
liquid sludge
Lime is added to raise sludge pH to greater than pH 12 for at least 2 hours
Liquid storage
Sludge is stored for a minimum of 3 months
Dewatering and storage
Untreated sludge is conditioned with lime, dewatered and stored for a

minimum of 3 months
Anaerobically digested sludge is stored for 14 days
Currently, there are three major sludge disposal pathways for municipal sewage sludge, these being
the application to agricultural land, incineration/combustion (Fytili, 2008; degaard, 2002), and
landfilling. Sludge may also be incorporated in cement production. Previously, disposal to coastal
waters (i.e. sea dumping) was also widely practiced, however this route has been banned within the
EU since 31 December 1998 (Directive 91/271/EEC). Other options also exist, such as pyrolisation,
gasification, reuse in building materials, etc, but these are presently of lesser importance in terms of
the sludge volumes processed via these techniques. Fytili (2008) reports that in the EU sludge is
mostly (49 %) used for agricultural application, landfilled (40%) or incinerated (11 %), however
interest in other pathways is increasing. Common sludge disposal pathways in Europe are further
documented in Table A2 and covered in detail for individual member states by Gendebein et al (2009)
and David et al (2009).
One of the major drivers for further reducing micropollutant influent loads to municipal WWTPs is to
facilitate the beneficial reuse of sewage sludge (i.e. biosolids) for soil conditioning of agricultural
land. The European Directive most pertinent to the agricultural use of sewage sludge is Directive
86/278/EEC (European Commission, 1986) which establishes concentration limits for a number of
metals that are typically present within sludge. The concentration limits are effectively ceiling limits,
meaning that if sludge exceeds the metal concentration limit for any of the listed metals it should not
be permitted for land application. Directive 86/278/EEC is currently under revision and the working
draft for the revised Directive indicates that future limits will be more conservative (European
Commission, 2000b). To enable some member states to achieve the new limits, it is probable that
water companies will need to further tighten trade effluent consents for industries and/or seek further
means of reducing WWTP influent loads of key pollutants. The alternative would be an unwanted
reduction in land recycling of sludge and a waste of a potentially beneficial resource. Currently, most
member states impose more stringent requirements than those in the EC Directive and some member
states (e.g. Switzerland) have banned the agricultural use of sewage sludge altogether.
10
Table A2: Common sludge disposal pathways used in Europe (Fytili, 2008)
Disposal
Description
Advantage
Disadvantage
Use in
agriculture
Sludge is treated and then

spread on agricultural
land
Soil conditioning
characteristics, including
organic carbon and
nutrient content, are
beneficial for crop growth
Micropollutants present
in the sludge may be
available for plant uptake
and thereby enter the
human food chain. Also,
as the quantity of sludge
produced is often higher
than the allowed
application rate (based on
the nutrient content) it
may be necessary to store
the sludge. Sometimes
guideline limits for key
pollutants may be
difficult to achieve.
Incineration
Sludge is treated and

incinerated
The volume of sludge is

drastically reduced
Potential for emissions of

hazardous substances to
air (e.g. metals, PAHs).
Need to have appropriate
filters/scrubbers to clean
exhaust gases.
Landfilling
Sludge (or sludge ashes)

are disposed of in landfill
sites
Generation of methane
gas that can be reused
This technique is
considered to be
unsustainable and is
increasingly being phased
out.
Forestry, land
reclamation
Used as a soil conditioner
Contains soil
conditioning components,
including organic matter
and nutrients
Potential for soil and

water pollution if
pollutant contents are
high.
Combustion
Sludge is used as fuel
It is possible to meet
strict quality control
limits
Potential for release of

gases and pollutants to
the atmosphere. Need for
air filters to meet EU
standards (additional
costs).
3.2 Treatment and disposal of sludge in ScorePP case cities

3.2.1 Case city A
There are two WWTPs in Case City A. At both plants sludge is collected from the secondary clarifier
and fed to a thickening tank. The sludge is then centrifuged and fed to an anaerobic digestion tank
with mixing. Following digestion the sludge is temporarily stored in tanks prior to dewatering. A
11
polymer is added to the dewatered sludge before centrifugation and the final sludge product is stored
in silos before being used for land application of various forms (e.g. as an agricultural fertiliser or to
prepare soils or restore degraded land areas).
3.2.2 Case city B
In Case City B sludge is collected from two different points in the WWTP, from the activated sludge
tanks and from the clarifiers. The sludge is then thickened and anaerobically digested. The digested
sludge is then centrifuged, dried (thermally) and stored in tanks. This case city is currently studying
several disposal possibilities for sludge including its use in cement production, agricultural spreading,
landfilling or incineration.
3.2.3 Case city C
At the WWTP in Case City C, sludge from the primary clarifiers is collected and fed to a mixing
vessel. A cationic polymer emulsion is added to the waste sludge from the secondary clarifiers and the
sludge is then sent to a pre-thickening tank. The pre-thickened sludge is then centrifuged and added to
the mixing vessel where the sludge from the primary clarifiers is retained. The mixing vessel
homogenises the sludge from the primary and secondary clarifiers before feeding it to thermophilic
digesters (between 55 and 56C). The digested sludge is then retained in storage tanks and the biogas
generated during the sludge digestion is used to produce electricity to heat boilers. Part of the sludge
from the storage tank is sent to sludge drying beds (10 km north of the waste water treatment plant)
whilst a cationic polymer is added to the other fraction prior to centrifugation. The treated sludge is
stored in silos and containers and then transferred to a waste composting facility.
3.2.2 Case city D
At the WWTP in Case City D, sludge from the secondary clarifiers is collected and transferred to a
mixing vessel. From there the sludge is transferred to a sludge thickener then on to a second mixing
vessel. A polymer is then added to the sludge prior to centrifugation. Lime is then added to the sludge
and it is further processed in a mixing centrifuge. The final sludge product is stored in tanks.
12
4. Priority pollutants in European sewage sludge

4.1 Literature data
Concentrations of PPs in sludge may vary greatly depending on the characteristics of the area covered
by the sewerage network. For example, some PPs may be more prevalent in the vicinity of particular
utilities or industrial installations whilst others may predominate in areas with high traffic density or a
predominance of horticultural land. In Tables A3 A7, data from the literature showing
concentrations of PPs in EU sewage sludge are presented together with other relevant information
(where available) such as the type of WWTP and number of inhabitants in the local area, type of local
industry etc. The literature review for this section of the report focused on literature published between
2000 and 2008 (i.e. since publication of the EU WFD). Concentrations of key sludge pollutants such
as metals are known to have decreased in the past few decades in response to increasing concerns
about sludge disposal pathways and contaminant associated risks and recent data is therefore of greater
relevance to the current situation than older literature data which may not reflect current levels.
Overall the literature data identified have shown that the PPs most often quantified in sludge from EU
countries include PAHs, DEHP, metals, selected pesticides and biocides (e.g. diuron, endosulphan),
and nonylphenols.
13
46.6 g/kg dw
11.2 g/kg dw
20 g/kg dw
26.5 g/kg dw
5 ng/g dw
6.8 ng/g dw
58 to 274 ng/g dw (4)
51 to 99 ng/g dw (11)
Diuron
Diuron
Diuron
Diuron
Endosulphan
Hexachlorobenzene
Lindane
Endosulphan
19 WWTP in the
province of Madrid
(Spain)
Thessaloniki WWTP,
Activated Sludge
(Greece)
Gazean, composting
unit (France)
Elancourt, WWTP,
Activated Sludge
(France)
Plaisir, WWTP,
Activated Sludge
(France)
St Cyr WWTP,
Activated Sludge
(France)
Waste water treatment

plant or facility
Concentration
Priority pollutant
After sludge digestion and

dewatering
Not mentioned
Before treatment
Before treatment
Before treatment
Type of sludge analysed
Combination of urban, rural and industrial

WWTPs
Combined system serving 1 million

inhabitants, residential communities, and
an industrial area which produces 5-10%
of the total wastewater (industries include
oil refining, petrochemical, fertiliser, nonferrous metal smelting, iron and steel
manufacturing, metal recovery,
electrolytic MnO2 production, scrap metal
incineration, tyre production and
lubricating oil recovery).
Mixture of sludge from moderate

industrial activity and agriculture activity
Separate system, moderate industrial

activity

activity
Combined system, moderate industrial

activity
Area covered by the sewer network
Table A3: Presence of biocidal priority pollutants in European sewage sludge (number of samples analysed given in brackets where available).
14
Sanchez-Brunete,
2008
Katsoyiannis,
2004
Ghanem, 2007
Ghanem, 2007
Ghanem, 2007
Ghanem, 2007
Reference
0.19 g/g dw
0.17 g/g dw
4 mg/kg dw
161.4 mg/kg dw
61.7 mg/kg dw
90.9 mg/kg dw
132.8 mg/kg dw
Nonylphenol
Nonylphenol
Nonylphenol
Nonylphenol
Nonylphenol
Nonylphenol
Nonylphenol
Gazean, composting
unit (France)
Elancourt, WWTP,
Activated Sludge
(France)
Plaisir, WWTP,
Activated Sludge
(France)
St Cyr WWTP,
Activated Sludge
(France)
Danish WWTP
(Denmark)
Different WWTP
Activated sludge
(Greece)
Roskilde WWTP,
Activated Sludge
(Denmark)
Waste water treatment

plant or facility
Concentration
Priority pollutant
Not specified
Before treatment
Before treatment
Before treatment
Not specified
Dewatered anaerobic digested

sludge and dewatered
secondary sludge
Sludge from secondary

treatment
Type of sludge analysed
Mixture of sludge from moderate

industrial activity and agricultural activity

activity

activity
Combined system, moderate industrial

activity
Not specified
Domestic and industrial
Domestic and industrial (20-25 %)
Ghanem, 2007
Ghanem, 2007
Ghanem, 2007
Ghanem, 2007
15
Jensen et al. , 2005
Stasinakis,2008
Fauser,2003
Reference
Table A4: Alkylphenol concentrations in European wastewater treatment plant sludges (number of samples analysed given in brackets where known).
0.12 to 16 mg/kg dw (19)
0.1 to 1.4 mg/kg dw (9)
0.2 to 1.4 mg/kg dw (7)
1.5 to 5.8 mg/kg dw (7)
0.5 to 7.35 mg/kg dw (17)
0.75 to 2.7 mg/kg dw (7)
1.1 to 2.1 mg/kg dw (2)
0.1 to 3.8 mg/kg dw (19)
0.2 to 5.3 mg/kg dw (20)
1.2 mg/kg dw
0.43 mg/kg dw
0.31 mg/kg dw
< DL to 0.83 mg/kg dw (5)

1.27 to 6.9 mg/kg dw(5)
0.25 to 1.03 mg/kg dw(5)
0.53 to 1.65 mg/kg dw(5)
PAHs
PAHs
PAHs
PAHs
PAHs
PAHs
PAHs
PAHs
PAHs
Fluoranthene
Benzo(b)fluoranthene
Benzo(a)pyrene
Naphthalene
Fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
water
plant or
Sludge from storage

chambers along roads
in Paris (France)
Achres WWTP,
(France)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
Waste
treatment
facility
Concentration
Priority pollutant
Raw sludge
After sludge treatment
Raw sludge
Raw sludge
Thermal dried
Thermal dried
Thermal dried and raw sludge
Raw and composted sludge
Origin of sludge
Traffic beltway
Not mentioned
Urban
Urban and industrial
Urban and industrial (1 facility)
Industrial (1 facility)
Urban and industrial (3 facilities)
Urban (1 facility)
Urban and tourism (2 facilities)
Table A5: PAH concentrations in European wastewater treatment plant sludges (number of samples analysed given in brackets where known).
16
Blanchard, 2004
Flotron, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Reference
Raw sludge
Sludge composted 76 days
Recycled sludge from the

activated sludge
Sludge from storage

in Paris (France)
South Eastern of
Poland (Poland)
Fusina WWTP urban

district of Venice
Activated sludge
(Italy)
4.92 to 7 mg/kg dw(2)

0.57 to 0.85 mg/kg dw(2)
0.83 to 1.35 mg/kg dw(2)
353.7 to 631.8 g/kg dw(4)

91.7 to 5121.1 g/kg dw(4)
115.5 to 289.2 g/kg dw (3)
110.5 to 382.8 g/kg dw (4)
101.4 to 267.8 g/kg dw(4)
68.7 to 201.2 g/kg dw(4)
31.5 ng/g dw
94.6 ng/g dw
105 ng/g dw
93 ng/g dw
87 ng/g dw
84 ng/g dw
Fluoranthene
Benzo(a)pyrene
Fluoranthene
Benzo(a)pyrene
Benzo(g,h,i)perylene
Indeno(1,2,3,-cd)pyrene
Naphthalene
Fluoranthene
Benzo(a)pyrene
Benzo(ghi)pyrene
Raw sludge
Sludge from storage

in Paris (France)
<DL to 1.7 mg/kg dw(7)

2.21 to 9.02 mg/kg dw(7)
<DL to 0.71 mg/kg dw(7)
0.53 to 1.65 mg/kg dw(7)
Naphthalene
Fluoranthene
Benzo(a)pyrene
Raw sludge
Sludge from storage

in Paris (France)
< DL to 8,25 mg/kg dw(7)

1.57 to 7.8 mg/kg dw(7)
0.25 to 0.81 mg/kg dw(7)
0.49 to 1.13 mg/kg dw(7)
Origin of sludge
Naphthalene
Fluoranthene
Benzo(a)pyrene
Waste water
treatment plant or
facility
Concentration
Priority pollutant
Table A5 contd.
Urban, pre-treated and untreated industrial

wastewater and urban runoff
Not mentioned
Expressways
Expressways
Inner ring of traffic beltway
Busetti, 2006
17
Oleszczuk, 2008
Blanchard, 2004
Blanchard, 2004
Blanchard, 2004
Reference
Not mentioned
Igualada WWTP
Catalonia (Spain)
73 to 93 g/kg dw(2)
56 to 83 g/kg dw(3)
33 to 70 g/kg dw(3)
17 to 19 g/kg dw(2)
32 to 79 g/kg dw(3)
46 to 295 to g/kg dw(2)
43 to 74 g/kg dw(2)
0.22 mg/kg dw
Naphthalene
Fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene
Naphthalene
Anaerobically digested and

dewatered sludge
Not mentioned
Manresa and Manresa

WWTP Catalonia
(Spain)
27 to 287 g/kg dw(4)

100 to 629 g/kg dw(4)
35 to 479 g/kg dw(4)
11 to 289 g/kg dw(4)
23 to 522 g/kg dw(4)
189 to 461 g/kg dw(2)
21 to 589 g/kg dw(2)
Naphthalene
Fluoranthene
Benzo(a)pyrene
Jyvvaskyl WWTP
Activated sludge
(Finland)
Treated sludge
Fusina WWTP urban

district of Venice
Activated sludge
(Italy)
28.4 ng/g dw
93.1 ng/g dw
93.2 ng/g dw
77.5 ng/g dw
86.8 ng/g dw
68.9 ng/g dw
Origin of sludge
Naphthalene
Fluoranthene
Benzo(a)pyrene
Benzo(ghi)pyrene
Waste water
treatment plant or
facility
Concentration
Priority pollutant
Table A5 contd.
Domestic, industrial, run off and landfill

leachate
Industrial wastewater
Domestic wastewater
Urban, pre-treated and untreated industrial

wastewater and urban runoff
Marttinen, 2003
Perez, 2001
Perez, 2001
Busetti, 2006
Reference
18
Not mentioned
Anaerobic digestion
Porto WWTP
(Portugal)
14 WWTPs
160 g/kg dw
685 g/kg dw
234 g/kg dw
95 g/kg dw
144 g/kg dw
156 g/kg dw
3.7 mg/kg dw
4.9 mg/kg dw
3 mg/kg dw
2.1 mg/kg dw
1.3 mg/kg dw
1.3 mg/kg dw
0.12 mg/kg dw
0.21 mg/kg dw
0.1 mg/kg dw
0.08 mg/kg dw
0.05 mg/kg dw
0.28 mg/kg dw
0.25 mg/kg dw
Naphthalene
Fluoranthene
Benzo(a)pyrene
Naphthalene
Fluoranthene
Benzo(a)pyrene
WWTP in the
Tarragona region
(Spain)
Activated sludge (10),

Percolating filter (3),
Activated sludge with
percolating filter (UK)
Not mentioned

dewatered sludge
Fluoranthene
Benzo(a)pyrene
Virrat WWTP
Activated sludge
(Finland)
0.18 mg/kg dw
Origin of sludge
Naphthalene
Waste water
treatment plant or
facility
Concentration
Priority pollutant
Table A5 contd.
Not mentioned
Urban and industrial
Industrial wastewater
Domestic, industrial and landfill leachate
Galvez, 2007
Stevens,2003
Perez, 2001
Marttinen, 2003
Reference
19
2.2 to 120.5 mg/kg dw (20)
3.2 to 50.2 mg/kg dw (10)
1.5 to 140.1 mg/kg dw (10)
6.4 to 42.1 mg/kg dw (7)
2.7 to 1002.4 mg/kg dw (16)
11.4 to 3513.8 mg/kg dw (7)
19.6 to 49.9 mg/kg dw (2)
2.1 to 258 mg/kg dw (20)
2 to 164.7 mg/kg dw (15)
267 ppm dw
38 ppm dw
182 ppm dw
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
WWTP Catalan area

(Spain)
WWTP Catalan area

(Spain)
WWTP Catalan area

(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
(Spain)
Waste water
treatment plant or
facility
Concentration
Priority pollutant
Aerobic then anaerobic

digested sludge and thermally
dried
Aerobic then anaerobic

digested sludge and
composted
Aerobic and anaerobic

digested sludge
Raw sludge sludge
Raw sludge sludge
Thermal dried sludge
Thermal dried sludge
Origin of sludge
Not mentioned
Not mentioned
Urban (8 facilities)
Urban (1 facility)
Urban and tourism (2 facilities)
Table A6: DEHP concentrations in European wastewater treatment plant sludges (number of samples analysed given in brackets where known).
Bago, 2005
Bago, 2005
Bago, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Abad, 2005
Reference
20
180 ppm dw
59 ppm dw
3.51 g/g dw
179 mg/kg dw
8 mg/kg dw
91 mg/kg dw
108 mg/kg dw
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
Virrat WWTP
Activated sludge
(Finland)
Jyvvaskyl WWTP
Activated sludge
(Finland)
Danish WWTP
(Denmark)
Espoo WWTP
Activated sludge
(Finland)
Roskilde WWTP,
Activated Sludge
(Denmark)
WWTP Catalan area

(Spain)
WWTP Catalan area

(Spain)
Waste water
treatment plant or
facility
Concentration
Priority pollutant
Table A6 contd.

dewatered sludge

dewatered sludge
Not mentioned

dewatered sludge
Sludge from secondary

treatment
Aerobic digested sludge and

composted
Aerobic digested sludge
Origin of sludge
Domestic, industrial, run off and landfill

leachate
Not mentioned
Domestic and industrial (20-25 %)
Not mentioned
Not mentioned
Marttinen, 2003
Marttinen, 2003
21
Jensen et al., 2005
Marttinen, 2003
Fauser,2003
Bago, 2005
Bago, 2005
Reference
35.2 to 52.5 g/kg dw(4)

1.95 to 76 g/kg dw(4)
17.7 to 58 g/kg dw(4)
63 mg/kg dw
300 mg/kg dw
37.9 to 59.5 g/kg dw (4)

1.9 to 76 g/kg dw (4)
21.7 to 155 g/kg dw (4)
38.12 mg/kg dw
13.02 mg/kg dw
402.8 mg/kg dw
63 mg/kg dw
300 mg/kg dw
95 and 123 mg/kg dw(2)

1.9 and 2.3 mg/kg dw(2)
29 and 21 mg/kg dw(2)
50 mg/kg dw
1.3 mg/kg dw
mg/kg d.w
20 mg/kg dw
13.4 mg/kg dw
35.8 mg/kg dw
69 mg/kg dw
Lead
Cadmium
Nickel
Nickel
Lead
Lead
Cadmium
Nickel
Lead
Cadmium
Nickel
Nickel
Lead
Lead
Cadmium
Nickel
Lead
Cadmium
Mercury
Nickel
Cadmium
Nickel
Lead
1.1
WWTP in the
Tarragona region
(Spain)
Danish WWTP
(Denmark)
2 WWTPs; Lynetten
and Hillerod
Centralrenseanlaeg
(Denmark)
Psittalia WWTP
(Greece)
Torun WWTP plant

(Poland)
South East Poland
Psittalia WWTP
(Greece)
South East Poland
Wastewater
treatment plant or
facility
Concentration
Priority pollutant
Not mentioned
Not mentioned
Sludge sedimentation tank for

the Hillerod
Centralrenseanlaeg WWTP
Not mentioned
Anaerobic digestion
Raw Sludge
Raw sludge
Sludge composted 76 days
Origin of sludge
Not mentioned
Not mentioned
Urban wastewater
Not mentioned
Not mentioned
Not mentioned
Urban basin (Athens)
Not mentioned
Table A7: Metal concentrations in European wastewater treatment plant sludges (number of samples analysed given in brackets where known).
Galvez, 2007
22
Jensen et al. , 2005
Ottosen, 2007
Stylianou, 2007
Sprynskyy, 2007
Oleszczuk, 2008
Stylianou, 2007
Oleszczuk, 2008
Reference
4.2 Case city monitoring data

As part of Work Package 2 of the ScorePP project a monitoring campaign was undertaken in a number
of European case cities in order to investigate the concentrations of PPs in various environmental
compartments. Samples from WWTPs in 2 different case cities were obtained as part of this
monitoring campaign and the results are presented in Table A8.
Table A8: Concentrations of PPs measured in sewage sludge at WWTPs in ScorePP case study cities
Case city 1
Case city 2
(2 monitoring events)
Compound
Biosolids mg/kg dw
Biosolids mg/kg dw
Biosolids mg/kg dw
Cadmium and its

compounds
1.06
Pentabromodiphenylether
<0.34
0.037
0.036
DEHP
31.34
58
61
Diuron
<0.1
<0.02
<0.02
Fluoranthene
0.305
0.08
0.03
Lead and its compounds
40.30
30
32
Mercury and its

compounds
0.9
1.1
Naphthalene
0.108
0.053
0.029
Nickel and its compounds
19.89
22
22
4-tert-Octylphenol
<0.5
0.532
0.291
Tributyltin
1.14
0.0177
0.0133
Monobutyltin
<0.001
0.0386
0.0771
Dibutyltin
<0.001
0.0864
0.104
Benzo(a)pyrene
0.123
0.04
<0.03
Benzo(b)-fluoranthene
0.180
n.a.
n.a.
Benzo(k)-fluoranthene
0.184
n.a.
n.a.
Pentachlorophenol
<4.89
<0.005
<0.005
Chlorpyrifos
na
na
na
Hexachlorobenzene
na
na
na
na = no data available
23
5. Treatment of PP contaminated sewage sludge

Literature data showing PP removal efficiencies for most sludge treatment methods were relatively
scarce and the majority of relevant studies were focused on PAHs, metals, nonylphenols and
phthalates (e.g. DEHP). These substances are known to accumulate in sludge and are of recognised
concern due to their toxic potential. The presence of certain PPs in sewage sludge is therefore already
a key issue when choosing suitable sludge disposal pathways, particularly when evaluating the
possibility of agricultural land application, but the removal efficiency and fate of many other PPs is
relatively unknown.
Tables A9 A12 contain a review of PP treatment efficiency data reported in the literature for sludge
containing PPs. The majority of studies summarised in these Tables are specific either to a single PP
or group of PPs from the same family (e.g. PAHs, metals). Some of the documented treatment
processes are already commonly applied whilst others are still being tested. The treatment options can
be divided into several different categories, and include many of the conventional treatment methods
documented earlier in this section, including:
Biological treatment: Biological treatment methods are already commonly applied in the
treatment of sewage sludge. These techniques involve aerobic and anaerobic processes that
use living organisms to treat and disinfect sludge.
Thermal treatment: Thermal treatment methods destroy the organic component of the sludge
and leave a primarily inorganic ash for final disposal. The most common thermal treatment
options include combustion, pyrolysis, gasification, and wet oxidation.
Electrokinetic treatment: Electrokinetic treatments use electricity to remove metallic

compounds from sludge.
Chemical treatments: Chemical treatments use a chemical catalyst (e.g. enzyme, ozone,
surfactant etc.) to remove or improve the removal of specifically targeted pollutants.
A combination of treatment techniques from the above categories may also potentially be applied in
order to improve the removal efficiency for key pollutants of concern. A combination of treatments
may particularly be required in order to ensure that sludge quality standards can be met when sludge is
to be integrated into construction materials or used for other specific reuse purposes.
The data presented in Table A9 indicate that removal of PAHs from sludge can be achieved using
biological treatment methods. PAHs are known to be highly persistent in the environment, with low
solubility and high affinities to organic substrates (e.g. sludge). They are also relatively recalcitrant to
biodegradation due to their low bioavailability (Chang, 2003; Trably, 2003). Anaerobic digestion is by
far the most common technique applied for sludge treatment in medium and large sized treatment
plants (Christensen, 2004), yet most of the reported research has been focused on the aerobic
biotransformation of PAHs in sludge (Chang, 2003; Christensen, 2004; Trably, 2003). The data in
Table A9 also suggest that aerobic treatments tend to achieve greater removal of PAHs than anaerobic
treatments. However, both methods have their advantages and disadvantages. Anaerobic digestion
may be less effective for PAH removal but it generally has lower operational costs than aerobic
methods and lower energy consumption. Higher molecular weight PAHs are more recalcitrant during
treatment than lower molecular weight PAHs and neither chemical or electrokinetic treatments offer
improved PAH removal efficiencies from sludge compared to biological treatment techniques.
Phthalate esters are among the most commonly used industrial chemicals and are present in a vast
range of commercial products including cosmetics, insect repellents, medicine coatings, polyvinyl
chloride materials, and construction materials to name a few. Nowadays, DEHP is also consistently
present in the environment (Xu, 2008). Due to its low solubility the compound readily accumulates in
sludge. Published articles investigating the removal of DEHP from sludge have mainly focused on the
potential for biological degradation, particularly under aerobic conditions. This may be explained by
24
the fact that the major metabolic breakdown path of phthalic esters is microbially mediated (Chang,
2007; Xu, 2008). Data in Table A10 shows that composting achieved removal efficiencies varying
between 34 % and 85 %. One study also investigated the potential for improved removal of DEHP
through the use of sonication and yeast extract addition, and concluded that microbial activity
increased as a result of ultrasonic treatment and yeast addition and thus enhanced the potential for
phthalate degradation. On the basis of the reviewed articles, aerobic degradation of DEHP appears to
be more effective than other investigated sludge treatment techniques although advanced techniques
such as sonication may be of value in further improving DEHP removal from sludge.
Literature data relating to the removal of metals from sludge have focused on four different types of
treatment: chemical extraction, bioleaching, electroreclamation, and supercritical fluid extraction. The
consulted studies focused more on Cd and Ni than on Pb and Hg, although Pb removals were noted to
range from 6 to 31 % using the investigated treatment techniques. Due to its high volatility Hg
probably partitions less strongly than other metals to sewage sludge. Due to their non-biodegradable
nature metals can only be separated from sludge, not broken down, therefore the techniques
investigated can potentially be used to separate the metals from the sludge for further concentration
prior to disposal. The methods investigated could potentially achieve up to 100 % removal (by
chemical extraction) however further research into these techniques is still needed in order to limit the
use of lime and acid and to try and improve their economic viability. It is important to note that Cd
should be recognised as a PP of major concern in relation to sludge quality, as it is highly toxic to
humans, has no known biological function and is one of the more mobile metals in soil. It is thus of
particular concern in terms of crop uptake potential as it can pose health risks to humans and animals
at levels well below phytotoxic concentrations (McLaughlin et al., 2000). Meeting the guideline limit
for Cd can therefore be a major determining factor in the choice of sludge disposal pathway where
agricultural reuse is an option.
Nonylphenol (NP) is a compound that has previously been widely used in Europe but which is
increasingly being phased out due to the 2003/53/CE Directive of the European Parliament and
Council limiting the marketing and uses of NPs to defined activities. Nevertheless there are still many
sources of NP in urban environments and it is still commonly identified in sewage sludge.
Nonylphenol is a hydrophobic compound with low water solubility and thus partitions relatively
strongly to sludge. The articles consulted regarding the removal of NPs from sludge tended to focus on
aerobic degradation, however anaerobic digestion has also been identified as being of potential benefit
from this perspective.
There is no single treatment that is most suitable for all PP contaminated sludge. This is because
different catchments receive different mixtures of PPs and the PPs have different characteristics
meaning that different treatment techniques may be more suited to different families of chemicals (e.g.
metals vs. PAHs). Further studies investigating research into the fate and removal of multiple PPs
using different sludge treatment techniques would be beneficial to ongoing discussions regarding the
most suitable sludge treatment methods and reuse/disposal pathways for PP contaminated sludge. In
some cases, combinations of treatment may be required to meet sludge quality targets for specific
reuse pathways. Where a single PP is of concern, targeted treatment for the removal of that substance
may be technically feasible but not economically viable. In any case, advanced sludge treatment
methods are an area of active research and future improvements will no doubt continue to be made.
25
Spiked municipal sludge

(Sequential batch reactor)



PAHs
PAHs
PAHs
PAHs
PAHs
Mesophilic
aerobic digestion
treatment (MAD)
Biological
method
Mesophilic
aerobic digestion
+ Tw80 (Tween,
a non-ionic
surfactant)
treatment
Biological
method
Simultaneous
sewage sludge
digestion (MetixBS) treatment
Chemical metal
leaching (MetixAC) treatment
Chemical
oxidation method
Chemical metal
leaching (MetixAC) + Tw80
treatment
Chemical
oxidation method
FLR* 2 4
BAP* 26
INP* 58
BPR* 145
FLR* 33 9
BAP* 263
INP* 211
BPR*811
3-ring PAH** 95 0.7

4-ring PAH*** 302.7
3-ring PAH** 940.5

4-ring PAH*** 791.1
6-ring PAH**** 363.8
3-ring PAH**970.3
4-ring PAH*** 57 1.8
6-ring PAH**** 22 5.4
Removal efficiency %

Sludge type
Priority
pollutants removed
Treatment
options
Table A9: Treatment and removal of PAHs in sewage sludge
High removal
efficiencies for 3ring PAH
High removal
Total PAH removal
yield higher than
MAD and Metix-BS
(60 %)
High removal
Advantage
Formation of unstable
intermediate (HOOH+2)
Addition of Tw80 is not
beneficial
PAH removal lower than

in biological processes.
Formation of unstable
intermediate (HOOH+2)
26
Zheng, et
al. 2007
Zheng, et
al. 2007
Zheng, et
al. 2007
Zheng, et
al. 2007
Low and slow removal
efficiencies for PAH (5
and 6 ring)
Higher removal
efficiencies for 5-ring PAH
than MAD

and 6 ring)
Zheng, et
al. 2007
Reference

and 6 ring)
Disadvantage

PAHs
PAHs
PAHs
Chemical
stabilization
treatment
(Stabiox)
Chemical
oxidation method
Anaerobic
digestion preozonation
Non ionic
surfactant
treatment
Better solubilisation yields for

3-ring PAH
FLR* 46
BKF* 382
BAP* 272
BPR* 272
INP* 272
FLR* 24 5
BAP* 152
INP* 115
BPR*73

Spiked industrial sludge

(Activated sludge)
Sludge type
Priority
pollutants removed
Treatment
options
Table A9 contd
Use of surfactant
promising when
combined with
biological and
chemical treatments
Lighter PAH are

degraded better
Improved removals
for light PAH
Advantage
Zheng, et
al. 2007
Use of surfactant only not
efficient. Use of required
amount of surfactant
expensive (for Tw80).
Use of required amounts of
surfactants can cause
environmental problems
(Tw80).
High cost to destroy,
recover or manage PAHs
from extracted sludge and
in liquid phase
27
BernalMartnez et
al. 2007
Zheng, et
al. 2007
Reference
Heavy PAHs have lower

removal rates
Low PAH removal yield

around 22 3.2
Disadvantage
PAHs
PAHs
Fluoranthene
Benzo(a)pyrene
Aerobic
bioreactors
Anaerobic
digestion
Fentons Reagent
process
Sludge (and spiked sludge) from

municipal WWTP
PAH contaminated sludge
Urban sludge (Activated sludge)
Sludge type
Fluoranthene 46,2% and 38 %

Benzo(b)fluoranthene 36,2 % and 42 %
Benzo(a)pyrene 48 % and 67 %
FLR* 52
ANT* 58
BBF* 52
BKF* 49
BAP* 52
BPE * 52
INP* 52
FLR* 93
ANT* 90
BBF* 87
BKF* 86
BAP* 88
BPE * 37
INP* 79
Priority
pollutants removed
Treatment
options
Table A9 contd
Trabby, E.
et al. 2003
Flotron et
al, 2005
Abiotic losses limited to

light PAH Need to select
PAH-degrading organisms
for effective removals
Long term acclimation of
methanogenic ecosystem
Competition between
organic matter and PAH
for the use of radical.
Formation of by-products
is possible. For low levels
of contamination important
amounts of hydrogen
peroxide would be needed
Production of
methane
28
Trabby, E.
et al. 2006
Important energy demand

PAH biodegradation
influenced by
bioavailability that
depends on hydraulic
parameters (Mixing and
aeration rate). Surfactant
can be added to improve
diffusion of PAH from
solids to liquid but
environmental
consideration need to be
investigated
Can be applied to
trace level
contamination
High PAH
degradation rates
with low abiotic
losses at 45C
Can attack all

oxidisable
pollutants. Solution
interesting when
dealing with a
mixture of pollutants
Reference
Disadvantage
Advantage
Doped industrial sludge

(Activated sludge)
PAHs
PAHs
Anaerobic
digestion preozonation with
tyloxapol
(surfactant)
Anaerobic
digestion postozonation
Not mentioned
FLR* 271
BKF* 271
BPR* 311
INP* 311
ANT* 221
BBF* 221
BAP* 221
Ozone reacts better with

light PAHs Soluble
organic matter in
competition with PAHs for
reaction with ozone
29
BernalMartnez et
al. 2005
BernalMartnez et
al. 2007
Negative impact on
anaerobic ecosystem
activity
Removal of heavy
PAH were enhanced
by tyloxapol
Increase in PAH
biodegradability or
bioaccessibility
PAH removal rates
improved by 50%
with post ozonation
Reference
Disadvantage
Advantage
* Fluoranthene :FLR, Benzo(a)pyrene: BAP, Indeno(1,2,3,-cd)pyrene: INP, Benzo(ghi)perylene: BPR, Benzo(k)fluoranthene: BKF, Anthracene: ANT, Benzo(b)fluroranthene: BBF,
benzo(b,j,k)fluoranthene:BPE **3-ring PAH acenaphthene, fluorene, phenanthrene ***4-ring PAH fluoranthene, pyrene, ****5-ring PAH benzo(b,j,k)fluoranthene, benzo(a)pyrene, *****6ring PAH indeno(1,2,3-cd)pyrene, benzo(ghi)perylene
Spiked urban sludge (Activated

sludge)
Sludge type
Priority
pollutants removed
Treatment
options
Table A9 contd
DEHP
PAH
DEHP
DEHP
DEHP
DEHP
DEHP
DEHP
Thermophilic
anaerobic
Composting
Composting and
aeration
Composting and
aeration
Ultrasonic pretreatment + aerobic

treatment
Enzymatic (lipase)
pre-treatment +
anaerobic digestion
Mesophilic
Anaerobic Digestion
Spiked and nonspiked sludge from

WWTP
Primary sludge
Sludge from
petroleum corp.
Aqueous Sludge
from WWTP
Raw sludge from

municipal WWTP
Sludge from
municipal WWTP
Sludge from
WWTP in
metropolitan area
Sludge type
DEHP (Spiked) 19 %
DEHP (Not spiked)
42 %
Not mentioned
Not mentioned
DEHP 34 %
DEHP 58 %
DEHP 86 %
DEHP 31.7 46.7

PAH 51 65
Removal efficiency
%
Production of methane gas
Can use raw sludge. Used before biological

treatment. Enzymes can be applied at high and
low concentration of biorefractory compounds
and wide pH range
Ultrasonics increase the activity of microorganisms and thus enhance DEHP degradation
Addition of yeast improves degradation of DEHP
but also nonylphenol degradation
Aeration of aqueous sludge
An alternative solution with rotating drum can be

made with treatment time shorter
Biodegradation preferred route for DEHP

removal. Compost can attain requirements of the
EU for land application.
High HRT positive effect on DEHP degradation

but none on PAH. Optimum conditions for PAH
and DEHP removal with HRT between 12 and 18
days
Advantage
Priority
pollutants
removed
Treatment options
Table A10: Treatment and removal of DEHP in sewage sludge
Accumulation of high DEHP

levels have negative effects on
degradation rate of DEHP
Enzymes are high cost
Sonification of important
amount of sludge may be
difficult
Composting period may be

longer
Amount of DEHP remains

binded to the compost so
possible problem may occur
while sludge spreading
High temperature enables better

degradation of DEHP
Light PAH are more readily

degraded
Disadvantage
Gavala et al.,
2003
Gavala, et al.
2004
Chang, et al.
2007
30
Marttinen et al.
2004
Marttinen et al.
2004
Cheng et al.
2008
Benabdallah ElHadj et al, 2006
Reference
Nickel
Lead
Nickel
Lead
Nickel
Cadmium
Lead
Cadmium
Cadmium
Nickel
Lead
Acid treatment
Electrokinetic
removal
Electrochemical
Electrodialytic
Electrodialytic
Sludge from
municipal
WWTP
Sludge from
municipal
WWTP
Sludge from
municipal
WWTP
Sludge from
WWTP
Sludge from
municipal
WWTP
Tannery
sludge
Sludge type
Cadmium 40 %
Nickel 39 %
Lead 6 %
Cadmium 69 %
Nickel 22 %
Cadmium 62 %
Lead 24 %
Nickel 90 %
Lead 19 %
Nickel 74 %
Lead 11 %
Cadmium 50 %
Lead 31 %
Removal achieved without the

addition of chemicals
Efficient on sediments and

human sewage
Several metals can be recovered

at the same time, short time
process, post treatment to
digested sludge
Metals can be recovered
Advantage
Metals
pollutants
removed
Priority
Composting
(50 days)
Treatment
options
Table A11: Treatment and removal of metals in sewage sludge
Compaction effects at the cathode. More efficient

when important concentrate metals. Only efficient
on metals. Should be used for very polluted
sludges
The use of a stirrer increase energy use
Can only be applied for metals removals. Should

be used for very polluted sludges
Use of acid to improve the treatment; space

requirement for the reactor. Not very efficient for
lead. Only efficient on metals. Should be used for
very polluted sludges
Uses acid. Should be used for very polluted

sludges
Metals found in leachate. Treatment of leachate is

necessary.
Disadvantage
31
Ottosen et al.,
2007
Jakobsen et
al. 2004
Matsumoto et
al. 2007
Wang et al.
2005
Stylianou et
al 2007
Haroun et
al.2007
Reference
Nonylphenol
Nonylphenol
Aerobic digestion
Anaerobic and post

aerobic treatment
Sludge from
municipal
WWTP
Sludge from
municipal
WWTP
Sludge from
WWTP
Sludge type
Nonylphenol
97,8 %
Nonylphenol
100 %
Not mentioned
Removal
efficiency %
Can be an advantage when dealing with a

mixture of micro pollutants in sludge that
need anaerobic degradation
High removal potential for nonylphenol
Performance can be improved by using

surfactants or yeast extracts
Advantage
Nonylphenol
pollutants
removed
Priority
Aerobic digestion
Treatment options
Table A12: Treatment and removal of nonylphenol in sewage sludge
Retention time of 20 days. Necessary to

aerate the digester.
Retention time of 20 days. Necessary to

aerate the digester.
Cannot use hydrogen peroxide (to

enhance PAH degradation) because toxic
for micro organisms
Disadvantage
HernandezRaquet et al.
2007
32
HernandezRaque et al. 2007
Chang et al. 2005
Reference
6. Conclusion
This sludge treatment methods used in the four ScorePP case cities included anaerobic
digestion and liming, both of which are common methods for sludge treatment throughout
Europe. Although anaerobic digestion is more economical than aerobic digestion and also
produces methane gas which can be reused as an energy source, literature data indicates that
this is not always the most efficient method in terms of PP removal during sludge treatment.
The studies published in the literature tend to be focussed on a relatively small selection of
PPs that have been the focus of concern in relation to the agricultural reuse of sludge,
including metals, PAHs, DEHP and nonylphenols. It is probable that limits for these and other
key substances will be lowered and/or added if the EU sewage sludge directive is revised. The
need for this revision and the likely scope of the revised directive are currently under
discussion in Europe and new regulations and updated guidelines relevant to PP contaminated
sludge are therefore to be expected in the relatively near future.
Currently, the mainstream disposal options for sewage sludge containing priority pollutants
remain rather limited and further work is needed to assess the sustainability of both these (e.g.
agricultural reuse, incineration) and other, more novel reuse pathways (e.g. in construction
products).
33
Section B:
Treatment
Industrial
Sludge
Production
and
1. Introduction
For many industries the production of process sludges and/or wastewater treatment sludge
presents a major management issue, potentially incurring substantial treatment and disposal
costs as well as serious logistic challenges. However, in addition to sludge wastes being
produced by industry they are also, in many cases, also used by industry for beneficial
applications. Thus, sludge management is related to industrial production processes and
manufacturing in two different ways. The first is in relation to sludge production from
industrial activities and/or on-site wastewater treatment. The second is in relation to sludge
reuse for beneficial applications in industry. For example, sludge can be used as a fuel for
industries using combustion processes for energy production (Luts et al., 2000), as a primary
material for use in products such as cement and building materials (Okuno et al., 2004;
Onaka, 2000), and even as the basis of wastewater treatment itself, as occurs when sludge is
employed in the production of activated carbon (Chen et al., 2002). Other disposal options
range from agricultural use and other types of land application to incineration and landfilling.
The following information on industrial sludge production, treatment and reuse/disposal is
based on information contained in the BREF documents prepared by the Joint Research
Council (JRC) in response to the EU Integrated Pollution Prevention and Control (IPPC)
Directive (Directive 96/61/EC). It should be noted that aside from the information regarding
specific sludge characteristics and best available technologies (BAT) for sludge treatment and
disposal presented in the individual BREF documents for particular industrial sectors, many
of these documents also refer to the BREF on Common Waste Water and Waste Gas
Treatment/Management Systems in the Chemical Sector (EC, 2006) for guidance on suitable
wastewater/sludge treatment steps. Many of the potential treatment industrial wastewater
options (e.g. chemical precipitation, coagulation and flocculation) include the addition of
alum, polyelectrolyte, and/or a combination of lime and metal salts, and subsequent settling
processes and sedimentation to produce sludge. This is also a feature of process steps such as
filtration, whilst biotreatment options such as the activated sludge process also produce
substantial quantities of waste sludge requiring treatment. It is thus a commonality of many of
the industry types covered in this report that sludge is produced largely as a function of
wastewater treatment and it is thus a key point, as noted previously in the section on
municipal sludge, that the benefits of reducing wastewater pollutant concentrations by
increasing the level of wastewater treatment (especially if this involves the addition of
biological treatment or the use of chemical flocculants) must be carefully weighed against the
complexities of dealing with greater quantities of (potentially contaminated) sludge.
Whilst the treatment options available for industrial sludges bear much in common with the
options that may be used for municipal sewage sludge treatment, waste streams from industry
can in many cases be more easily source separated for pollutant control. This means that in
some cases more specific sludge treatment approaches may be feasibly used to recover
valuable resources (e.g. valuable metals) that may otherwise act as environmental pollutants
complicating sludge disposal pathways. Typical treatment approaches incorporate sludge
thickening; stabilization; conditioning; dewatering, and drying. BAT for sludge treatment is
included in the BREF on Common Waste Water and Waste Gas Treatment/Management
Systems in the Chemical Sector (EC, 2006). For example, when sludge from waste water
facilities is treated on-site, it is BAT to:
34
concentrate sludge using appropriate thickening and dewatering techniques;

stabilise sludge for further treatment or disposal (e.g. using anaerobic digestion);
use waste energy from chemical production processes as far as possible when thermal
treatment (e.g. sludge drying) is practiced; and
operate appropriate waste gas treatment when contaminated sludge is incinerated.
The choice of sludge treatment is largely influenced by the use and disposal options available
to the industrial facility operator. The range of options may include land application, disposal
by landfill, use as a sealing material, incineration, co-incineration, wet oxidation, pyrolysis,
gasification, and even vitrification. Recycling pathways may also be available. The choice of
pathway is frequently determined on the basis of cost although new sludge regulations and
incentives to reduce waste production may also play an increasing role in deciding this. For
instance, it is worth noting that environmental legislation is increasingly limiting the disposal
options available and/or significantly increasing their cost (e.g. landfill opportunities are
becoming increasingly restricted).
In the following sections a summary is given of the major sludge fractions requiring
management in each of the industrial sectors covered by a specific BREF document. Details
given cover the production of sludge waste materials and sludge by-products, characteristics
of different sludge fractions, PPs likely to be present in the specified sludge fractions, and
sludge treatment and disposal options, including BAT where specified.
2. Sludge production and management in key European

industrial sectors
2.1 Cement and Lime Manufacturing Industries
Reference:
European Commission (2001). Integrated Pollution Prevention and Control (IPPC) Reference
Document on Best Available Techniques in the Cement and Lime Manufacturing Industries. Accessible
via: http://circa.europa.eu/Public/irc/env/ippc_brefs/library
This BREF includes processes involved in the production of cement and lime. The main operations
covered are:
raw materials storage and preparation
fuels storage and preparation
kiln systems
preparation and storage of products
packing and dispatch.
Although recognised as a highly polluting industry on the basis of greenhouse gas emissions,
the cement and lime manufacturing industries are not considered to be major polluters in
terms of water quality. Wastewater discharge from cement and lime manufacturing sites is
generally limited to surface runoff and cooling water. Cooling water may potentially be
contaminated by biocides used for cleaning and anti-slimicide paints (e.g. tributyltin has
previously been used for this application) but as discharge waters are predominantly released
directly to receiving waters the build-up of contaminated wastewater sludge does not appear
35
to be an issue for this industry. Similarly, storage and handling of fuels used during
production may potentially lead to contamination of soil and groundwater but will not lead to
the production of wastewater sludge.
One key area where sludge is involved in the cement and lime manufacturing industry is in
relation to the use of sludge as a raw material in the cement production process. For example,
efforts to increase the sustainability of cement production have resulted in increased use of
industrial waste materials as raw materials, and paper sludge has been identified as one of the
waste streams most frequently used as a partial replacement for natural raw materials in the
European cement industry. Paper sludge and sewage sludge are also frequently used as
combustion fuels by the European cement industry. As with any industrial use of sludge as a
fuel, this can potentially lead to the release of pollutants contained within the sludge, and thus
may potentially be related to the release of PPs present as sludge contaminants. The types of
PPs associated with the use of sludge in the cement and lime manufacturing industries are
identified in Table B1.
The concentrations of metals in sludge materials used for cement production is of particular
relevance. Wastes fed through the main burner in a production kiln will be decomposed in the
primary burning zone at temperatures up to 2000 C and non-volatile metal contaminants
present in the combusted waste material may thereafter be chemically incorporated into the
cement clinker. However, wastes fed to a secondary burner or preheater/precalciner will be
burnt at lower temperatures, which may not always be high enough to decompose
halogenated organic substances, and wastes that are fed in at the upper end of the kiln do not
pass the primary burning zone and may not be decomposed or bound in the cement clinker.
Feeding kiln system with materials containing volatile metals should be avoided. Volatile
metals such as mercury and semi-volatile metal compounds such as those of cadmium and
lead will not be full incorporated in the clinker matrix and may be partially emitted. Highly
metal contaminated sludges should therefore not be used without adequate consideration of
emission control. For example, mercury emissions can be reduced by careful management
(e.g. temperature control, maintenance) of the dust filtration and collection system.
Furthermore, activated carbon filters can potentially be fitted to all dry kiln systems and the
use of such emission abatement systems can be used to facilitate the safe use of waste
materials such as digested sewage sludge as process fuels. Removal efficiencies of 85 % and
95 % have been reported for the removal of metallic and ionic mercury by powdered activate
carbon injection. Currently (as of 2009) the only activated carbon filter installed at a cement
works in Europe is at a production site in Siggenthal, Switzerland. This system was installed
specifically in order to enable the cement works to use digested sewage sludge as fuel.
Table B1: Summary of sludge production and use by the cement and lime manufacturing
industries and relevant PPs potentially present in sludge from these sectors.
Sludge is
Wastewater treatment
Requires
Relevant PPs
produced
sludge is used
management of PP
contaminated
sludges
NO
YES Use of sewage
YES
Metals
sludge for fuel and raw
PAHs
materials is possible
Halogenated organic
compounds
36
2.2 Ceramic Manufacturing Industry
Reference:
Document on Best Available Techniques in the Ceramic Manufacturing Industry. Accessible via:
http://circa.europa.eu/Public/irc/env/ippc_brefs/library
This BREF covers industrial installations for the manufacture of ceramic products by firing
stoneware and porcelain. This industrial sector encompasses a wide range of raw materials and
manufacturing techniques, but all involve the selection of clays or other mainly inorganic materials
which are processed, dried and fired. The major sectors which are based on the ceramic products
manufactured are as follows:
wall and floor tiles
bricks and roof tiles
table- and ornamental-ware (household ceramics)
refractory products
sanitaryware
technical ceramics
vitrified clay pipes
expanded clay aggregates
inorganic bonded abrasives.
The production of sludge is a major waste management issue for the ceramics manufacturing
industry. Process losses from the manufacturing of ceramic products result in the production
of a variety of different sludge types, including glazing sludge, plaster sludge, and grinding
sludge. In addition, wastewater treatment facilities for ceramics manufacturing produce a
variety of sludges due to the treatment of wastewater from activities such as raw materials
preparation, cleaning body preparation, glaze preparation, and the cleaning of casting units
and application equipment. Sludge is also formed during the process of wet grinding for
manufacturing purposes. Due to the variety of different production processes producing
wastewater and sludge, and the variety of different raw materials (e.g. different glazes, clays
etc.) being used in these different processes, the quantity and composition of sludge varies
considerably both between different facilities as well as temporally within a single facility.
In terms of the presence of PPs in sludge from ceramics manufacturing there is a dearth of
readily available information. However, it is anticipated that metals such as Cd, Pb and Ni
will be present in the pigments used for some ceramics manufacturing processes. Typical
pigment systems employed for ceramics decorating purposes include lead-antimony yellow,
cadmium red pigment, and grey and black pigments including nickel. Pigment systems are
therefore a potential source of metal pollution for this industry and metals can thus be
expected to be present in some waste sludge fractions. Notably, PbO has been identified as
one of the main chemical components of sludge resulting from the manufacture of floor and
wall tiles, ranging from 0.115% of total sludge mass.
It is stated in the BREF that process wastewater from this industry may have high turbidity
and colouring owing to the very fine suspended particles of glaze and clay minerals present.
The typical chemical characterisation given also indicates the presence of metal contaminants.
Given the tendency for metals to adsorb to charged particulate matter during wastewater
treatment it is apparent that the resulting wastewater sludge will have a tendency to
37
accumulate metals. Indeed, process waste water analysis from a porcelain tableware
manufacturer treating waste water by homogenisation, flocculation, sedimentation, sand
filtration and reverse osmosis indicates highly efficient removal of lead and cadmium from
the waste water, indicating that the metals will be concentrated in the sludge fraction. Results
from a household ceramics plant also suggest this to be the case, showing 95% removal of
Pb and Zn during treatment and >67% removal of Cd.
The BAT guidance recommends that ceramics industry sludge should be recycled/reused as
much as possible by applying sludge recycling systems where appropriate and/or by reusing
sludge in other products. A specific example is given in relation to the re-use of sludge
formed during the production of wall or floor tiles where it is recommended that the sludge
arising from wastewater treatment in the ceramic body preparation process is recycled back
into the production process at a ratio of 0.41.5% of added dry sludge relative to the quantity
of raw materials used. Experience has shown that 1-1.5% sludge addition during tile
manufacturing should not adversely affect the ceramic products thereby produced.
Sludge recycling systems can more easily be implemented in facilities using wet milling for
raw materials preparation as the sludge can be introduced directly without requiring major
pre-treatment (other than simple physical or physico-chemical treatments). Sludge reuse may
also be possible if a dry body preparation process is in use, however management of this
system may be more complex due to the need for preparatory sludge drying before use.
It should be noted that sludge reuse is not applicable in all cases. For example, the reuse of
sludge containing glaze waste as a glaze constituent is possible but can in reality be relatively
difficult to manage due to considerable temporal heterogeneity in the composition of glazing
sludges (owing to the diversity of glazes simultaneously used in production in most facilities).
Although it may be a very good solution in some cases, especially if only one or a few
different glazes are applied in a facility, the use of this kind of sludge in glaze preparation
cannot be considered a general solution.
Sludge may however also be re-used in sectors of the ceramic industry other than the ceramic
sector generating the sludge. For instance, it is noted that sludge from the manufacture of
household ceramics or sanitary ware can be used as a raw material/additive in clay block
making and in the manufacture of expanded clay aggregates.
Sludge production and use by the ceramics manufacturing industry are summarized in Table
B2.
Table B2: Summary of sludge production and use by the ceramics manufacturing industry and
relevant PPs potentially present in sludge from this sector.
Sludge is
produced
sludge is used
Requires
management of PP
contaminated sludges
Relevant PPs
YES
YES - Some recycling/reuse

of sludge from ceramics
process wastewater treatment
is possible
YES
Cd, Pb, Ni
38
2.3 Chlor-alkali manufacturing industry
Reference:
Document on Best Available Techniques in the Chlor-alkali Manufacturing Industry. Accessible via:
This BREF focuses on the processes involved in the production of chlorine and caustic solutions by the
electrolysis of brine and covers:
the unloading and storage of salt
the purification and resaturation of brine
the different electrolytic processes
the position of process engineering of caustic solution concentration, purification, storage and
loading
the position of process engineering of chlorine cooling, drying, purification and liquefaction before
storage and loading
the process engineering of hydrogen cooling, purification and compression before storage and
loading.
The primary activity of the chlor-alkali manufacturing industry is to produce chlorine and
caustic solutions (e.g. sodium hydroxide, potassium hydroxide) through the electrolysis of
brine (e.g. sodium chloride, potassium chloride). The main technologies applied during chloralkali production are the mercury cell process, the diaphragm cell process and the membrane
cell process. The mercury cell process and the diaphragm cell process have been used in
chlorine production since the late 1800s, whereas the membrane cell process was introduced
much more recently in the 1970s.
In the year 2000, approximately 55% of the production capacity of chlorine in Western
Europe was associated with the mercury cell process, with a further 22% of production
capacity derived through the diaphragm cell process, 20% through the membrane cell process,
and 3% through other processes in which chlorine is produced as a by-product (e.g.
electrolysis of hydrochloric acid, molten alkali-metal, and alkaline-earth-metal chlorides).
Due to the use of mercury cell technology in chlor-alkali production, mercury is by far the
pollutant of greatest concern for this industry, potentially being emitted from the mercury cell
production process to air, water, and wastes (e.g. sludge) as well as being present to some
extent in the specific products formed. Significantly, and as noted previously, the mercury
cell process is also the predominant process used by the European chlor-alkali industry.
Process wastes are responsible for the majority of mercury emissions. In addition, future
waste disposal of mercury from decommissioned mercury cell production lines is expected to
pose a significant challenge for EU member states involved in this industry. Changeover to
the newer and environmentally preferable membrane cell technology production system has
been relatively slow throughout Europe because a large proportion of the existing chlorine
production plants were built in the 1970s, have a plant life of 40-60 years, and thus have not
yet needed replacement. Nevertheless, for many plants the time for replacement is now
approaching, and this, coupled with increasing pressure to phase out mercury cell technology
means that decommissioning of mercury cell process facilities is likely to be an imminent
39
management problem in future years. For example, Decision 90/3 of 14 June 1990 of the
Commission for the Protection of the Marine Environment of the North-East Atlantic
(PARCOM2) recommended that existing mercury cell chlor-alkali plants should be phased
out as soon as practicable, and preferably phased out completely by 2010. The listing of
mercury as a WFD PHS (i.e. requiring the cessation of emissions by 2020) has also increased
pressure on the chlor-alkali industry in Europe.
Mercury contaminated sludge from this industry is a side effect of the measures applied to
remove mercury from contaminated gas flows, water streams and products. The resulting
wastes and sludges have to be appropriately treated and carefully disposed of. One important
factor to take into account is that process methods which generate less waste, or which can be
used to facilitate the recycling of process waste streams (e.g. exhaust gas, waste waters and
other wastes), do not necessarily achieve the lowest emissions. For example, the once through
process system generates more wastewater but also generates brine sludge that is not
contaminated by mercury.
Mercury containing sludge wastes potentially produced by chlor-alkali industry facilities
using the mercury cell process include:
brine purification sludge (filter residue),
sludges from waste water treatment, and
sludges from caustic filters.
Brine purification sludges are one of the largest waste streams of the chlor-alkali industry.
Brine purification sludge from once-through brine process systems is not contaminated with
mercury as the purification and filtration step is carried out before the brine enters the process
cell and comes into contact with the mercury. On the other hand, brine purification sludge
from mercury cell process plants with brine recirculation systems does contain mercury. The
actual quantity of sludge precipitated depends on the purity of the salt used to make the brine.
For example, for plants using vacuum salt, values in the range of 120-775 g sludge per tonne
of chlorine produced have been reported for the production of brine purification sludge. For
plants using rock salt an average of about 30 kg of brine sludges are generated for every tonne
of chlorine produced. The mercury content in such sludge may differ widely (see Table B3).
Brine purification sludge may also contain other metals such as nickel if these are present in
the salt used to generate the brine. It is generally recommended however that purchase orders
for salt specify the exclusion of metal contaminated salt in order to minimise any problem
with associated process complications. For example, even trace amounts of metals in mercury
cells can cause the release of dangerous quantities of hydrogen.
Table B3: Mercury content in chlor-alkali industry brine purification sludge (reproduced from
BREF)
Sludge fraction
Mercury content/release
Year
Brine
purification
sludge from plants
using vacuum salt to
make brine
Plant A (chlorine production capacity ~ 120000 tonnes):

1.8 kg Hg in 21.3 tonnes of sludge
1.8 kg Hg in 18 tonnes of sludge
1997
1998
Plant B (chlorine production capacity ~ 110000 tonnes):

60 kg Hg in 60 tonnes of sludge
Not reported
40
Depleted brine from the once-through process should be treated for mercury removal as some
dissolved mercury is typically contained in the depleted brine from the production cells.
Much of this mercury is recirculated back into the cells (e.g. mercury may be precipitated as
sulphide and recycled back into the brine) however some is lost during brine circuit purging.
The purge water, together with any filter washings and waste liquors from the brine
purification plant is generally treated to remove mercury before discharge. As a result
mercury contaminated sludge is produced. This sludge is either distilled at the plant for
mercury recovery, stored or sent to a waste deposit.
As an indication of the type and quantities of sludge wastes generated by plants using the
mercury cell process the yearly waste generation and treatment/disposal path for Akzo Nobel
plant in Bohus (Sweden) and HydroPolymers AB plant in Stenungsund (Sweden) are
presented in Tables B4 and B5. Note that both the amount and mercury content of waste
varies between years depending on the type of maintenance work that is carried out as well as
other factors.
Table B4: Waste generation and final treatment at Akzo Nobel Bohus in 1998/99 Annual plant
capacity: 100000 tonnes of chlorine. Production based on vacuum salt (reproduced from BREF).
Waste type
[tonnes/year]
Hg
content Treatment
Final
mercury
before treatment
content [mg/kg]
Brine sludge
12 - 20
50- 150 mg/kg
Waste water
treatment sludge
30-40
15-30 g/kg
Carbon sludge
150-300 g/kg
Decomposer
carbon (graphite)
15-30 g/kg
Stabilised, then
landfilled
Distilled
Landfilled after
stabilisation
Distilled
Landfilled after
stabilisation
Distilled
Landfilled after
stabilisation
<10
20-200
20-200
Table B5: Yearly waste generation and final treatment at Hydro Polymers AB. Annual plant
capacity: 120000 tonnes of chlorine. Production based on vacuum salt (reproduced from BREF).
Waste type
[tonnes/year]
Hg
content Treatment
Final
mercury
before treatment
content [mg/kg]
Brine sludge
20-25
50-100 mg/kg
Landfilled
Waste water
treatment sludge
5-15
5-10 g/kg
Carbon sludge
2-3.5
150-450 g/kg
Decomposer
carbon (graphite)
0.5-1
150-300 g/kg
Distilled
Landfilled after
stabilisation
Distilled
Landfilled after
stabilisation
Distilled
Landfilled after
stabilisation
<10
20-200
20-200
41
Recovery of mercury is possible from caustic treatment sludges, water treatment sludges, and
the mercury distillation unit. The mercury recovery retorting or distillation process can be
applied to most materials containing metallic mercury, such as caustic treatment sludges,
decomposer graphite, stock tank sludges, etc. The distilled mercury is recovered and the final
solids typically contain from less than 10 up to 200 mg mercury/kg, although it is reported
that in some cases, particularly for materials having very fine pore sizes, this may increase to
about 1000 mg mercury/kg.
In cases where no mercury recovery retort is present, sludge has to be stored on site (generally
after treatment with sodium sulphide to convert the mercury as the insoluble sulphide), and/or
disposed of without mercury recovery. For example, in Germany, mercury contaminated
sludges are stored in disused salt mines in barrels without being pretreated. In other cases they
are offered without on-site treatment to specialised companies for treatment and/or secured
landfill.
Nickel catalysts can be used for several applications (e.g. decomposition of amalgam) within
the mercury process and thus may also be present as contaminants in sludge.
The cathode material used in membrane cells is either stainless steel or nickel. The cathodes
are often coated with a catalyst that is more stable than the substrate. Coating materials
include Ni-S, Ni-Al, and Ni-NiO mixtures, as well as mixtures of nickel and platinum group
metals. Nickel can also dissolve to a certain extent from the stainless steel equipment used in
these plants and is also released to wastewater during brine softener regeneration.
Finally, chlorinated hydrocarbons are also relevant PPs that may be formed in chlor-alkali
plants through a reaction between organic contaminants in the electrolyser and free oxidants.
Examples of chlorinated hydrocarbons which can be found in the effluent of chlor-alkali
plants are chloroform, dichloromethane, carbon tetrachloride, and tetrachloroethylene.
Although these substances are relatively volatile a small proportion can also be expected to be
found in the sludge from these facilities. The range of different PPs which have been
associated with the sludge produced in the chlor-alkali manufacturing industry is summarized
in Table B5.
Table B5: Summary of sludge production and use by the chlor-alkali manufacturing industry
and relevant PPs potentially present in sludge from this sector.
Sludge is
produced
Wastewater
treatment sludge is
used
Requires
management of PP
Relevant PPs
YES
NO
YES
Hg, Ni, chloroform,

dichloromethane, carbon
tetrachloride,
tetrachloroethylene
42
2.4 Industrial cooling systems
Reference:
Document on the application of Best Available Techniques to Industrial Cooling Systems. Accessible
This BREF addresses the following industrial cooling systems or configurations:
once-through cooling systems (with or without cooling towers)
open recirculating cooling systems (wet cooling towers)
closed circuit cooling systems air-cooled cooling systems
closed circuit wet cooling systems
combined wet/dry (hybrid) cooling systems
open hybrid cooling towers.
It is stated in the BREF for industrial cooling systems that little information has been reported
regarding the wastes/residues from cooling systems operation. This is consistent with the
limited amount of material reported in Table B6 summarising sludge production and use by
these systems. Nevertheless, the following sludges can be identified as relevant to these
systems:
sludge from the pre-treatment (e.g. decarbonation ) of intake water
sludge from the treatment of cooling water or blowdown from the operation of
recirculating wet cooling towers
waste water treatment sludge from cleaning operations
Lime softening works by raising the pH of intake water so as to precipitate the calcium and
part of the magnesium in the form of carbonates and hydroxides. This process results in the
production of a large amount of sludge and due to the high pH required (~ pH 10) may also
result in the precipitation of any metals present in the intake water. The sludge produced by
precipitation in the lime softening process is collected in the bottom of a clarifier and is
usually then pumped to a sludge thickener, where the injection of polyelectrolyte is typically
used to induce further sedimentation and thus an increase in the solids concentration. The
concentrated sludge is generally further dehydrated in vacuum drum filters or belt filters and
the resulting cake (with a remaining water content of approximately 50%) is removed for
disposal as landfill. According to the BREF document no environmental effects have been
reported from softening sludge landfill sites.
Sludge formation can also occur in the collecting basins of wet cooling systems. No particular
measures have been reported on reducing the formation of sludge although appropriate
cooling water conditioning is likely to reduce the settlement of sludge. Currently, the
chemical composition of the sludge and the local (or national) legislation will determine the
permissible disposal method for such sludges.
In several European member states, industrial installations are under increasing pressure to
limit/optimise their water use. For example, industrial facilities may be encouraged to change
from once-through systems to recirculating cooling systems and to operate recirculating
cooling towers at higher cycles of concentration. In recirculating systems a range of
techniques to improve cooling water quality are typically applied. These pre-treatment
techniques (such as flocculation, precipitation, filtration or membrane technology) help to
43
reduce the water requirements but they also lead to the production of sludge that must
subsequently be disposed of.
In addition, industrial cooling water is sometimes treated in a wastewater treatment
installation before discharge (also potentially producing sludge). For example, blowdown in
refineries is often treated together with other wastewater streams. This treatment can help to
lower the impact on receiving waters by removing biocidal substances used in the facility for
antifouling purposes but may also produce sludges containing biocidal substances. For
example, tributytin-based formulations have formerly been widely applied in cooling towers
as antifouling paints to reduce the fixation of organisms to walls, reinforce the velocity effect
and facilitate cleaning. It is reported, however, that no paints containing tributyltin are now in
use in large installations such as power plants thus this issue is likely to be of decreasing
importance in terms of the specific PPs of interest here (i.e. WFD PS/PHS).
Table B6: Summary of sludge production and use by industrial cooling systems and relevant PPs
potentially present in sludge from these sectors.
Sludge is
produced
sludge is used
Requires
management of PP
Relevant PPs
YES
NO
POSSIBLY
Metals, biocides
2.5 Ferrous Metals Processing Industry

Reference:
Document on Best Available Techniques in the Ferrous Metals Processing Industry. Accessible via:
This BREF is closely linked to the BREF on production of iron and steel which covered the
production of iron and steel to the casting process. This BREF includes activities for the processing of
semi-finished products (i.e. ingots, slabs, blooms and billets) obtained from ingot casting or continuous
casting, like hot rolling, cold rolling, drawing, hot dip metal coating and the related pre- and posttreatment of the shaped steel products.
The main operational steps regarding continuous processing that are covered are:
reheating and heat treatment of input materials, like slabs, blooms, billets and ingots
surface rectification and preparation processes: scarfing, grinding, descaling, degreasing, pickling
shaping of steel: rough milling, hot rolling, cold rolling, drawing
processes yielding special material or product qualities: annealing, temper rolling/skin pass rolling
hot dip metal coating and finishing.
Regarding batch hot dip coating of fabricated steel products, the following operational steps are
addressed:
surface preparation of fabricated steel: degreasing, rinsing, pickling, fluxing, drying
coating with molten metal
post treatment/finishing: cooling, greasing.
The ferrous metals processing sector incorporates a number of key sub-sectors, including Hot
and Cold Forming, Continuous Coating, and Batch Galvanising. Given the nature of the
44
processes and raw materials used in this industrial sector it is clear that the most important
PPs in terms of sludge management are the metals, particularly Pb, Cd and Ni, all of which
are specifically referred to in the BREF.
The hot and cold forming sub-sector involves a range of manufacturing methods including hot
rolling, cold rolling, and drawing of steel. Emissions to water from the hot rolling process
comprise oil- and solid-containing effluents, and oil containing sludges from waste water
treatment associated with this process have been reported to range from 0.4 36 kg/t
depending on the particular mill type in use. It is recommended that such oily sludge be
dewatered to allow for thermal reuse or safe disposal. Substantial quantities of cooling water
are used in hot rolling mills and the actual steel, rolls, saws, cropped ends, coilers and hot run
out tables are cooled by direct contact. Water is also used for scale breaking and flushing.
Wastewaters thus contain both scale and oil and should be collected and treated prior to
discharge, typically by sedimentation (with the sedimented solids potentially being returned
to the production process via the hot metal route), followed by filtration (often through gravel
beds). The sludge bearing waters from backwashing of the filter batteries are generally
separated in a thickener, then further dewatered and either disposed of or recycled back into
the process. BAT is to implement semi-closed and closed water circuits. Grinding sludge
from roll shops is also generated and generally requires conditioning before internal
recycling. Further details of wastes generated in hot rolling mills and reported disposal/reuse
statistics are shown in Table B7.
Cold rolling is used to change the properties of the hot rolled strip products by compression
between rollers without previously heating the material. Related activities produce acidic
wastes and waste water, oil containing wastes and waste water, and dusts from descaling and
decoiling. It is recommended that water curtains attached to decoiling operations be
transferred to wastewater treatment systems where the solids can be separated and collected
for reuse (i.e. for iron content). Pickling baths should be subject to mechanical filtration and
recirculation, whilst overflow from rinsing systems should be internally used for further
process applications (e.g. in pickling baths or wet scrubbers). Acid regeneration sludges
(approximately 0.0515 kg dry mass per tonne of steel produced) can be recycled in steel
plants or given to external recycling firms for the production of iron oxides for reuse as high
quality input in other industrial applications (e.g. for the production of iron powder,
ferromagnetic materials, construction material, pigments, glass and ceramics). These sludges
have an iron content of 55-66% and, in the case of stainless steel processing, between 3-5%
Ni. BAT is to neutralise acidic/alkaline wastewater (e.g. using calcium hydroxide sodium
hydroxide, or hydrochloric acid) and follow with appropriate wastewater treatment such as
flocculation, sedimentation, filtration and/or clarification. Sludges thus produced are
dewatered to reduce sludge volume and disposed of. Alternatively, it has been reported that
virtually waste water free operation for hydrochloric acid pickling is in fact possible, with
waste water streams being recycled rather than neutralised. The majority of wastewater
treatment sludge is typically disposed of to landfill although a small amount may be internally
reused. For example, oils and oil-containing sludges may be separated in emulsion splitting
plants and re-used in blast furnaces. Further details of wastes generated in cold rolling mills
and reported disposal/reuse statistics are shown in Table B8.
45
Table B7: Wastes generated in hot rolling mills and disposal/reuse statistics (reproduced from
BREF)
46
Table B8: Wastes generated in cold rolling mills and disposal/reuse statistics (reproduced
from BREF)
The EU has the worlds largest wire drawing industry, producing about 6 million tonnes of
wire per year. With regards to this process (in which wire rods/wires are reduced in size by
drawing them through cone-shaped openings of a smaller cross section) many aspects of
sludge management are similar to those already covered for hot and cold rolling. For
example, typical wastewater/sludge types produced include pickling sludges, grinding
sludges, acidic wastewater and related treatment sludges, and oil-containing sludges from the
use of drawing lubricants. Significantly, the use of lead baths for continuous annealing of low
carbon wire and patenting results in Pb contaminated wastes. BAT is to recycle these Pbcontaining wastes in the non-ferrous metals industry and to instigate a closed loop operation
of quench baths.
Continuous hot dip coating refers to a process whereby steel sheet or wire is continuously
passed through molten metal to produce an alloying reaction. Lead is one of the metals
typically used for this process, although the majority of coatings thereby applied are zinc.
BAT is to treat wastewater from these operations for metal removal. In the case of Pbcontaining wastewaters arising from Pb-tin coatings the BAT is wastewater treatment by
neutralising with sodium hydroxide solution, flocculation/precipitation. Sludge filter cake
should be dewatered and disposed of to landfill.
Hot dip galvanising is a further corrosion protection process generating sludge wastes in this
sector. This is a zinc coating process involving degreasing, pickling, fluxing, galvanising, and
47
finishing and as such can be understood to generate similar wastes to those already covered
above. As may be expected, BAT is to reuse as many waste components as possible, and to
have wastewater free operation of the rinsing step by reusing rinse water to replenish the
preceding process baths.
Overall there is much potential for the recycling and reuse of waste products produced in this
industry and it is important to keep the relevant waste streams separate in order to maximise
this potential. The sludge production scenarios for the ferrous metals processing industry are
summarized in Table B9.
Table B9: Summary of sludge production and use by the ferrous metals processing industry and
Sludge is
produced
Wastewater
treatment sludge
is used
Requires
management of PP
Relevant PPs
YES
POSSIBLY
YES
Pb, Cd and Ni, PAHs (from oils),

organic degreasing agents
(solvents)
2.6 Non-ferrous metals industry

Reference:
Document on Best Available Techniques in the Non Ferrous Metals Industries. Accessible via:
http://eippcb.jrc.es/reference/nfm.html
This BREF covers the techniques for the production of both primary and secondary non-ferrous
metals. The production of 42 non-ferrous metals and the production of ferro alloys are addressed. Ten
groups of metals with similar production methods are dealt with in the document:
Copper and its alloys, Tin and Beryllium
Aluminium and its alloys
Zinc, Lead, Cadmium, Antimony and Bismuth etc.
Precious metals
Mercury
Refractory metals, e.g. Chromium, Tungsten, Vanadium, Tantalum, Niobium, Rhenium, Molybdenum
Ferro alloys, e.g. Iron/Chromium, Iron/Silicon, Iron/Mn, Silicon/Manganese, Iron/Titanium,
Iron/Molybdenum, Iron/Vanadium, Iron/Boron
Alkali and alkaline earth metals, Sodium, Potassium, Lithium, Strontium, Calcium, Magnesium and
Titanium
Nickel and Cobalt
Carbon and graphite electrodes. The production of carbon and graphite anodes is included because
of the production of anodes at some aluminium smelters as an integral part of the production process.
At least 42 non-ferrous metals plus ferro alloys and carbon and graphite are produced in the
EU for use in a variety of applications in the metallurgical, chemical, construction, transport
and electricity generation/transmission industries. They are also used in many high
48
technology developments, particularly in the defence, computing, electronic and

telecommunications industries.
Non-ferrous metals are produced from a variety of primary and secondary raw materials.
Primary raw materials are derived from ores that are mined and then further treated before
they are metallurgically processed to produce crude metal. The treatment of ores is normally
carried out close to the mines. Secondary raw materials are indigenous scrap and residues and
may also undergo some pre-treatment to remove coating materials.
The non-ferrous metals industry covers the production of all four metals listed as PPs (i.e. Pb,
Ni, Cd, and Hg) and is clearly a primary sector of importance in relation to the environmental
emissions of these pollutants. European ore deposits have progressively been depleted over
the years and most concentrate for non-ferrous metals production is now imported from
outside Europe. The products of this sector are either refined metal or products known as
semis or semi manufactures which are basically metal and metal alloy castings in various
shapes. Recycled materials also constitute a key component of the raw material used for some
metals. For example, Pb is one such metal which can be recovered from waste products or
residues and returned to the production process without a loss of quality.
The structure of the industry and the relevant processes vary metal by metal and installations
tend to specialise in particular metals rather than producing all non-ferrous metals at once. In
many cases the actual process choice is governed by the nature of the raw materials available
and the characteristics and extent of impurities present. This will also affect the quantities and
nature of residues produced. Large quantities of wastewater are generated by this sector from
sources such as wet cleaning systems, acid and non-acid pickling tanks, cooling water, wet air
pollution control equipment, and other site related effluents. Common wastewater treatment
techniques that are used by this industry include precipitation, sedimentation, filtration,
flotation, ultrafiltration, and electrolysis. Process residues and by-products include slag, metal
contaminated sludge, and filter dust residues. These materials are already recycled and reused
to a large extent within the industry (e.g. rich slag can be used as raw material for other ferroalloy production chains; precipitated wastewater sludge containing metals may be returned to
the smelter or sinter machine) however room for further improvement in this respect no doubt
remains. Table B10 gives an overview of some process residues from this sector and potential
options available for dealing with them. Importantly, there is potential for residues, sludges
and slags to be treated for the recovery of valuable metals, thereby rendering the residues
suitable for other uses, such as for use as construction materials for example and potentially
creating saleable products in the process.
Organic chemicals may also be used for some aspects of the non-ferrous metals production
and may therefore be present in waste materials. For example, organic solvents may be used
for degreasing and chlorinated hydrocarbons may thereafter be entrained in wastewater
sludges. Oil may also be present. Nevertheless it is the metals which are the key PPs in this
sector as shown in table B11.
49
Table B10: Overview of residues and options for dealing with them (reproduced from BREF)
50
Table B11: Summary of sludge production and use by the non-ferrous metals processing
industry and relevant PPs potentially present in sludge from this sector.
Sludge is
produced
Wastewater
treatment sludge
is used
Requires management of
PP contaminated sludges
YES
POSSIBLY
YES
Relevant PPs
Pb, Ni. Cd, Hg, PAHs,

Solvents
2.7 Food, drink and milk industries
Reference:
Document on Best Available Techniques in the Food, Drink and Milk Industries. Accessible via:
http://ftp.jrc.es/eippcb/doc/fdm_bref_0806.pdf
This BREF addresses activities for the treatments and processes intended for the manufacture of food
products from:
animal raw materials (other than milk)
vegetable raw materials, and
treatment and processing of milk.
The scope includes the whole range of activities that may be found in European installations.
Compared with many other industrial sectors the food, drink and milk (FDM) sector is very
diverse, encompassing an extremely wide range of raw materials, products and processes. The
FDM sector is a net exporter from the EU and is spread throughout Europe, with installations
present in both industrialised and rural regions.
Many of the processes used in this sector produce sludge. For example, sludges may be
produced via production processes involving the use of fat traps, flotation techniques,
clarification and separation processes (e.g. centrifugation).
Centrifuges are used in many food production processes (e.g. to separate sludge from oil etc.)
and their use typically generates a sludge fraction. In some cases centrifugal separator sludges
may be re-used in the production process but in other cases they may need to be disposed of.
In fact, many sludge-type by-products/waste streams produced by the FDM industry are reused to make further useful products or used for animal feed whilst other non-conforming
products, waste sludges, and wastewater treatment sludges are sent for landfill. In some cases
authorities may approve the land spreading of wastewater treatment sludges and sludge-like
by-products but land spreading of these substances must in any case be carried out in
accordance with the relevant EU legislation, including adherence to the specifications of the
nitrate directive in order to protect soil quality and agricultural output. It is reported that
some FDM sector sludges and residues are recycled through the land disposal pathway.
51
Specific examples include potato fruit water, wheat solubles and the sludge from wastewater
treatment in the starch industry and sugar beet transport water, possibly after settlement.
It is difficult to gather specific information regarding the concentrations of PPs in sludges
produced by the FDM sector, however it is clear that potential exists for some PPs such as
pesticides and metals to be present in foodstuffs as contaminants and to subsequently become
incorporated in sludges produced by this industry. Some specific examples of sources of PPs
within the FDM industry which may lead to the development of PP contaminated sludges
include the following activities:
Cleaning of pipes and wastewater storage tanks (e.g. nickel)
Wearing of machines (e.g. conveyors in packaging lines) (e.g. nickel)
Blanching of raw fruit or vegetables (e.g. metals, herbicides, pesticides)
Cleaning of smoke houses (e.g. combustion byproducts such as PAHs)
Production of olive oil (e.g. PAHs).
Use of solvents (e.g. water, dichloromethane (methylene chloride)) in extraction
processes (e.g. for production of oils), for solvent decaffeination of coffee (e.g.
dichloromethane)
PPs specifically referred to in the FDM BREF document include Ni which can be used as a
catalyst in some processes (e.g. hydrogenation of oils) and may also be used as a pigment
(e.g. in oil refining). The cleaning water from these operations may thus contain traces of Ni
that may accumulate in wastewater treatment sludge. As seen above Ni may also be sourced
from the abrasion of stainless steel process equipment and machinery used in production.
Whereas traditional smoking techniques use smouldering wood or sawdust to smoke meat and
other products and do not generate significant wastewater other than that used for cleaning
purposes, mass production of smoked products is generally done using liquid smoke which is
applied by spraying, dipping or atomisation, and larger quantities of contaminated wastewater
are produced when containers or equipment that have been in contact with this liquid smoke
are cleaned. In particular, there tends to be a tar-like build-up which condenses on the walls of
the smoking chambers and which is removed using hot water and an alkaline cleaning
solution. The wastewater thus produced is highly contaminated and has a PAH content of 15
mg/l. This wastewater stream is recommended for separate disposal due to the high PAH
content, and it is clear that any sludge produced as a result will also be highly contaminated
with PAHs.
In Table B12 the quantity of WWTP sludge produced by the dairy industry (reported by the
European Dairy Association for the year 2002) for a given quantity of product is presented. It
is evident that the quantity of sludge produced can vary substantially as a function of the
quantity of solid production output, which is of course also partly dependent on the type of
wastewater treatment in use at the production site.
Table B12: WWTP sludge produced by the dairy industry (reproduced from the FDM BREF)
Solid output (kg)
WWTP sludges
Liquid milk and yoghurt
1.7 45.0
0.2 18.0
Cheese
1 20
0.2 24
Milk and whey powder
0.5 16
3 30
52
Table B13: A summary of waste water treatment processes used in different food drink and milk industry sectors (reproduced from the FDM BREF)
53
Another significant source of sludge from the FDM sector is the starch industry. Starch is produced in
Europe from maize, wheat and potatoes, and as is typically the case for the FDM sector, the quantity
of sludge produced as a result of starch production varies depending on the type and efficiency of the
manufacturing process used. Sludge production is greatest for the production of starch from potatoes,
with a maximum sludge quantity of 3 kg/t (dry mass) of raw material processed. Apparently, where
anaerobic wastewater treatment is used prior to release to the municipal WWTP, very little sludge is
produced at all.
Washing of vegetables (especially root vegetables, sugar beets etc.) produces soil sludge which can
also contain pesticides, heavy metals and other soil contaminants. It must be recognized that some
substances which are already banned or undergoing substitution or phase-out in Europe may still be
present as residues on imported food products from countries with less stringent regulations.
A wide range of primary, secondary and tertiary wastewater treatment techniques (including many
which produce sludge) are included in the FDM BREF document and hence are applicable to this
sector (see Table B13). Sludge-like materials from some treatment processes may be recoverable byproducts. For example, dissolved air flotation (DAF) sludges in the meat and dairy sector are often
recovered and reused for animal feed. Similarly, sedimented sludge from the starch sector may also be
recovered as animal feed. It should be noted that for such sludges to be recovered it is generally
necessary to avoid the use of coagulants and flocculants or else to ensure the use of suitable substances
for these purposes.
Sludge production in the FDM sector is summarized in Table B14 and, in general, the applied
treatment techniques include:
chemical/thermal sludge conditioning (to improve dewaterability and reduce volumes);
chemical, thermal, anaerobic and aerobic processes for sludge stabilisation (to improve sludge
thickening and/or dewatering and reduce odour and pathogens);
thickening by sedimentation, centrifugation or dissolved air flotation (DAF);
physical dewatering using centrifugation, belt filter presses, filter presses or vacuum filters;
sludge drying by natural evaporation, by recovery of heat produced in the installation, or by direct
energy consumption.
As stated in the BREF, BAT for the treatment of waste water sludge is to use one or more of the
following techniques: stabilization, thickening, dewatering, drying (if natural heat or heat recovered
from processes in the installation can be used). On the other hand, BAT has not yet been identified for
the use or disposal of waste water sludges from this sector although the recovery, valorization and
reuse of waste materials are encouraged. The use of brewery sludge for land application has been
reported.
Table B14: Summary of sludge production and use by the food, drink and milk industries and relevant
PPs potentially present in sludge from these sectors.
Sludge is
produced
Wastewater
treatment sludge is
used
Relevant PPs
YES
NO
POSSIBLY
Metals (e.g. Ni), PAHs,

biocides, solvents (e.g.
dichloromethane)
54
2.8 Storage activities
Reference:
European Commission (2006). Integrated Pollution Prevention and Control (IPPC) Reference Document on
Best Available Techniques on Emissions from Storage. Accessible via: http://eippcb.jrc.es/reference/esb.html
This BREF addresses the storage and the transfer/handling of liquids, liquefied gases and solids, regardless of
the sector or industry. It addresses emissions to air, soil and water. However, most attention is given to
emissions to air. Energy and noise are also addressed but to a lesser extent. In particular for the storage of
liquids and liquefied gases, the following types of tanks are addressed:
open top tank
external floating roof tank
fixed roof tank
above ground horizontal storage tanks (atmospheric)
horizontal storage tanks (pressurised)
vertical storage tanks (pressurised)
spheres (pressurised)
mounded storage tank (pressurised)
lifter roof (variable vapour space) tank
refrigerated storage tank
underground storage tank.
In particular for the solids storage methods the following are addressed:
heaps
sacks and bulk bags
silos and bunkers
packaged dangerous solids.
The other storage modes addressed are:
containers and the storage of containers
basins and lagoons
mined caverns
salt leached caverns
floating storage.
For the transfer and handling of liquids and liquefied gases, techniques such as piping systems and loading and
unloading equipment are addressed, such as as valves, pumps, compressors, flanges and gaskets, etc. For the
transfer and handling of solids, techniques such as mobile unloading devices, grabs, dump pits, fill pipes,
thrower belts, conveyors and feeders are described, and in each case the emission sources are identified.
The BREF document for emissions from storage covers the storage, transfer and handling of liquids,
liquefied gases and solids for all industry types and sectors. In terms of emissions, the document
focuses most heavily on emissions to air, specifically in relation to the emission of dust during
handling and transfer of solids. Sludge is only referred to very briefly in this document, although
sludges and residues do form during the storage of some liquid products such as oils. Examples of
storage modes for liquid products which may be linked to the production of sludge include: open top
55
storage tanks; underground storage tanks; containers; basins and lagoons. For example, tanks are used
for the storage of a very wide range of substances such as manure, cooling water, and all kinds of
chemicals and petrochemicals. Other relevant sludge sources may be derived from above ground open
and closed piping transfer systems; underground piping transfer systems; and in the cleaning of
transporters such as tanker trucks. Specific recommendations for the treatment of sludge waste that
may arise during transfer and storage of products are not given in the BREF, although the need for
special handling and disposal of sludges produced through the storage of flammable or other
hazardous liquids is referred to. For example, during the demolition of tanks that have held such
substances, any sludge must be carefully handled if removal is necessary and appropriately disposed
of. This may require the use of specialised equipment and workers.
Sludge deposition in storage tanks occurs by the mechanisms of molecular diffusion, gravity and
chemical reactivity and depends on operating conditions. Sludge formed in tanks can include a
mixture of the stored product, water and solids, such as sand, scale, wax crystals, and rust particles,
and contaminants. Sludge deposition during storage is usually uneven and does not necessarily build at
the same rate in different tanks and situations. This is because the amount of sludge formed can
depend on the temperature, product type, standing time, mixer capacity, tank shape, type of tank
bottom, and method of product receipt (i.e. via tanker, pipeline etc.). Mixing of products (e.g. by
impeller or jet mixers) during storage is considered the best method for reducing the quantity of sludge
formed. The use of air for mixing and homogenisation of liquids is not considered as BAT due to
potential for the loss and emission of volatile compounds to air (i.e. stripping).
For situations where tank sludge deposits become problematic a number of methods are available to
re-suspend deposits, and thereby minimise losses. Some such methods such as the use of chemical
additives, centrifuging or product circulation do not require the opening of the tank and can thus be
particularly useful. However, in cases where sludge depth in tanks becomes unacceptably high and
cannot be reduced by mixing technologies, tank cleaning is necessary. As an example, the cleaning of
crude oil storage tanks would require removal of the relevant tank from operational service,
discharging of any remaining stored stock in the tank, appropriate purging of any hazardous
atmosphere, and finally the manual removal and safe disposal of the sludge (e.g. by incineration) builtup in the bottom of the tank.
Specific PPs are not referred to in relation to sludge from storage facilities in the BREF document but
it is nevertheless clear that any PP-containing product which is stored in liquid form in a tank and
which may form sludge would require appropriate disposal (Table B15). It is probable that most of
this sludge would be landfilled or incinerated following appropriate pre-treatment. The cleaning of
transport/storage facilities for solid products and subsequent generation of wastewater and wastewater
sludge is another potential pathway of sludge production from the storage and transport of PP
containing products.
Table B15: Summary of sludge production and use by storage activities and relevant PPs potentially
present in sludge from this sector.
Sludge is
produced
sludge is used
Relevant PPs
YES
NO
POSSIBLY
Multiple
56
2.9 Glass manufacturing industry
Reference:
European Commission (2001, 2008). Integrated Pollution Prevention and Control (IPPC) Reference Document
on Best Available Techniques in The Glass Manufacturing Industry. Accessible via:
http://eippcb.jrc.es/reference/gls.html
This BREF covers the industrial installations for the manufacture of glass including glass fibre and
installations for melting mineral substances. It considers the different glass manufacturing industries and it is
based on the products manufactured, but inevitably there is some overlap between them. The eight glass types
covered are:
container glass
flat glass
continuous filament glass fibre
domestic glass
special glass (without water glass)
mineral wool (with two subsectors-glass wool and stone wool)
high temperature insulation wools
frits.
The main use of water by the glass manufacturing industry is for cooling and cleaning purposes. As a
result the major sources of wastewater being treated and thus potentially resulting in sludge production
are from aqueous emissions during cooling water system purges, cleaning activities, and surface water
runoff from glass manufacturing production sites. The cleaning waters do not present particular
hazards when compared with other industrial cleaning waters, but may potentially contain some
degree of oil and a mixture of inert solids. Cooling system waters may contain dissolved salts and
water treatment chemicals, whilst surface water quality depends on the site characteristics and
surrounding pollution sources and will not be considered in detail here.
The main PP of concern in relation to the potential for build up in wastewater treatment sludge from
the glass manufacturing industry is lead. Lead is used in considerable quantities due to its use in lead
containing glassware such as lead crystal products Table B16). The cleaning waters from areas where
production material may have been stored or spilled, together with the water used in the cutting and
grinding of lead containing products are particularly relevant in this case. In most cases appropriate
treatment will be applied to remove solids (e.g. settlement, precipitation, or flocculation) in order to
achieve compliance with local requirements for wastewater discharge quality. Sludge produced
through such treatment must also be disposed of in a suitable manner.
The acid polishing process, by which the glass is dipped in acid and then washed with hot water,
results in a small proportion of the glass dissolving, thereby producing lead containing wastewater as
well as "etching sludge" from precipitation of salts in the acid bath itself. This sludge is processed by
filtering and washing in order to obtain lead sulphate, or by reaction with calcium or sodium carbonate
in order to obtain lead carbonate. Both products can be reused as raw materials or recovered.
Moreover, the liquid fraction from the processing of the etching sludge produces an acidic solution
which can be reused in the polishing bath.
In general, waste separated from the process water systems during glass manufacturing is not recycled
and is disposed of to landfill. However, in some sectors, and particularly in the domestic glass sector,
initiatives are ongoing to recover and valorise key waste streams (i.e. lead crystal cutting sludge).
57
Table B16: Summary of sludge production and use by the glass manufacturing industry and relevant PPs
potentially present in sludge from this sector.
Sludge is
produced
Wastewater
treatment sludge is
used
Requires management of PP
Relevant PPs
YES
NO
YES, especially Pb crystal

production sites
Pb
2.10 Intensive rearing of poultry and pigs
Reference:
Best Available Techniques for Intensive Rearing of Poultry and Pigs. Accessible via:
http://eippcb.jrc.es/reference/irpp.html
This BREF addresses installations for the intensive rearing of poultry and pigs. Poultry is identified for the
purpose of this BREF as chicken, laying hens and broilers, turkeys, ducks or guinea fowl. The following relevant
farm activities are described, although it is acknowledged that not all of the activities will be found on every
farm:
farm management (including maintenance and cleaning of equipment)
feeding strategy (and feed preparation)
rearing of animals
collection and storage of manure
on-site treatment of manure
landspreading of manure
wastewater treatment.
The main sludge related issue for this sector is that of the slurry produced on intensive pig farms, with
approximately 37 kg of solid produced per pig per day. This slurry is removed by scraper to a solid
manure heap. Metals, particularly Cr and Zn which are used as feed additives, are present at relatively
high concentrations in pig slurry, and PPs such as Cd and Ni may also be present as can be seen in
Tables B17, B18 and B19. Pb is also potentially present, albeit at relatively low concentrations.
Systems for pig slurry treatment are typically site specific, taking into account the loading rate and the
time the treated slurry needs to be stored before land application. Pig slurry is often treated by
mechanical separation (using sieving, sedimentation or centrifugation) to convert raw slurry into 2
fractions: a fibre/solids fraction (about 10 % of the original volume and containing 18-30% dry matter)
and a liquid fraction (about 90% of the original volume). Sometimes additives are also added to induce
sedimentation of floating material in liquid manure and subsequent filtering of the liquor may result in
the formation of a sludge residue that is difficult to dispose of. Aeration of liquid manures may also
result in the production of sludge that is difficult to precipitate and may require lime dosing for further
management.
In some areas of the EU, for example in parts of Italy, there is a requirement to separate pig slurry
before disposal. The liquid produced during separation is often pumped to an aeration tank or basin
58
where it remains for approximately 2-3 weeks during which time it is treated by the activated sludge
process in order to reduce odour emissions and potentially also the nitrogen content. The activated
sludge and treated liquid are then transferred together to a settling basin to allow the activated sludge
to settle. Some of this sludge is then wasted and some returned to the aeration basin. The waste sludge
from this step is held in a storage basin to further concentrate it, before it is reused (sometimes after
composting) as fertiliser. In some areas wastewater from household and agricultural activities may
also be mixed with the slurry and applied to land, however this is not allowed in all EU member states.
Land spreading is common practice and generally the most favoured disposal method and may
therefore be a considerable source of emissions from this waste material.
On some pig farms, anaerobic digestion is used to reduce odour emissions and stabilise the slurry.
Digestion in the mesophilic temperature range is most common although the thermophilic process may
be applied in large reactors. A mechanical separation step is often applied after digestion.
In warmer regions (e.g. Greece), pig slurry is often treated using anaerobic lagoons. A typical example
would involve the use of mechanical separation to obtain a solid and liquid fraction, then transfer of
the liquid to a settling basin or lagoon, before subsequent transfer into an anaerobic lagoon system.
This type of system often takes the form of 3 to 5 earth- banked structures.
A variety of detergents are used for cleaning purposes and these will later end up either in the
wastewater treatment facilities or in the slurry.
Table B17: Example metal concentrations in slurry and dry manure (reproduced from BREF)
59
Table B18: Metal concentrations in Belgian pig slurry and poultry waste (from BREF).
Table B19: Summary of sludge production and use by intensive poultry and pig rearing industries and
relevant PPs potentially present in sludge from these sectors.
Sludge is
produced
sludge is used
Relevant PPs
YES
NO
POSSIBLY
Cd, Ni, Pb, biocides
2.11 Large combustion plants

Reference:
Best Available Techniques for Large Combustion Plants. Accessible via: http://eippcb.jrc.es/reference/lcp.html
This report deals mainly with combustion installations with a rated thermal input exceeding 50 MW. Plants with
a thermal input lower than 50 MW are, however, discussed where technically relevant because smaller units can
potentially be added to a plant to build one larger installation exceeding 50 MW.
All kinds of conventional power plants (e.g. utility boiler plants, combined heat and power plants, district
heating plants) used for mechanical power and heat generation are covered in this work. Industrial combustion
installations are covered if they use conventional fuel. The commercial availability of the fuel on the market has
been used as an indicator to identify conventional fuels. The criterion for classifying a fuel as a 'conventional
fuel' is a known composition which remains relatively constant, and indeed is usually standardised. Coal, lignite,
biomass, peat, liquid and gaseous fuels (including hydrogen and biogas) are regarded as conventional fuels. The
use of waste as a secondary fuel is also covered in this work.
Large combustion plants may both produce and use wastewater treatment sludge. For example,
wastewater sludge is generally produced through the treatment of make-up water for the steam cycle
and through the treatment of other wastewater fractions such as the wastewater from wet scrubbers
used to reduce metal emissions to air. In addition, co-combustion of sewage sludge is currently
60
practiced in some European combustion plants, particularly in countries where the land application
pathway is viewed with suspicion.
Water is usually pretreated for softening and demineralization to prevent scaling before use in a large
scale combustion plant. These pretreatments also generate wastewater which requires further
processing prior to recycling back into the various stages of the industrial process. Other wastewaters
include the spray water from belt strainers (for cleaning of surface water), filtrate from sludge draining
(with and without chemical additions) and back flushing water from sand filters. Blowdown water
from cooling towers and from occasional tower flushing may also require treatment in once through
systems in order to remove biocides or other additives. Treatment of cooling tower make-up water is a
significant source of sludge from this sector, and the sludge is typically either disposed of to landfill or
spread on agricultural land. Lime sludge from cooling tower water treatment may also potentially be
used in the cement industry.
All wet-type flue-gas cleaning systems produce wastewater that, among other things, contains metals.
This is due to the constituents of the fuel and materials used. The pH of the flue gas desulphurisation
wastewater must be increased (usually using lime milk or caustic soda) in order to precipitate metals.
Wet limestone scrubbers are the most widely used Flue Gas Desulphurisation (FGD) systems at the
current time and in Europe these are generally operated in forced oxidation mode rather than natural
oxidation mode. The system works by fresh limestone slurry continuously being charged into the
absorber whilst reaction products are withdrawn and sent for dewatering and further processing, and
forced oxidation has the advantage that the by-product gypsum slurry is easily dewatered and reused
in making plaster, wallboard, cement etc. This is in contrast to the slurry produced in natural oxidation
mode which is a mixture of calcium sulphite hemi-hydrate and gypsum. This slurry is difficult to
dewater and requires a thickener for primary dewatering, followed by secondary thickening with filters
or centrifuges. Even then the final by-product is generally 4050% water. FGD wastes are treated
differently at different plants, with some companies using flocculents and flocculation aids and others
using flocculation auxiliaries and organic sulphides. On the other hand, some operators use all three.
Organic sulphides are typically added in systems with high Hg inputs (e.g. systems co-combusting
wastes) as the precipitation as sulphides is more effective than hydroxides. This has the disadvantage
that the metal sulphides need to be disposed of and cannot be co-combusted in the process as the sulfur
and Hg would be re-released.
The aim for BAT is to strive to obtain by-products from the residues that can be recycled for use in
other industrial sectors and this aim is increasingly being met in the EU. For instance, in 1998 the
recycling rate of the various products was 89% including the proportion used for reclamation of land
and quarries. Sludge from the treatment of wastewaters from FGD systems can potentially be reused
as reaction agents in the same system if the calcium components of the waste stream are captured and
reprocessed. They can also be used as additives in other combustion related activities (e.g. to improve
ash melting behavior in coal fired combustion). Recovered gypsum from FGD sludge can be used for
various applications in the gypsum industry (e.g. as a setting retarder in cement). Sludge from the
treatment of raw waters is decarbonised and thus has a high content of calcium carbonate (e.g. 30% or
more). Such sludges may be useful as calcium fertilisers for agricultural use, however skepticism
towards this kind of residue due to the potential metal content has kept this reuse pathway to a
minimum. If no reuse options exist sludges are generally deposited in landfill.
Exhaust gas recirculation can be practiced in order to reduce NOx emissions from large bore engines
used in this sector, but clean-up of the exhaust gas also results in the production of an acidic, oily
sludge which requires treatment and disposal. Oily sludges are also collected from large combustion
plants using liquid fuels such as diesel, with oil treatment typically involving centrifugal separation
units and the integration of an oil recovery and sludge treatment system. Recovered oil is typically
burned in an auxiliary oil fired boiler and the oily sludges are dewatered, dried, solidified and
incinerated or disposed of by special contractors.
61
A particular area of interest in terms of sludge disposal relates to the combustion of secondary fuels
such as dewatered sewage sludge and other waste sludge materials (e.g. pulp and paper industry
sludges such as de-inking sludge). As this is also covered in the BREF on waste incineration, it will
not be covered in detail here. However, it should be noted that this type of activity for sludge disposal
is on the increase, largely because current legislation discourages the disposal of waste with high
calorific values (e.g. >6000 kJ/kg dry substance). Combustion of secondary fuels may be practiced
either as co-combustion (i.e. together with conventional fuels such as coal) or mono-incineration
depending on the characteristics of the treatment plant and the secondary fuel. Most secondary fuels
require pretreatment prior to combustion in order to separate the combustible from non-combustible
parts and thereby increase combustion efficiency. Sewage sludge is a typical example of a secondary
fuel requiring pretreatment to reduce the moisture content. It is worth noting that power plants are
usually not equipped with systems specifically designed for the reduction of gaseous emissions of
metals such as mercury (e.g. acid wet scrubbers and activated carbon systems), hence emissions of
these substances to air, fly ash, and other residues (e.g. FGD by-products) will increase if secondary
fuels with high concentrations of these substances are combusted. In some cases, additional pollutant
removal systems such as those specified above may be installed at the power plant to facilitate the cocombustion of secondary fuels with high metal contents, particularly if Hg emissions are problematic.
In some cases the need for these additional measures (e.g. injection of coke or activated coke) may
prove economically preventative. Leachability of metals from the residues arising from combustion of
such products will also need to be investigated if these residues are destined for landfilling.
Co-combustion of sewage sludge is increasingly commonly practiced throughout Europe and has been
demonstrated successfully in both pulverised coal-fired boilers and fluidised bed combustion plants.
The feed mix in co-combustion plants is generally determined by the drying potential of the installed
coal mills as the water content of sewage sludge is usually much higher than that of the coal. In some
cases, co-combustion may be limited to the use of sewage sludge with a dry mass content of more than
90%. Secondary fuels such as sewage sludge may contain higher concentrations of metals than
conventional fuels (see Table B20). Indeed, monitoring has shown that the concentration of metals in
waste streams may increase when sewage sludge is added for co-combustion although this is of course
highly dependent on the concentration of metals present in the sludge to begin with. Most of the
metals are fixed in the fly ash or in the by-products of the FGD. Fly ash is valued for its building
properties and can be used in the manufacture of cement, concrete and concrete products. It is also
used in the production of mortar, bricks, masonry blocks, paving and mining mortar.
Table B20: Comparison of hard coal and sewage sludge used for co-combustion (from BREF)
62
Table B21: Summary of sludge production and use by large combustion plants and relevant PPs
Sludge is
produced
Wastewater
treatment sludge is
used
Relevant PPs
YES
POSSIBLY
YES
Cd, Ni, Hg, Pb, PAHs
2.12 Pulp and paper industry
Reference:
Best Available Techniques in the Pulp and Paper Industry. Accessible via: http://eippcb.jrc.es/reference/pp.html
This BREF covers the processes involved in the production of pulp and paper in integrated pulp and paper mills
as well as for non-integrated pulp mills (market pulp) and non-integrated paper mills using purchased pulp for
paper production. The main operations covered are:
chemical pulping
kraft (sulphate) pulping
sulphite pulping
mechanical and chemi-mechanical pulping
recovered paper processing with and without de-inking
papermaking and related processes
Despite the competition from modern electronic information media, paper and board manufacturing is
a growth industry and is predicted to remain so for the foreseeable future. Pulp and paper making is a
complex area encompassing a range of different process stages and products. Pulp for paper making
may be produced either from virgin fibre by chemical or mechanical means or from recovered paper
by re-pulping. There are several environmental issues of relevance to this industry, including the large
amount of process water used by pulp and paper installations and the subsequent release of
contaminated wastewater. Nevertheless, in recent decades this sector has seen some significant
reductions in emissions largely as a result of increasing emission controls.
There is substantial potential for the increased recovery of energy from pulp and paper manufacturing
process wastes (including sludges) as well as the possibility to continue to increase process efficiency,
both of which would also help to reduce waste disposal issues. The major fuels used to generate heat
for production purposes in this sector are coal, fuel oil, natural gas, peat and wood waste, however
there is also the potential to use fibrous sludge retrieved from the effluent treatment facilities for this
purpose (although auxiliary fuel is also needed unless the sludge is mixed with bark and other wood
waste material). The resulting ash is generally landfilled. Due to the high content of inorganic matter
and water, sludge from chemical precipitation cannot be burned alone without the use of auxiliary fuel
and is thus often disposed of as landfill. If only synthetic organic polyelectrolytes are used for
flocculation the sludge is generally considered suitable for incineration.
Major sludge categories requiring management include the inorganic sludge (dregs and lime mud)
from the chemical recovery steps relevant to kraft pulp production; the wastewater treatment sludge
(including inorganic materials, fibres and biological sludge); and green liquor sludge. A large amount
of sludge is generated during primary wastewater treatment (e.g. chemical flocculation and settling).
This sludge may be used as a secondary material in the brick industry or may be incinerated on or off
63
site. Sludge is also produced during biological treatment. The most commonly used biological
treatment methods in this industrial sector are aerated lagoons and the activated sludge process.
Considerably less sludge is produced using aerated lagoons compared with the activated sludge
process, however the former is less efficient in terms of pollutant removal and is (partly for this
reason) becoming less common in this sector. In fact, it is questioned in the BREF whether the use of
aerated lagoons can still be considered as BAT. In any case it is estimated that approximately 6075%
of biological effluent treatment plants in this sector use the activated sludge process. It has also been
reported that anaerobic pretreatment prior to aerobic biological treatment can significantly reduce (i.e.
by 7080%) the excess sludge production as compared with stand-alone aerobic treatment systems.
Table B22 presents some data showing the composition of primary sludge and waste activated sludge
from the WWTP at a mechanical pulp and paper mill in Germany.
Biological treatment sludges are usually thickened prior to dewatering in a filter press, screw press or
on a vacuum filter, with the final solids content of the dewatered sludge reaching up to 4050% with
the use of a screw press following steam pretreatment. It is reported that the sludge from aerobic
lagoons is more difficult to dewater than waste activated sludge and thus typically requires more
dewatering chemicals and support fuel if disposed of by incineration. If the sludge is to be transported
for incineration it is reasonable to dry the sludge using excess heat (i.e. hot air) from the production
process. Excess biological sludge may also be recycled back into the paper production process, with
the quantity of sludge being reintroduced typically constituting less than 1% of the total amount of raw
materials used in order to avoid any adverse effects on the quality of the finished product.
Table B22: Composition of primary sludge and waste activated sludge from a German mechanical pulp
mill (reproduced from BREF)
Green liquor sludge is generally landfilled, following pretreatment to decrease the water content. For
example, drum filters with a precoat layer of lime mud may be used for drying. This type of
pretreatment results in a much higher solids content (3070%) than can be achieved by centrifugation
(820%). Table B23 shows the average concentration of a range of metals in green liquor sludge
treated with different amounts of lime mud.
64
Table B23: Average metal concentrations in green liquor sludge with different amounts of lime mud
(reproduced from BREF)
Installations carrying out activities related to the re-pulping of recycled paper and board also produce
de-inking sludge. Pigments, binders, wet strength agents, dispersion and lubrication agents, defoaming
agents, and slimicides are all potentially used or present in such installations and may become
entrained in de-inking sludges. Ink particles are also a potential source of metal contaminants (see
Table B24). De-inking sludge is generally landfilled or incinerated. Meanwhile, paper residue sludge
is also generated during fibre recovery, with the consistency and quantity produced depending largely
on the type of recovered paper being processed. This sludge may also contain metals as indicated by
the data in Table B25 which shows the composition of sludge from fibre recovery and chemicalmechanical treatment of wastewater. Paper residue sludge is sometimes recycled back into the
production process (e.g. for the production of board and corrugated medium) but tends not to meet the
quality requirements for higher-grade products, in which cases it is likely to be either incinerated or
landfilled
Table B24: Typical pollutant content of de-inking sludge from recycled fibre paper mills compared to
sludge from municipal wastewater treatment plants.
65
Table B25: Composition of sludge from fibre recovery and chemical-mechanical treatment of wastewater
(reproduced from BREF)
It appears that composting of sludge from recycled fibre plant paper mills is encouraged in some EU
Member States whilst actively discouraged in others (e.g. Germany). In general it appears that a large
proportion of this sludge is still sent to landfill although this pathway is likely to become increasingly
restricted in the future. Sludge from paper mills may also be used in the brick industry for improving
porosity of brick products, whilst co-incineration of paper industry residues is sometimes practiced in
cement kilns, coal power plants, municipal waste incinerators, blast furnaces and foundries.
A large number of chemicals are used in the paper industry and may lead to pollutant build-up in the
sludges produced by this sector (Table B26). For example, a Swedish survey reportedly found that
around 1300 different products containing around 800 different substances are used in the Swedish
paper industry. It is difficult to determine which of the PPs are most likely to be present in sludges
from this sector. Aside from the metals which are known to be present in some dyes, a range of
dispersion agents, surfactants and biocides are also known to be used in pulp and paper industry
installations, potentially including some PPs. Previously, alkylphenols, including nonylphenols and
nonylphenol ethoxylates were frequently used in this sector. Their use should now be increasingly
avoided due to recognition of their toxicity and potential endocrine disrupting properties but has
certainly been an issue in the past. The use of biocides may also be of some relevance here, although
as many of the biocidal PPs are now subject to restricted use throughout the EU this should also be of
decreasing concern. Solvents, surfactants and dispersants may also be present in biocide formulations
however and some such solvents may also potentially be PPs.
Table B26: Summary of sludge production and use by the pulp and paper industry and relevant PPs
potentially present in sludge from these sectors.
Sludge is
produced
Wastewater
treatment sludge
is used
Relevant PPs
YES
NO
YES
Metals, nonylphenols, solvents,

biocides, other
66
2.13 The tanning of hides and skins
Reference:
Best
Available
Techniques
for
the
tanning
of
hides
and
skin.
Accessible
via:
http://eippcb.jrc.es/reference/tan.html
This BREF addresses installations for the tanning of hides and skins. The types of hides and skins are restricted
to those of ovine and bovine origin because the production capacities for any other type of raw material for the
production of leather and furs are far below the threshold value given in the IPPC Directive (i.e. treatment
capacity exceeding 12 tonnes of finished products per day).
The activities carried out by the tannery industry focus on the treatment of putrescible hides and skins
to convert them into leather which can be used to produce a wide range of products. The BREF for this
industry focuses on facilities treating hides and skins of ovine and bovine origin as the facilities
processing these materials are generally the only ones above the threshold production capacity of 12
tonnes of finished products per day specified by the IPPC Directive. Production capacities for other
types of raw materials used for the production of leather and furs are typically below the threshold
production capacity of 12 tonnes. In terms of scale the EU is currently the worlds largest supplier of
leather (with Italy being the largest producer in Europe) and is a net importer of both bovine hides and
sheepskins. European tanneries are generally classed as SMEs.
The tannery process involves a complex sequence of chemical reactions and is a relatively pollutionintensive industry. Tannery production processes can generally be split into the following four
categories: hide and skin storage and beamhouse operations (e.g. soaking, unhairing, liming, fleshing),
tanyard operations (e.g. degreasing, deliming, bating, pickling, and tanning), post-tanning operations
(e.g. samming, setting, splitting, shaving, retanning, dyeing, fatliquoring and drying) and finishing
operations (e.g. conditioning, buffing, milling, surface coating etc.). Some of the intermediate products
are also tradeable products and some by-products may also be sold as raw materials for other
industries. The main sources of tannery wastewater originate from wet processing in the beamhouse,
the tanyard and the post tanning operations. Wastewaters from this industry can contain substantial
quantities of biocides, surfactants, and organic solvents. Tannery effluents are often pretreated on-site
and then discharged either to a municipal wastewater treatment plant or to a targeted industrial
treatment plant (e.g. for large scale tanneries). The level of on-site treatment in European plants varies
extensively however, from basic mechanical and physic-chemical pretreatment to full biological
treatment.
The tannery sourced pollutant receiving the greatest attention is chromium, with 80-90% of the
worlds tanneries using chromium III salts in the tanning process. Whilst Cr is not considered as a PP
for the purposes of the ScorePP project and is not listed as a WFD PS/PHS, chromium can be highly
toxic and its presence in waste sludges from this industry therefore warrants a mention. Sludges may
also contain recalcitrant compounds used as biocides (e.g. halogenated biocides), these being used
extensively in the curing, soaking, pickling, tanning and post-tanning processes, as well as organic
solvents (from degreasing activities) and metals (from pigments and fixing agents). Importantly,
surfactants are used in a wide range of tannery processes such as soaking, liming, degreasing, tanning
and dyeing, and nonylphenol ethoxylate has been particularly extensively used for these applications
due to its very useful emulsifying properties. Nevertheless, action to decrease the emissions of PPs
through substitution with less toxic alternatives is increasingly being taken in this sector. However,
67
substitution is not always 100% satisfactory. For example, alcohol ethoxylates can be used instead of
NPEs in the leather industry, but when degreasing of very fatty sheepskins is undertaken, only NPE
has been found to achieve the desired results to date. Brominated flame retardants are also potentially
found in sludges from this sector, but are increasingly being replaced by phosphate-based flame
retardants.
The suitability of dewatered wastewater treatment sludge from tanneries for further treatment such as
composting or anaerobic digestion and reuse options such land application must be assessed on a case
by case basis, as this is highly dependent on the composition of the sludge and national regulations.
The amount of waste sludge produced can be reduced to a large extent by segregating waste streams to
ensure that all potential options for recycling and commercialisation of by-products and waste matter
can be utilised. Some sludges, such as finishing sludges and sludges from wet scrubbers may require
further treatment prior to disposal. For example, lime-protein sludge and grease sludge can be recycled
after further treatment (but not for re-use in the tannery process itself). Landfilling is not considered to
be BAT for waste sludges from the tannery sector but may in some cases be the only option available.
Table B27 gives an estimate of the disposal route for tannery sludge in several different EU Member
States for the year 1997 and Table B28 summarises sludge production from this industry.
Table B27: Disposal routes of sludges from wastewater treatment in European tanneries (reproduced
from BREF)
Table B28: Summary of sludge production and use by tanneries and relevant PPs potentially present in
sludge from this sector.
Sludge is
produced
Wastewater
treatment
sludge is used
Requires management of PP
Relevant PPs
YES
NO
YES
Biocides, organic solvents,

surfactants (e.g. NPs), metals (e.g.
Cd, Pb), PBDEs
68
2.14 The production of polymers

Reference:
Best Available Techniques in the Production of Polymers. Accessible via: http://eippcb.jrc.es/reference/pol.html
This BREF focuses on the production of polymeric materials in plants on an industrial scale such as:
basic plastic materials (synthetic fibres and cellulose-based fibres)
synthetic rubbers
hydrocarbons containing oxygen such as alcohols, aldehydes, ketones, carboxylic acids, esters, acetates,
ethers, peroxides, epoxy resins.
An enormous variety of produced substances are covered by this BREF. Therefore, the document describes the
production of polymers selected according to production volume and potential environmental impact of their
manufacture as well as the availability of data. The BREF deals with environmentally relevant unit processes
and unit operations as well as with the usual infrastructure found on a typical site. It provides general guidance
for the early stages of process design. The document mainly deals with process modifications, plant operation
and maintenance, and especially with the management of unavoidable waste streams.
The list of products covered is this BREF document is not all inclusive for the sector but covers the
major polymers in terms of production volume and environmental impact. Production of the following
substances is covered: polyolefins, polystyrene, polyvinyl chloride, unsaturated polyesters, emulsion
polymerised styrene butadiene rubbers, solution polymerised rubbers containing butadiene,
polyamides, polyethylene terephthalate fibres and viscose fibres. The chemistry of polymer production
consists of three basic reaction types, polymerisation, polycondensation and polyaddition.
Large amounts of water are used for cooling purposes in this industry. In many cases this water is
fresh water sourced from rivers or wells, which is then discharged with a higher temperature, however,
in other cases a closed circuit system of cooling towers is employed.
Much of the water used in the polymerization process is recycled. Gaseous emission abatement
equipment is one of the main sources of wastewater and these may have high loads of organic
compounds. Such wastewater is typically treated by a treatment train incorporating biological
treatment (aerobic activated sludge process) and hence generating wastewater sludge. Due to the large
quantities of solvents used in this industry there is the potential for some solvents of interest to the
ScorePP project to be present in such sludge, although due to the volatility of such compounds the
main issue in relation to solvents is related to gaseous emissions of volatile organic compounds.
The wastewater treatment facility may be a dedicated plant on the site of the polymer installation, a
central facility on the site containing the polymer installation, or an external urban WWTP connected
by dedicated pipeline or a sewer with little risk of storm overflow prior to the WWTP. Optional sludge
treatment facilities (e.g. digesters, thickeners, incinerators) may also be present at the receiving
wastewater treatment plant.
Generally the sludges from the different sedimentation processes used in the wastewater treatment
process and the primary and waste activated sludge are mechanically dewatered to approximately 35
50% solids, then incinerated by fluidised bed combustion. The press water from the sludge dewatering
is recycled back into the influent wastewater to the treatment plant. Ashes from the incineration
process are often reused for material recovery, in the cement industry for example.
69
Table B29: Summary of sludge production and use by the polymer production industry and relevant PPs
Sludge is
produced
Wastewater
treatment sludge
is used
Relevant PPs
YES
NO
YES
Solvents
2.15 Surface treatment using organic solvents
Reference:
Best Available Techniques on Surface Treatment using Organic Solvents. Accessible via:
http://eippcb.jrc.es/reference/sts.html
This BREF addresses installations for the surface treatment of substances, objects or products using organic
solvents, in particular for dressing, printing, coating, degreasing, waterproofing, sizing, painting, cleaning or
impregnating. The activities addressed are:
printing (by heatset web offset, flexography and packaging gravure, publication gravure)
painting and other coating activities (winding wires, cars, trucks, buses, trains, agricultural and construction
equipment, ships and yachts, aircraft, wood and mirrors, furniture, metal coil, metal packaging, and other metal
and plastic goods)
waterproofing (by painting and wood preservation)
adhesive application (in the manufacture of abrasives and adhesive tapes)
cleaning and degreasing in conjunction with other surface treatment activities
impregnation for the preservation of wood.
This industry is based on the treatment of substances, objects or products using organic solvents. A
wide range of substances and products may therefore be involved. BAT relevant to sludge production
includes the reduction of water use and hence effluent discharge and wastewater treatment sludge
production, along with process optimisation to minimise paint sludge build-up. Furthermore, paint
sludge should be dewatered to minimise the volume for disposal, or may be recycled.
Key types of sludge produced aside from the wastewater treatment sludge include paint sludges, ink
sludges/residues, and cleansing bath sludge. Paint sludge results from the use of water to capture
overspray during spray painting. The addition of coagulation agents to the water to facilitate
separation generates a residual paint sludge requiring management. These sludges consist of paint
particles, small amounts of organic solvents, coagulation agents and water and can potentially be
incinerated with energy recovery. Surplus inks that are not disposed of as waste are generally distilled
in-house in order to recover the solvent content for cleaning purposes. The residual ink sludge from
the distillation of cleaning agents still contains a high proportion of solvent (approx. 26%) and must
subsequently be disposed of as waste. Distillation of surplus ink and cleaning agents for solvent
recovery nevertheless helps to minimise the waste sludge produced. Moreover, where water-based
coatings, paints or inks are applied, ultrafiltration or similar techniques may be used to recover paint or
ink for reuse in new paint/ink mixes. In addition, where cleaning is carried out without the use of
70
solvents and/or where water based inks are used, the resulting wastewater may be discharged to sewer
and treated by conventional means. Generally speaking, BAT for minimising waste sludge production
from activities such as the coating of cars, trucks, buses etc. is to dewater the sludge to reduce the
volume and/or to recycle the sludge. Operational approaches may also be changed, for example, the
water emulsion technique may be adopted for use in spray painting activities (this concentrates the
paint overspray in an emulsion, thus eliminating water booth usage and paint sludge waste).
Priority pollutants potentially present in sludge waste materials from this sector include various
solvents, metals, organotin compounds, and possibly some biocides (Table B30). Solvent use is the
major activity of this industrial sector and hence the most obvious environmental contamination issue.
Metals such as Cd, Pb, and Ni are sometimes present in water-based pretreatments and pigments for
ink and paint but are not widely used in large scale surface treatments using organic solvents. Water
based coatings are however a key substitute for solvent-based coatings and their use may also entail
the use of biocides to prevent their degradation during storage and use. Organotin compounds may be
used as catalysts in electrocoat paint systems, and tributyltin contaminations of wastewater sludges
may also result from the removal and/or application of antifouling coatings on ships. Finally,
phosphate coatings (for corrosion protection and adhesion stability) may also contain metals such as
Ni, which is therefore a further source of potential metal pollution.
Table B30: Summary of sludge production and use by the organic solvents surface treatment industry and
Sludge is
produced
Wastewater
treatment sludge
is used
Relevant PPs
YES
NO
YES
Solvents, metals (e.g. Cd, Pb, Ni),

organotin compounds (e.g. TBT),
biocides
2.16 Surface treatment of metals and plastics
Reference:
Best Available Techniques on Surface Treatment of Metals and Plastics. Accessible via:
http://eippcb.jrc.es/reference/stm.html
This BREF includes installations for the surface treatment of metals and plastics using an electrolytic or
chemical process. Many installations operate a mixture of small and large production lines, and a mixture of
electrolytic and chemical processes, as well as associated activities. Thus all processes, irrespective of the scale
on which they are carried out, were considered in the information exchange. In practical terms, the electrolytic
and chemical processes currently used are water-based. Directly associated activities are also described.
Surface treatment of metals and plastic is generally based on the use of aqueous solutions as the
treatment medium. Process wastewaters from this industry are often treated on-site in dedicated
71
wastewater treatment plants prior to discharge to the municipal wastewater treatment network (and
may be segregated to facilitate substance recovery and recycling). However, in some cases discharge
may also be direct to surface waters. This particular industrial sector has been identified as potentially
posing a high risk to water resource operations and may potentially disrupt sewage sludge
management. The BREF for surface treatment of plastics and metals covers an extremely wide range
of industrial activities and hence the range of substances potentially used and emitted by this sector is
extremely varied. Nevertheless, most facilities will work with a specific set of materials and will thus
only emit some of the substances that may potentially be relevant overall. Aside from the presence of
particulate and soluble metals in wastewater from this industry, other types of pollutants that may
frequently be found in wastewaters and sludge include both immiscible (e.g. oil, greases, solvents) and
soluble organic materials (e.g. wetting agents, brighteners, organic ligands, detergents etc.).
Substances of particular concern which are likely to be emitted from facilities involved in this
industrial sector as indicated in the BREF document include a number of PPs of particular relevance to
the ScorePP project including cadmium, lead, nickel, alkylphenols (including nonylphenol) and
alkylphenol ethoxylates, trichloroethylene, tetrachloroethylene, and methylene chloride. It is suggested
that discharge problems from surface treatment plants can be addressed by considering the substitution
of problem substances, and by careful management of processes and rinsing systems to reduce the
amount of chemicals present on the items being treated when they enter the rinse phase following
surface treatment.
Metals released to wastewater during surface treatment activities will typically accumulate in the
wastewater sludge fraction. Although Cd is a PHS and complete cessation of emissions to the
environment are thus stipulated under the conditions of the WFD, this metal has key properties which
are of special importance in surface treatment, particularly for applications with high fail safe
requirements (e.g. for applications in the aeronautical, aerospace, nuclear, mining and communications
sectors). The use of Cd is still allowed for products destined for these sectors. However, the use of Cd
in more substitutable applications has been considerably reduced in recent years leading to a reduction
in Cd emissions from the surface treatment industry. Similarly, there are also restrictions in place
restricting the permissible concentrations of Pb in some products treated by this industry in an effort to
decrease Pb emissions.
Incoming components are typically degreased prior to surface treatment. Solvents used for this
application include PPs such as trichloroethylene and tetrachloroethylene which are relatively heavy
solvents and have been known to cause problems due to accumulation in sewage systems.
Sludge wastes produced by this industry are typically derived from treating the waste process solutions
and other wastewater produced at surface treatment installations. These wastes are typically classed as
hazardous. In the case of metal contaminated wastes from these sources it is generally possible for
metals to be recovered to some degree.
Other sludge related management problems potentially arising at surface treatment plants include the
increased production of sludge due to high iron contents in the wastewater as caused by excessive
attack of the metal surface.
Key processes used in this sector include pickling, descaling and desmutting (to brighten and remove
oxides from metallic surfaces prior to subsequent surface treatment), metal stripping (for reclaiming
defectively electroplated components without losing the base material and/or recovering precious
metals for reuse), chemical milling, nickel electroplating (various forms), chromium plating, zinc and
zinc alloy plating, and cadmium plating, and phosphating. Although this list is not exhaustive it serves
to show the wide variety of different processes and substrates that are relevant to this industry. Note
that zinc and zinc alloy coatings are the most widely used electrolytic surface treatment and that as
zinc ores also contain cadmium, effluents and sludges from zinc based surface treatment processes
may therefore also be expected to contain some cadmium.
72
Phosphating process waste can form large proportions of the sludge produced by this sector and
contains significant quantities of Ni. For example, monitoring of the phosphating process by the
automotive industry shows that up to 37 % of the Ni used in the process remains in the phosphate
sludge and 55% in the wastewater, with Ni uptake efficiency in the plating process typically only 8
16%. As Ni is a toxic substance and causes allergic reactions in many people, exhaust extraction and
mist eliminators are often employed on relevant premises and the effluents can usually be treated with
other wastewaters.
An investigation of consumptions and emissions by Ni electroplating facilities in Italy between the
years 1998 and 2000 found the sludges following dewatering by batch filter pressures to be around
30% solids, with a Ni concentration of between 1800 and 42000 mg/kg. The calculated emission
factor for Ni emitted to sludge per total amount of Ni used was between 4 and 8% (4080 g/kg).
Electroplating sludge from a facility in Germany was documented in the BREF as containing 49.5
g/kg Ni and 319.3 mg/kg Pb. The electroplating sludge from wastewater treatment at this facility is
100% re-used as a secondary raw material in a pyrometallurgical recycling plant.
By managing activities such as the removal from treatment baths carefully it is possible to minimise
drag-out losses and thus decrease the concentration of metal contaminants in rinse water and effluent
and thereby minimise treatment requirements and subsequent sludge production. Effluents containing
high concentrations of dissolved metals typically lead to the production of large quantities of sludge.
Wherever possible, efforts should also be made to decrease metal concentrations in treatment
solutions, for example the development of Ni free processes for phosphating layer conversion
coatings. Metal recovery from effluents and waste materials may also be practiced to minimise
environmental impacts and releases.
Techniques commonly applied for water and wastewater treatment in this sector include filtration,
polymer filtration and absorption (e.g. to selectively bind target metals), electrolysis (e.g. plating out
of transition metals on high surface area electrodes for metal recovery), ion exchange (e.g. for
concentrating multivalent cations for subsequent treatment or recovery), evaporation, and reverse
osmosis (e.g. for concentrating metal impurities).
Very briefly, the traditional order of wastewater treatment for this sector has been to use
sedimentation/precipitation followed by flotation, however filtration techniques are increasingly being
introduced during upgrading of facilities in order to lower emission levels and help meet the objectives
of increased water recycling and sludge reuse. Sedimentation and flotation can both be of benefit in
the recovery of sludges containing metals but the increased move towards the implementation of zero
discharge techniques highlights alternative methods that may be of greater benefit in this regard (e.g.
thermal techniques, membrane technologies, and ion exchange). At the same time it is important to
bear in mind that in some cases the use of such techniques may actually result in the production of
sludges that are more toxic and/or more difficult to handle than the waste produced from conventional
wastewater treatment plants (e.g. evaporation techniques produce a mixture of soluble salts requiring
disposal in landfill). Nevertheless, closed production loops are increasingly being introduced in this
sector, particularly for specific processes such as Ni or Cr plating. Reclamation and recycling of
metals from spent process solutions and sludges may also be practiced by relevant third parties where
appropriate (e.g. hydro and pyrometallurgical companies engaged in non-ferrous metal refining may
be able to recycle materials reclaimed from electroplating sludges).
In terms of the wastewater sludge treatment, settled floc or filtrate typically contains about 5% solids
and is therefore normally dewatered to increase the solids content. This may be done by filter press,
belt press or centrifuge to give a filter cake with around 1535% solids, which may also be subjected
to a further stage of drying. In some cases dewatered sludge may be stabilised by the addition of
binders such as cements or fly ash or by the addition of hydrocarbons such as tars or bitumen. Sludges
may also be valorised by recycling for use in metals refining or in the regeneration of waste acids. For
73
example, in 2003, approximately 30% of electroplating sludge from Germany was used as secondary
raw material in the non-ferrous metal industry, whilst the remainder was disposed of in hazardous
waste landfills. The sludge is usually considered to be hazardous waste, and the industry produces in
the order of 300000 tonnes of hazardous waste a year in Europe (approximately 16 tonnes a year per
installation) and requires managing according to the appropriate regulations.
Although this is a relatively highly polluting industry in terms of water based emissions and sludge
production it is clear that there are many additional measures that can be taken to reduce the emissions
of metals and other substances from this sector, and to reduce the volume and pollutant content of the
sludges produced. The overall aims of BAT for this sector are to introduce additional measures to
prevent and reduce material losses, and reuse, recycle and recover materials as much as possible.
Table B31: Summary of sludge production and use metals and plastics surface treatment industry and
Sludge is
produced
Wastewater
treatment sludge
is used
YES
YES
YES
Relevant PPs
Cd, Pb, Ni,

nonylphenols, octyphenols,
trichloroethylene,
tetrachloroethylene, methylene
chloride
2.17 Waste incineration

Reference:
Best Available Techniques for Waste Incineration. Accessible via: http://eippcb.jrc.es/reference/wi.html
This BREF covers installations for the incineration of hazardous and municipal waste. Although incineration
provides the main focus of this BREF, three main thermal treatment techniques are also described in general, as
they relate to some common waste streams. These are:
incineration
pyrolysis
gasification.
In addition to the thermal treatment stage of the installation, this BREF also covers:
the reception, handling and storage of waste
the effect of waste pretreatment on the selection and operation of waste incineration processes (in some cases,
this includes a description of the techniques applied)
applied flue-gas treatment techniques
applied residue treatment techniques (for the main residues commonly produced)
applied waste water treatment techniques
some aspects of energy recovery, the performance achieved and the techniques used. Details of electrical
generation equipment, etc. are not included.
74
In the case of waste incineration there are two sludge related issues. One is specific to the incineration
of sludge wastes, particularly sewage sludge, and the other is regarding the production of sludge
through wastewater treatment and gas treatment due to the combustion of other waste products (e.g.
municipal solid waste). Regarding the incineration of sewage sludges, these may either be incinerated
separately from other wastes in dedicated installations or they may be combined with other wastes
(e.g. municipal wastes) for incineration.
The scale of use of incineration for waste management varies considerably throughout EU member
states. For example, incineration of municipal waste varies from 0% in some member states to >60%
in others. This geographical variation in the use of incineration for waste disposal purposes is reflected
in the difference in number of incinerators located in the different Member States as can be seen in
Table B32.
The main types of waste to which incineration is applied as a treatment are:
municipal wastes (residual wastes - not pretreated)
pretreated municipal wastes (e.g. selected fractions or RDF)
non-hazardous industrial wastes and packaging
hazardous wastes
sewage sludges, and
clinical wastes.
Table B32: Geographical distribution of incineration plants for municipal, hazardous and sewage sludge
waste in Europe (reproduced from BREF).
Pretreatment of sludges (including but not limited to sewage sludge) may be required prior to
incineration. This depends on the nature of the sludge, the design of the installation, selected coincineration materials etc. For example, industrial sludges may require neutralisation prior to
incineration, and drainage, thickening, and even solidification of the sludge with binding agents may
also be carried out. As the composition of sewage sludge varies greatly both geographically and
temporally (depending on the particular industries connected to the sewer, local climatic conditions,
75
type of treatment applied etc.) this needs to be taken into account when considering the incineration
disposal option. Factors of particular importance in controlling the incineration process include the dry
solids content of the sludge, whether the sludge is digested, concentrations of conditioning agents such
as lime in the sludge, and the treatment source of the sludge (i.e. whether it is primary sludge,
secondary sludge, combined sludge etc.). Pretreatment of sewage sludge prior to incineration typically
involves some degree of sludge dewatering (to reduce sludge volume and increase calorific value). It
is reported that a dry solids content of between 10% and 45% can be achieved through the mechanical
drainage of sewage sludge using decanters, centrifuges, belt filter presses, or chamber filter presses. It
is also common for the sludge to be conditioned with organic conditioning substances (i.e. flock
building materials) prior to drainage. Organic conditioners such as polymers are more suitable for this
purpose than inorganic conditioners such as Fe and Al salts because although the inorganic substances
are effective flocking agents they also increase the inorganic content of the sludge and hence the
incombustible proportion of the sludge.
For co-combustion of sludge and other wastes additional drying of sewage sludge is generally
required. Frequently a thermal drying plant for additional drying of the sludge is installed prior to the
incineration furnace. A range of dryer plants may be utilised for this purpose including fluidised bed
dryers, disk dryers, drum dryers, belt dryers and so on. Drying thus achieved may be either partial
drying (approx. 6080% dry solids) or complete drying (approximately 8090% dry solids). An
alternative option is to dry the sludge in-situ by co-incinerating the dewatered sludge with higher
calorific waste. Thermal drying is not necessarily required for auto thermal incineration in mono
sewage sludge incineration plants, where sludge with 35% solids content is generally sufficient
(although this is dependent on the composition and energy content of the sludge and thus may be
dependent on the application of sludge treatment techniques such as digestion). Note that digested
sewage sludge can generally be dewatered more easily than non-digested sludge.
Incineration can be carried out in a variety of different systems including rotary kilns, multiple hearth
furnaces, or fluidised bed incinerators. Co-combustion in grate-firing systems, coal combustion plants
and industrial processes is also possible. As contaminants in sewage sludge can be an issue during
combustion it is common to add a post-combustion chamber to the incinerator in order to increase the
destruction of toxic compounds. In addition, sludge vapours may be extracted from the drying stage
and condensed for further treatment prior to disposal. Dedicated sewage sludge incinerators are
generally designed and operated at temperatures between 850 and 950 C.
More recent alternatives to incineration of waste materials include pyrolysis and gasification. These
techniques are currently applied on a smaller scale than incineration but research and piloting is
ongoing. Both technologies work by attempting to separate the different stages of reactions occurring
in conventional waste incineration plants by careful control of process temperatures and pressures.
These techniques are also often coupled with downstream combustion of the syngas (i.e. process gas)
generated during the initial treatment stage. A major difference between incineration and
pyrolysis/gasification is that the latter methods may be used to recover some of the chemical value of
the waste rather than only the energetic value. Recovered chemical products may in some cases be
used as feedstock for other processes, however the solid residues arising from these processes may
contain pollutants which would otherwise (i.e. in an incineration system) be transferred to the gas
phase and subsequently removed with FGT residue.
Metals are a key component of concern in many types of potentially combustible waste, including
municipal, hazardous and sewage sludges. The presence of Hg in sewage sludge is a major
management issue in relation to emission control during combustion due to its high volatility. In most
cases, waste incineration installations cannot meet the stringent emissions limits imposed by European
legislation (0.05 mg/m3) without the application of special gas cleaning measures for Hg. The
selection of suitable mercury abatement measures depends both on the feed load at the plant and on
the chlorine content of the waste being burned. As the chlorine content in gas from sewage sludge
76
combustion may be relatively low much of the Hg in the emitted gas will be elemental rather than
ionic and will therefore not be efficiently removed by wet scrubbers. Where chlorine content in the dry
sewage sludge is < 0.3% by mass measures other than the addition of wet scrubbers are often required.
In this case, metallic Hg may be removed from the flue gas stream by the addition of oxidants to
transform elemental Hg into ionic Hg to increase wet scrubber removal efficiency, or by direct
deposition of Hg on sulphur doped activated carbon, furnace coke, or zeolites. Activated carbon may
also be used to lower the emissions of other metals from these installations. The retention of these less
volatile (and semi-volatile) metals such as Ni, Cd and Pb depends largely on the effective separation
of dust from flue gas.
Other PPs which are likely to be emitted in flue gas from the combustion of sludge materials include
PAHs, chlorobenzenes, and a wide range of halogenated organic compounds. Ensuring that the plant is
operating with high combustion efficiency is particularly important for reducing the emissions of such
compounds. Further reductions of organic and metal contaminant emissions can be achieved by
additional measures to deposit dust and aerosols and by enforced flue gas cooling (i.e. condensation).
Waste water from wet flue-gas scrubber systems should be fed to a wastewater treatment plant with
metal deposition facilities, where the Hg can be converted to a more stable form such as HgS prior to
further disposal. There is also the possibility to separate the treatment of wastewater from the first and
last steps of the scrubber system in order to optimise the treatment process for these two effluent
streams which have different pH levels. In doing so, both gypsum and household table salt can
potentially be recovered from the scrubber effluents and the mass of residual waste can thereby by
substantially decreased, leaving only the precipitated sludge of metal compounds for disposal.
The nature and quantity of residues produced upon incineration are a key management issue for this
industry. The types and quantities of residue produced may vary greatly, being dependent on the
system design, operational decisions and waste input, however the key residues produced typically
include ashes and/or slag, filter dust, residues from flue gas cleaning, and sludge from wastewater
treatment. Following incineration some residues (e.g. bottom ashes) can potentially be recycled
(following some degree of treatment) as an aggregate replacement for construction materials. Ferrous
and non-ferrous metals may also potentially be recovered from bottom ashes. Fly ash can potentially
be used as filling material for applications in civil construction (if permitted by national regulations),
or as filling material in mines. If the fly ash is not reused for such applications it is typically landfilled.
In some cases, fly ash is also combined with the sludge produced by treating the wet scrubber effluents
to produce a product called Bamberg cake. This combination uses the sulphides in the sludge to
decrease the leachability of metals from the Bamberg cake prior to landfilling.
Table B33: Summary of sludge production and use by the waste incineration industry and relevant PPs
Sludge is
produced
sludge is used
Requires management
of PP contaminated
sludges
Relevant PPs
YES
YES
YES
Hg, Ni, Cd, Pb, PAHs,

chlorobenzenes, halogenated
organic compounds
77
2.18 Large volume organic chemical industry
Reference:
Best Available Techniques in the Large Volume Organic Chemical Industry. Accessible via:
http://eippcb.jrc.es/reference/lvoc.html
This BREF covers the manufacture of organic chemicals produced in large volumes. LVOC processes are
considered to have the following features:
the products are rarely consumer products in their own right, but are basic chemicals that are used in large
quantities as raw materials in the synthesis of other chemicals
production takes place in continuously operating plants
products are not produced in a range of formulations or compositions (grades)
products have relatively low added value
the product specifications are defined to allow a wide range of applications (as compared, for example, with
fine chemicals).
General principles of management systems, unit processes, unit operations and infrastructures that are valid for
all LVOC production processes are included in this BREF. It also contains generic product groups that are
linked by common chemistry or production techniques. Finally, it contains specific information on the
manufacture of a small number of selected illustrative processes:
lower olefins by the cracking process
aromatics such as benzene/toluene/xylene (BTX)
oxygenated compounds such as ethylene oxide, ethylene glycols and formaldehyde
nitrogenated compounds such as acrylonitrile and toluene diisocyanate
halogenated compounds such as ethylene dichloride (EDC) and vinyl chloride monomer (VCM)
sulphur and phosphorus compounds
organo-metallic compounds.
The Large Volume Organic Chemical industry encompasses a wide range of chemicals and processes.
The products produced by this industry are generally bulk chemicals which have been transformed
by a series of physical and chemical reactions from basic refinery constituents into commodities with
particular chemical specifications and which are then usually used in large quantities as raw materials
in the synthesis of higher value chemical products such as plastics, solvents, or pharmaceuticals. The
relevant industrial facilities are typically continuous production facilities. For the purposes of the
BREF document the sector has been divided into sub-sectors on the basis of the functional chemistry
of the products produced. Emissions to sludge naturally vary depending on the particular process in
question and on the characteristics of the actual production plant, as well as the particulars of any
wastewater treatment practices. But in any case, given the large scale of operations in this sector it is
anticipated that emissions may be quite substantial.
Wastewater arises from a wide variety of processes in this sector, and may include process water
where the contact during production was as steam, diluents or absorbent, as well as process
wastewater that has been used as the liquid phase reaction system (e.g. as reactant solvent or carrier).
In addition wastewater can also be generated by the formation of reaction water during a process (e.g.
78
through condensation reactions), from process purges and bleeds, and from quenching of organic
vapour steams, from product washing, through cleaning operations, and the dewatering of sludges.
The main water pollutants from large volume organic chemical production have been identified as
mixtures of oil/organics, biodegradable organics, recalcitrant organics, volatile organics, heavy metals,
acid/alkaline effluents, and suspended solids. Most of the waste water constituents are biodegradable
and hence biological based treatment in centralised waste water treatment plants is common, although
segregation and pretreatment of waste streams containing metals or toxic or non-biodegradable
organic compounds by oxidation, filtration, extraction, steam stripping, hydrolysis or anaerobic
processes is also typically required.
Organic sludges may arise from different processes in this sector (e.g. the steam cracking process).
These are typically liquid, pasty or solid materials collected during normal operation, start-up,
shutdown, drainage and cleaning of production units, generally arising from API separators, quench
oil systems, spent solvents, spent lubricating oil, bottom drains of vessels and settlers and polymeric
material removed from pump strainers and filters.
Process residues/sludges such as heavy organic residues from distillation columns (e.g. tars and
waxes) used in the steam cracking process may well contain substances such as PAHs, but may also
have value as a by-product, as feedstock for another process or as fuel. Where this is not possible they
are generally incinerated (under appropriate conditions). The majority of the process sludges and
wastewater sludges (e.g. biological sludge and filter cakes) produced by this sector appear to be either
incinerated or sent to landfill. For example, a CEFIC survey reported that 27 respondent facilities
disposed of organic sludges by incineration, and 18 by landfill, and that sometimes both approaches
were combined. Some of these wastes were also processed off-site by specialist contractors to recover
valuable light fractions, or used as additives in construction materials. BAT is to treat each waste on a
case by case basis and to aim for recycling, reclamation or post treatment re-use of waste sludge
matter.
In the case of aromatics production different types of solid wastes, including sludges, are usually
treated and disposed of by third parties off the production site. Sludge removed from process
equipment during maintenance activities is typically incinerated off-site but can also be used on-site
as a fuel source. Oily sludges from solvents, bio-treatment and water filtration are incinerated under
carefully controlled conditions, with associated heat recovery.
Of the PPs relevant to the ScorePP project, those which are likely to be present in wastewaters and
sludges from this type of industry include metals (from the use of catalysts and the production of
organo-metal compounds). Organo-lead compounds are still in production to some extent within
Europe, although the market is continually declining. As the presence of water can potentially
adversely affect the reactions during production of organo-metal compounds, extensive quantities of
organic solvents are used to protect the production process. Consequently, wastewater from these
facilities potentially contains both metals and organic components of relevance. All existing processes
used for the production of lead alkyl products (e.g. tetramethyllead, tetraethyllead) are based on the
batch-wise reaction of lead/sodium alloy with ethyl or methyl chloride and as a large excess of lead
needs to be used in this process, up to 75% of the lead is not incorporated into the product and thus
needs to be recovered. Lead rich sludges resulting from wastewater treatment following this process
can be collected and sent for recovery. Wastewater containing metals should be pretreated to prevent
inhibitory effects on biological treatment processes, and to prevent sludge deterioration effects by
removing the risks associated with high metal levels in sludge.
The BTX aromatics industry, which includes the production and use of benzene, a PP, and other
aromatics such as toluene, and xylenes, is a significant sector of the European chemicals industry. For
benzene alone there are at least 57 production units with a combined capacity of 8100 kt/yr. The most
widely used production process is based on the separation and isolation of pure products from mixed
79
hydrocarbons using solvent extraction followed by distillation. Wastewater is generally pretreated for
oil separation and then passed through a biological treatment WWTP. Oily sludge materials produced
by this industry are incinerated with the additional aim of heat recovery thus constituting BAT. Spent
clay absorbents used in these processes should be landfilled or incinerated.
The production of ethylene dichloride (EDC) and vinyl chloride monomer (VCM) is presented in the
BREF document as an example of the halogenated compounds production sector. Ethylene dichloride
is also a PP and is currently being produced at 30 production sites in the EU with a total VCM
capacity of 5610 kt/yr. EDC and other PPs such as carbon tetrachloride, hexachlorobenzene,
pentachlorobenzene, and hexachlorobutadiene may be present in wastewaters from VCM production
sites and hence may become entrained in sludges relevant to this sector. Aside from wastewater
sludges, there is also the generation of spent oxychlorination catalyst (which may be recovered in wet
form after settling and filtration of wastewater), and formation of tank/vessel sludges from these
facilities (e.g. direct chlorination residues) to consider. Waste catalyst is generated at a rate of
approximately 10 to 200 g dry mass /t VCM produced, whilst direct chlorination residues are produced
at around 10 to 50 g dry mass / t VCM. Spent lime waste may also be produced from these facilities as
a function of the final purification of VCM as this may involve the neutralisation of acidity using lime.
BAT for effluent pretreatment from these facilities is the steam/heat air stripping of chlorinated
organic compounds to concentrations of <1 mg/l with off gas passing to condensation and recovery, or
incineration; flocculation, settling and filtration of semi- or non-volatile chlorinated organic
compounds adsorbed on particulates; and alkaline precipitation and settling to lower Cu
concentrations. Final effluent treatment should be biological treatment. Due to the contaminated nature
of sludges from this industry they are not considered suitable for land application. BAT for the sludges
produced from EDC/VCM facilities is stated in the BREF as incineration in a dedicated or multipurpose hazardous waste incinerator. These sludges often contain dioxins and furans. In some cases,
where the waste contains lower concentrations of halogenated compounds (e.g. <1000 mg/kg dry
matter) then disposal to a chemical waste landfill may also be considered as BAT.
As with many industries covered by the BREFs, a major aim for BAT is to minimise the production of
waste in the first place by optimising production processes; to valorise waste streams as much as
possible; and to recover valuable components (e.g. metals from spent catalysts) from waste streams
prior to disposal.
Table B34: Summary of sludge production and use by the large volume organic chemical industry and
Sludge is
produced
Wastewater
treatment sludge is
used
Relevant PPs
YES
NO
YES
Pb, benzene, ethylene dichloride,

carbon tetrachloride,
hexachlorobenzene,
pentachlorobenzene,
hexachlorobutadiene,
80
2.19 Large Volume Inorganic Chemicals - Ammonia, Acids and Fertilisers

Industries
Reference:
Best Available Techniques for the manufacture of Large Volume Inorganic Chemicals Ammonia, acids and
fertilisers. Accessible via: http://eippcb.jrc.es/reference/lvic-aaf.html
This BREF covers the production of ammonia, acids and fertilisers where large volumes of the specified
inorganic compounds are produced. Generally, the ammonia and acid processes covered here are considered to
have the following feature: the products from the processes are not consumer products in their own right, but
are basic chemicals that are then used in large quantities or as raw materials in the production of other
chemicals. NPK, AN/CAN, superphosphates or urea fertilisers, however, are produced primarily for a particular
user although the production of these other chemicals are also carried out in dedicated continuously operating
plants. This BREF covers substances such as:
ammonia
nitric acid
sulphuric acid
phosphoric acid
hydrofluoric acid
NPK (nitrogen, phosphorus, potassium) fertilisers nitrophosphate and mixed acid route
urea, urea ammonium nitrate
ammonium nitrate/calcium ammonium nitrate (AN/CAN)
superphosphates.
This industrial sector is characterised by large scale production processes carried out in continuously
operating dedicated production facilities. The substances produced in this sector form the basis for the
production of nitrogen-based and phosphate-based fertilisers but the chemicals produced are also
important in a range of other applications aside from fertiliser production. For example, a major
activity in this sector is the production of sulphuric acid, which is the most extensively produced
chemical in the world (with EU production estimated to be about 22 Mtonnes per year). Wastewaters
from these sulphuric acid production facilities arise mainly from wet scrubbing of exhaust gases,
particularly from the cleaning of metallurgical tail gases, from cleaning of pyrite roasting gases, and
from cleaning gases from spent acid regeneration. It can be expected that metal contaminants may be
present in pyrite sources used in this industry and therefore some wastewaters may contain metal
contaminants. These wastewaters are typically treated by sedimentation and filtration to remove solids
which thereby produces a sludge fraction for further management. Similar wastewater treatment
procedures are followed for wastewaters from the production of phosphoric acid and hydrofluoric
acid. Moreover, due to the inorganic components in the wastewater from many of these processes
coagulation agents may also be added in addition to sedimentation and filtration.
Means of reducing the production of wastewater sludges from this sector include revisions to waste
management procedures that reduce the production of wastewater requiring subsequent treatment. For
example, the exhaust gases from neutralisation/evaporation and granulation steps in the production of
NPK fertilisers can be combined for treatment rather than undergoing separate treatment. In addition,
waste waters should be recycled back into the process wherever possible. For example, the scrubbing
and washing liquors from NPK production facilities can potentially be recycled, as can the washing
81
liquor from sand washing. In fact, several examples are given in the BREF of NPK production
facilities where all scrubbing liquor is recycled into the process, rinsing and cleaning waters are
collected and reused as scrubbing liquid, and no wastewater is generated. This is clearly of great
significance in terms of sludge management and BAT for this sector is to minimise wastewater
production volumes by recycling wastewaters in this manner. Biological wastewater treatment (with
nitrification/denitrification) may be used for the final treatment of effluents from the production of
NPK and AN/CAN facilities, particularly if stipulated water quality parameter aims cannot be met.
BAT for disposal of this sludge is not specified in the BREF.
Table B34: Summary of sludge production and use by the large volume inorganic chemical (ammonia,
acids and fertilisers) industries and relevant PPs potentially present in sludge from these sectors.
Sludge is
produced
Wastewater
treatment sludge
is used
Relevant PPs
YES
NO
YES
Metals
2.20 Manufacture of organic fine chemicals
Reference:
Best Available Techniques for the Manufacture of Organic Fine Chemicals
Accessible via: http://eippcb.jrc.es/reference/ofc.html
This BREF focuses on the batch manufacture of organic chemicals in multipurpose plants and addresses the
manufacture of a wide range of organic chemicals. Some production sites may also include dedicated production
lines for larger volume products with batch, semi-batch or continuous operation. The list is not exhaustive but
includes for example:
dyes and pigments
plant health products and biocides
pharmaceutical products (chemical and biological processes)
organic explosives
organic intermediates
specialised surfactants
flavours and fragrances
pheromones
plasticisers
vitamins
optical brighteners
flame-retardants
This sector encompasses installations manufacturing an extremely wide range of organic chemicals,
generally using batch operations in multipurpose plants. Examples of the types of products relevant to
this industry are given in the preceding summary box. This list is so encompassing, ranging from dyes
and pigments to specialised surfactants, plasticisers and flame retardants that it is feasible to assume
82
that most substances considered as PPs for the purposes of the ScorePP project will be produced
and/or used in this sector. Whether they will also therefore become entrained in wastewater sludge
from this sector and or solid waste residues is less certain but it is clear that this is a sector of key
importance for the purposes of managing PP releases to the environment.
The substances produced by this sector are typically of a high added value and are usually produced in
relatively low volumes by industrial standards. They are generally sold to other chemical companies
and industries serving a wide range of end-user markets. Given the diversity of products covered it is
clear to see that the chemistry of the intermediates and products used in this sector will also be very
varied. Nevertheless, the actual range of reactions and processes used is relatively small, including
charging/discharging of reactants and solvents, inertisation, reactions, crystallisations, phase
separations, filtrations, distillation, product washing. Cooling, heating, and the application of vacuum
or pressure are also commonly involved.
Key processes in which PPs may be utilised and produced include:
diazotisation and azo coupling (involves the use of metals to give metal complex dyes
esterification (esters are widely used as solvents, extractants and diluents, plasticisers (e.g.
phthalates), fragrances, flavours, and as intermediates
nitration (important for the production of a wide range of aromatic intermediates for dyes,
agrochemicals, pharmaceuticals, explosives etc. and typically involves the use of halogenated
aromatics as raw materials)
reduction of aromatic nitro compounds (e.g. by catalytic hydrogenation)
sulphonation (halogenated compounds are among the typical raw materials, whilst arylsulphonic
acids are used chiefly as intermediates in the manufacture of dyes, insecticides, pharmaceuticals,
plasticisers etc.), and processes involving metals (i.e. where the feedstock or product contains
metals and/or where metals are used as auxiliaries such as redox partners, catalysts etc.)
Perhaps the greatest environmental management issue facing this industry is the emission of volatile
organic compounds, but of more relevance to this report are the issues surrounding the production of
wastewaters with high loads of non-degradable organic compounds, as well as the generation of large
quantities of spent solvents and non-recyclable wastes. Relevant wastewater streams from this industry
which may lead to the production of sludge include wash waters from product purification loaded with
residual substances, cleaning waters, vapour condensation waters, quench water, wet scrubber
effluents, and cooling waters and blowdown amongst others. Mother liquors and initial wash-waters
contribute up to 90% of the contaminant loads, although their share of the total volume is only about
10 to 30%.
Waste streams from different unit processes relevant to the production of organic fine chemicals can
produce both exhaust gases and mother liquors (wastewater) containing various organic compounds
(including potentially lost product and/or by-products) and metals. Exhaust gases are often treated by
thermal oxidation but may also, in the case of high water solubility be treated by adsorption in wet
scrubbers before further treatment in a biological WWTP. Other wastewater streams from installations
in this sector include wastewater from extractions and product washing. In general, all wastewater
streams are considered for pretreatment, disposal by incineration, or direct treatment in a biological
WWTP, with this decision being largely dependent on the load and bio-eliminability of the organic
content. In cases where wastewater streams have high loads of COD/AOX with recalcitrant or toxic
properties (e.g. aqueous mother liquors from halogenation reactions) pretreatment should be carried
out prior to mixing with other waste streams for total effluent treatment.
Wastewaters from product formulation can potentially have serious impacts on biological treatment
plants if not appropriately pretreated. For example, wastewaters from the production of biocides and
health products (e.g. pharmaceuticals) are typically pretreated by means of stripping, extraction,
pressure hydrolysis or activated carbon adsorption. Examples of pretreatment options which typically
83
lead to wastewater sludge production include biological treatment, activated carbon adsorption, and
precipitation/filtration (if metals are present). Waste streams, including concentrated wastewater
streams and sludges, may also undergo treatment by wet oxidation with O2, with the generated
effluents fed back to biological treatment. Metals may be separated out as metal oxides following wet
oxidation and COD is greatly reduced (average elimination of >99% can be achieved). From the
perspective of sludge management, wet oxidation presents a very favourable option for treatment of
difficult waste streams.
Total effluents from installations in this sector are normally treated in a biological wastewater
treatment plant (either on-site or together with other waste streams in a municipal wastewater
treatment plant). Wastewaters not considered suitable for treatment with combined waste streams
should be kept separate and may be incinerated in some cases (e.g. pharmaceutical company process
wastewater).
Decisions relating to the segregation and pretreatment of wastewaters are crucial management issues
for the multi-purpose production facilities common to this industrial sector. The decision rests on the
potential for toxic effects on the activated sludge at the biological treatment plant facility and the
biodegradation potential of key contaminants in the waste stream. The aim is, of course, to protect the
activated sludge from toxic shock in order to ensure high operational stability of the biological
treatment stage. On-site pretreatment options should be considered for all waste streams containing
priority substances and metals. In some cases, highly toxic mother liquors must be pretreated (for
recovery or abatement) and/or disposed of by alternative means such as incineration to ensure that the
biological WWTP is protected. The ability to maintain segregation between different waste streams
from multi-purpose production facilities is very important. This is because the most suitable
destination of component waste streams may change frequently during production. For example, the
following scenario is given as an example in the BREF document:
Product 1
Mother liquor pretreated by wet oxidation
Initial wash-water sent to biological WWTP
Secondary wash-water sent to biological WWTP
End of production campaign - Rinsing water sent to biological WWTP
Product 2
First mother liquor pretreated by extraction
Second mother liquor pretreated by wet oxidation
Wash-water sent to biological WWTP
A wide range of BAT specifications that may affect the concentrations of PPs in wastewater and
sludge from this sector are given in the BREF. These include:
The segregation and pretreatment or disposal of mother liquors from halogenations and
sulphochlorinations
The pretreatment of waste streams containing biologically active substances that could disturb
subsequent waste treatment processes
Segregation and collection of spent acids from relevant production processes
Segregation and pretreatment of wastewaters containing significant refractory organic loadings
Recovery of solvents from wastewater streams for on-site or off-site reuse (e.g. by stripping,
distillation/rectification, extraction or a combination of these techniques)
Removal of purgeable halogenated hydrocarbons from wastewater streams (e.g. by stripping,
rectification or extraction)
Pretreatment of waste streams containing high levels of metal contaminants
84
To apply online toxicity monitoring in combination with online TOC measurement in treatment
plants where residual toxicity has been identified as a potential concern (i.e. where biological
treatment performance is observed to fluctuate)
Improvements in sludge quality may be achieved directly through improvements in process and plant
design, together with appropriate segregation and treatment of wastewater streams.
Table B35: Summary of sludge production and se by the organic fine chemicals manufacturing industry
and relevant PPs potentially present in sludge from this sector.
Sludge is
produced
Wastewater
treatment sludge is
used
Requires management
of PP contaminated
sludges
Relevant PPs
YES
NO
YES
It is assumed that most PPs still

produced or used in the EU will be
relevant here
85
2.21 Manufacture of large volume inorganic chemicals solids and other

industry
Reference:
Best Available Techniques for the Manufacture of Large Volume Inorganic Chemicals solids and other
industry. Accessible via: http://ftp.jrc.es/eippcb/doc/lvic-s_bref_0907.pdf
Large Volume Inorganic Chemicals - Solids and Other Industry
This BREF covers chemical installations for the production of basic inorganic chemicals, which are:
soda ash (sodium carbonate, including sodium bicarbonate)
titanium dioxide (chloride and sulphate process routes)
carbon black (rubber and speciality grades)
synthetic amorphous silica (pyrogenic silica, precipitated silica, and silica gel)
inorganic phosphates (detergent, food and feed phosphates).
Other selected illustrative products (or groups of products) are addressed at a lesser level of detail and they are:
aluminium fluoride
calcium carbide
carbon disulphide
ferrous chloride
copperas and related products
lead oxide
magnesium compounds
sodium silicate
silicon carbide
zeolites
calcium chloride
precipitated calcium carbonate
sodium chlorate
sodium perborate
sodium percarbonate
sodium sulphite
zinc oxide
A wide range of chemical production activities are covered by this BREF as indicated in the summary
box above. Moreover, the production facilities operating in this sector use large quantities of water for
a wide variety of purposes, including: as a heat transfer agent for cooling or heating (generally semiclosed cooling water network and steam generators); as a feedstock for boiler plants; as a carrying
agent for transport of insoluble materials; as a component of the chemical products being produced
(e.g. crystallisation water); as a solvent; as a washing/cleaning agent; and as an air contaminant
abatement fluid, etc.
In addition to these potential sources of wastewater from facilities in this sector, wastewater may also
arise from distillation processes during production (e.g. production of soda ash), from brine
purification, and from vacuum pump sealing fluids.
86
Due to the great diversity of products produced in this sector it is difficult to generalise between the
different processes regarding key inputs to sludge formation and pollution. Nevertheless, it is typically
the case that wherever ores are in use in these processes, if the impurities present in the ores are not
incorporated in the final chemical products being produced they will eventually end up as wastes.
Thus the source of raw materials used for production may significantly affect the amount and
characteristics of the solid wastes (including sludge) formed. It is emphasised in the BREF that a
distinction should be made between treatable and untreatable wastes, whereby untreatable wastes are
directly related to the type and quality of the processed ore, and treatable wastes can be upgraded,
reprocessed, and utilised in the form of by-products. With the aims of BAT generally stated as the
valorisation and reuse of by-products as far as is practicable and economically viable it is important to
note that this aim really only applies to treatable wastes.
Key water contaminants for this sector, and which thus have potential to become entrained in sludge
materials requiring management, are mainly salts and inorganic substances, acidifying and alkalising
substances, suspended matter, and metals. It is noted that the presence of organic contaminants and
suspended organic matter in the wastewater from this sector is unusual. Thus it can be assumed that
the major PPs of relevance in terms of sludge contamination are the metals. With precipitation a
common technique used in onsite wastewater treatment plants servicing this sector it is reasonable to
assume that a fair proportion of the metals present in wastewater will in fact be transferred to sludge
during treatment. Although metals are not deliberately used in the production examples given in the
BREF, they do occur naturally in the raw materials (e.g. limestone, coke, and brine) used by these
facilities and generally pass through the process to be released together with the suspended solids
present in the wastewater. The installation of settling ponds to allow highly-efficient sedimentation of
settleable matter is one way to reduce the discharge of suspended solids and heavy metals to water but
naturally has the side effect of producing metal contaminated sludge. To reduce this metal content as
far as possible it is important to select high quality raw materials with a low metal content for
production (e.g. high quality limestone, phosphate rock etc.).
Oily sludges do not appear to be a major issue for this industrial sector, although some oily sludge is
produced by the carbon black industry. For example, oil sludge settled in the bottom of storage tanks
may need to be managed but as this sludge can potentially be reused as feedstock it is generally not a
major management issue.
Metal contaminated sludge from the production of inorganic phosphates is not considered to be
recyclable. However this sludge can be easily dehydrated by filter presses and is non-flammable,
therefore landfilling is typically considered to be a suitable solution.
A variety of measures to reduce water use and/or avoid wastewater emissions are specified in the
BREF and generally speaking such measures can also be expected to reduce the volume of sludge
produced, particularly in the case of introducing water free techniques for activities such as vacuum
generation and waste gas cleaning. Minimising drag-out etc. will also help to improve sludge quality
by reducing the wastewater pollutant load.
Table B36: Summary of sludge production and use by the large volume inorganic chemicals (solids and
other industry) sector and relevant PPs potentially present in sludge from this sector.
Sludge is
produced
Wastewater
treatment sludge is
used
Relevant PPs
YES
NO
YES
Metals
87
2.22 Production of specialty inorganic chemicals.
Reference:
Best Available Techniques for the Production of Specialty Inorganic Chemicals.
Accessible via: http://eippcb.jrc.es/reference/sic.html
This BREF covers the chemical installations for the production of speciality inorganic chemicals such as:
speciality inorganic pigments
silicones
phosphorus compounds (PCl3, POCl3, PCl5)
inorganic explosives
cyanides (NaCN, KCN)
soluble inorganic salts of nickel (sulphate, chloride, carbonate and nitrate).
The production of specialty inorganic chemicals concerns the manufacture of inorganic chemicals
which are produced in relatively small quantities and which are typically tailored to meet the
requirements of a particular end-use industry or sector (e.g. pharmaceuticals production). As such this
sector covers an enormous range of inorganic chemicals, associated raw materials and production
processes, pertaining to products such as specialty inorganic pigments, cyanides, phosphorus
compounds and soluble inorganic salts (e.g. Ni salts). As with other BREFs relating to the inorganic
and organic chemicals industry, the approach taken here has been to select a few families of specialty
inorganic chemicals for detailed consideration of their manufacture and associated BAT. Specialty
inorganic chemical installations are located all over Europe, and are generally small to medium size
using either batch or continuous modes of production. Plants may be either multi-purpose or specific
to the production of one particular chemical.
Due to the wide variety of products produced and raw materials used the range of potential pollutants
emitted from this sector is substantial. In fact the BREF states that any substances might conceivably
be released to any environmental compartment because of the huge number of chemicals produced. It
can therefore be concluded that PP contaminated sludge is likely to be a key issue for this sector.
Wastewater with high COD and toxic organic substance, heavy metal and salt loads are certainly
identified as key issues and the production of highly fluid sludges with significant water content is also
acknowledged. Much of this is in relation to the sludge produced through various methods of
wastewater treatment, although process sludges are also of primary importance. Sludge treatment
methods including thickening, dewatering, stabilisation, conditioning, and thermal sludge reduction
are referred to in the BREF, although it is noted that thermal sludge reduction is not usually performed
at specialty inorganic chemical production installations as this is typically only practiced at large
production sites.
PPs specifically referred to in the BREF include all of the metals listed under the WFD. Formation of
specialty inorganic salts are production activities relevant to this sector, hence metal contaminated
sludge from these and other relevant industries are anticipated. As for many of the activities covered in
other chemical industry BREFs, the quality of the raw materials used for these processes, the operation
and maintenance of plants, and the wastewater treatment pathways can all affect the quality of sludge
produced. BAT is to reduce the amount of residues generated by using one or all of the following
measures: using high purity feedstock, improving reactor efficiencies, improving catalyst systems.
88
Wastewater treatment regimes described for the indicative production processes documented in the
BREF frequently include treatment of wastewater from off-gas scrubbing, mother liquors, product
washing (e.g. pigment washing), and cleaning activities. Concentration of wastewater volumes by
evaporation or drying is potentially practiced, as is pretreatment for removal of metals by precipitation
and flocculation and recycling of recovered metals back into processes where feasible. For example,
in the production of specialty pigments recycling of filtration residues and precipitation sludges
(hydroxides) is feasible in the manufacture of cadmium pigments but not in the production of lead
chromate. Metal sludges from some processes are also recycled externally, for example the metal
sludges produced during the manufacture of zinc sulphides and lithopone pigments are supplied to
zinc and copper smelters. Pretreatment of wastewater loaded with heavy metals should always be
practiced to minimise contamination and inhibition of activated sludge in biological wastewater
treatment plants.
Whilst it is difficult to generalise to all types of production covered by this BREF it is feasible to
assume that sludges will generally be either incinerated, landfilled or sent to off-site metal recovery
plants for further processing.
Table B37: Summary of sludge production and use by the specialty inorganic chemicals industry and
Sludge is
produced
Wastewater
treatment sludge is
used
YES
NO
YES
Relevant PPs
Cd, Pb, Ni, Hg,

various organic PPs
89
2.23 Management of tailings and waste-rock in mining activities
Reference:
Best Available Techniques for the Management of Tailings and Waste-rock in Mining Activities. Accessible via:
http://eippcb.jrc.es/reference/ref.html
The underlying theme of this work covers mineral processing, tailings and the waste-rock management of ores
that have the potential for a strong environmental impact or that can be considered as examples of 'good
practice'. The following metals are covered irrespective of the amounts produced or the mineral processing
method used (e.g. whether mechanical methods are used, such as flotation, or whether they are produced by
chemical or hydrometallurgical methods such as leaching, etc.):
aluminium
cadmium
chromium
copper
gold
iron
lead
manganese
mercury
nickel
silver
tin
tungsten
zinc.
The following industrial minerals are also included:
barytes
borates
feldspar (if recovered by flotation)
fluorspar
kaolin (if recovered by flotation)
limestone (if processed)
phosphate
potash
strontium
talc (if recovered by flotation).
Other minerals covered are:
coal is only included when it is processed and there are tailings produced (thereby following the abovementioned theme). Generally, this means that hard coal (or rock coal or black coal) is covered, whereas lignite
(or brown coal), which is usually not processed, is not covered
oil shale.
This BREF is focussed on the management of tailings and waste-rock generated in the mining and
processing of metal ore, coal, and selected industrial minerals such as feldspar, kaolin, phosphate and
90
talc. The PPs of primary importance in this industrial sector are the metals. Indeed, Cd, Pb, Hg and Ni
mining operations are all specifically referred to in the BREF as relevant to this industrial sector, and
all are mined and/or processed in either the European Union, the acceding countries, the candidate
countries, or Turkey.
A wide range of methods is used for mining and processing of metal ores and industrial minerals.
Methods for processing include mechanical methods, flotation, chemical methods, and
hydrometallurgical methods such as leaching. Many of the methods used for mineral processing result
in the production of highly fluid tailings requiring careful management (e.g. containment in
ponds/dams, filtering, dewatering and storage in dry heaps, or use as backfill on mine sites). In fact,
one of the most serious management issues facing this industry is the monitoring of tailings dams for
ongoing stability, as dam collapse can cause serious environmental effects and loss of life. The tailings
must be managed on the basis of their particular mineralogy and chemical and physical characteristics,
and the techniques used in the mineral processing procedure has an important impact on these
characteristics.
Slurried tailings from this sector (e.g. from wet processing techniques) are frequently contained within
tailings dams for long-term management. Other management approaches include backfilling,
management on heaps, thickening, underwater management, and the potential for use in other
applications. Where tailings are used for backfilling in a slurry form, binders may need to be added to
increase stability. It should be noted that not all mineral processing sites produce tailings, whilst some
of those which do are able to sell the tailings as aggregate.
Slurried tailings from the refining of alumina (known as red mud) have an elevated pH and are
generally either stored in conventional tailings pond systems, are thickened to allow dry stacking, or
are discharged to sea. Red mud has also been investigated as a potential land remediation amendment
for fixation of metals and prevention of acid rock drainage issues (i.e. potential beneficial reuse).
Meanwhile, base metal ores containing significant quantities of sulphides (i.e. higher than the acid
buffering capacity of the material) have an acid-rock-drainage potential and the tailings should be
carefully managed to minimise environmental degradation (e.g. subaqueous discharge to prevent
oxidation). Materials previously investigated for use as oxygen consuming covers for long term
management of tailings dams with acid rock drainage potential include compacted sewage sludge and
paper sludge. Sewage sludge may also be used on mineral processing sites to increase organic matter
contents in order to assist with revegetation plans.
BAT is the removal of suspended solids and dissolved metals prior to effluent discharge, and the
installation of sedimentation ponds to capture eroded fines. In some cases ferric salts may also be used
to remove contaminants (e.g. arsenic) from effluents.
Other sludge products relevant to this industry include the production of various process sludges such
as clarifier sludges, calcium fluoride sludge from hydrofluoric acid neutralisation by lime amendment
during feldspar processing, and water treatment sludges.
Table B38: Summary of sludge production and use in the management of tailings and waste-rock in
mining activities and relevant PPs potentially present in sludge from this industry.
Sludge is
produced
sludge is used
YES
YES
YES
Relevant PPs
Cd, Pb, Hg, Ni
91
2.24 Mineral oil and gas refineries
Reference:
Best
Available
Techniques
for
Mineral
Oil
and
Gas
Refineries.
Accessible
via:
This BREF addresses the mineral oil refining industry as well as natural gas plants. Other related activities
such as exploration, production, transportation or marketing of products are not included in this BREF.
All types of mineral oil refineries regardless of capacity and all types of process activities typically found in this
sector are covered in this document. Some activities that are or may be found in refineries are not covered in the
document because they are covered in other BREFs (e.g. low olefins and solvent production, generation of
power with natural gas). Other activities are not fully covered because they are partially covered in other
BREFs (e.g. cooling, storage, waste water and waste gas). Thus, when implementing IPPC permits for a specific
site, other BREFs should also be considered. Soil remediation is not included in this BREF because it is not a
contamination prevention or control technique.
The mineral oil and gas refinery industry is a very extensive and strategically important industrial
sector, with installations in Europe processing around 700 million tonnes per year. Refineries are
generally very large installations with well integrated processes, managing huge quantities of raw
materials and consuming very large quantities of energy and water. The major pollution management
issues for this industry tend to be the emissions to air, however the extensive use of water for both
process water and cooling water also leads to significant production of oil contaminated wastewater.
The main water contaminants are hydrocarbons and metals, indicating that PPs in these groups will
also be the most relevant in relation to contaminated sludge management. Sludges and spent chemicals
(e.g. acids, amines, catalysts) are important waste fractions generated by refineries.
Sludges originate from various sources within the refinery such as crude and product tank bottoms,
desalters, alkylation units, boiler feed water preparation, effluent biotreatment, the cleaning of heat
exchanger bundles and equipment, oil spills and soil remediation (see Table B39). Sludges produced
from these installations can typically be divided into either oily sludges (e.g. from tank bottoms) and
non-oily sludges (e.g. boiler feed water sludges and some waste water treatment sludges), with oily
sludges representing the largest refinery waste category in terms of volume. This is partly due to the
presence of sediment and water in the crude. Oils retained in such sludges represents a loss of product
and efforts are therefore made to recover such oil if feasible. Waste generation trends for this sector
over the last decade show that oily sludge production is declining. This also helps to minimise waste
volumes, which is an added benefit in view of the significant operating costs of waste disposal. On the
other hand, biological sludge production has been increasing due to the increasing implementation of
biological wastewater treatment for refinery effluents.
92
Table B39: Percentage distribution of different types of waste sludge produced by refineries. API =
Oil/water/sludge separator (developed by American Petroleum Institute); DAF = Dissolved air
flotation. (Reproduced from BREF).
Catalytic reforming also generates sludge with a recognised PP content. For example, sludges
generated in the unit separator of an ultraformer are reported as containing (on a dry matter basis) 898
ppm Ni, 109 ppm Pb, 93 ppm benzene, 79 ppm naphthalene, 7 ppm benzo(a)pyrene, and 0.02 ppm Hg.
Likewise, hot oil blowdown sludges generated from the coking process include 273 ppm Pb, 230 ppm
Ni, 32 ppm naphthalene, 6 ppm benzo(a)pyrene, 2 ppm benzene, and 1ppm Hg.
Natural gas refining only gives rise to relatively small quantities of process waste, however Hg can be
present as a constituent in natural gas, and collection of this Hg for proper disposal generates a Hg
contaminated sludge. For every 1000 kg of such sludge treated, 12 kg of metallic Hg is produced.
Lead was previously a common contaminant in storage tank bottom sludge due to the storage of
leaded petrol, however this should be declining now that leaded petrol is no longer in general use in
Europe.
Effluent treatment sludges are generated from a number of different wastewater treatment units used in
this sector. For example, primary treatments generate API separator sludge (phenols, metals and up to
10% oil), chemical precipitation sludge (chemical coagulants, oil), DAF floats (up to 30% oil),
biological sludges (metals, <0.5% oil, suspended solids) and spent lime. Secondary treatment
generates biological sludge waste which is typically treated anaerobically and then dewatered.
Flotation units and biotreaters generate the largest quantities of sludges in the wastewater treatment
plants. DAF units also produce significant quantities of sludges. Table B40 gives examples of the
composition of sludges from different wastewater treatment stages used by refineries.
By using oily sludges and wastewater sludges as feedstock the coking process can be used to destroy
residues and waste sludges. In fact, in principle any refinery with a coker is able to reduce its oily
sludge production to zero. Certainly the use of sludge as a feedstock has increased significantly in
recent years and is currently carried out by most refineries.
Apparently, in 1993, 44 % of European refinery sludges were incinerated, 9% was land farmed and
30% land filled. As land filling and land farming of sludges is likely to be increasingly restricted by
forthcoming EU legislation, it is to be expected that moves to reduce sludge production and also
increase incineration are likely to continue to rise. Decanter centrifuges are currently the most widely
used system for dewatering for both oily sludges and biosludges. Steam dryers are almost exclusively
applied for biosludge, often functioning as a pretreatment step for incineration. Dewatered biological
and oily sludges can be further processed using drying and/or incineration techniques. Oily sludge
dewatering is only applied at refineries that dispose of sludge cakes outside their premises in order to
reduce the volume and associated disposal cost. De-oiling/dewatering (centrifuging or filtration) of
sludges gives small volumes of solid, low solvent waste. Disposal to cement kilns, coal fired power
93
plants, dedicated sludge incinerators, municipal and hazardous waste incinerators are all practised.
Drying is rarely employed by refineries due to safety risks.
Table B40: Examples of the composition of wastewater treatment sludges from refineries (reproduced
from BREF).
94
Table B41: Summary of sludge production and use by mineral oil and gas refineries and relevant PPs
potentially present in sludge from these installations.
Sludge is
produced
Wastewater
treatment sludge
is used
Requires management
of PP contaminated
sludges
YES
NO
YES
Relevant PPs
PAHs (e.g. benzene, naphthalene,

phenanthrene, anthracene,
benzo(a)pyrene), and metals
(including Pb, Ni and Hg).
2.25 Textiles industry
Reference:
Best Available Techniques in the Textiles Industry. Accessible via: http://eippcb.jrc.es/reference/txt.html
This BREF addresses installations for the pretreatment (operations such as washing, bleaching, mercerisation)
or dyeing of fibres or textiles. Particular attention is given to the following processes:
fibre preparation
pretreatment
dyeing
printing
finishing.
Upstream processes which may have a significant influence on the environmental impact of the subsequent wet
processing activities are also briefly described. The backing of carpets is also included.
All main textile fibre types, namely natural fibres, man-made fibres derived from natural polymers such as
viscose and cellulose acetate as well as man-made fibres derived from synthetic polymers are described,
including their blends.
The textiles industry constitutes a very long and complicated industrial chain. The sector is relatively
fragmented and dominated by SMEs with the three main end uses comprising clothing, home
furnishings, and industrial uses. Key sub-sectors involving wet processes include wool scouring,
textile finishing, and the carpet sector, whilst relevant finishing processes include pretreatment,
dyeing, printing, coating, washing and drying. Overall the sector is a significant source of emissions to
water, and the chemical load of effluents and wastewater sludges is thus a key environmental
management issue for this sector.
All of the effluent treatment processes employed by wool scouring mills produce sludge or concentrate
requiring disposal. Wool scouring is noted to result in the discharge of effluents with a high organic
content and variable concentrations of micropollutants, potentially including any pesticides applied to
the sheep. Importantly, it is noted that organochlorine pesticides, although increasingly stringently
regulated in Europe, may still be found in imported wools from some grower countries, and may
95
thereby also potentially contaminate wastewater treatment sludges. The removal of auxiliaries such as
spinning lubricants, knitting oils and preparation agents by wet treatment may reportedly result in the
release of PPs such as PAHs, nonylphenolethoxylates, and biocides. Furthermore, the process of
sodium hypochlorite bleaching gives rise to secondary reactions that form organic halogen compounds
such as trichloromethane.
The dyeing process is a major source of emissions from the textiles industry, with pollutants (e.g.
metals) potentially arising not only from the dyes themselves (where metals such as Ni are sometimes
used as catalysts and/or structural elements) but also from auxiliaries contained in the dye formulation
(e.g. dispersing agents, anti-foaming agents etc.), basic chemicals and auxiliaries used in dyeing
processes, and residual contaminants present on the fibre (e.g. residues of pesticides on wool).
To summarise, PPs of particular relevance to this industry, particularly in relation to the contamination
of wastewater treatment sludges and process residues of sludge-like character include organochlorine
insecticides, hexaclorocyclohexane (lindane), dieldrin, DDT, chlorfenvinphos, chlorpyrifos,
pentachlorophenol, nonylphenols, polybrominated diphenylethers, metals, PAHs, and
trichloromethane. Others may also be relevant.
In order to reduce the environmental emissions of hazardous substances from this industry it is
important to ensure that manufacturers have adequate information about the raw materials used in the
manufacturing process. For example, the type and amount of preparation agents and sizing agents,
residual monomers, metals, biocides (e.g. ectoparasiticides for wool) present on the fibre. This allows
manufacturers to employ source control options for reducing the emissions of key pollutants (e.g.
organochlorine pesticides). Recently, co-operation programmes between trade associations and major
grower countries has led to a reduction in the average organochlorine pesticide residues occurring in
wool, along with the development of low-residues certification schemes. These approaches also help
ensure that wastewater and hence wastewater treatment sludge will have lower residues of these PPs.
Further substitution of particularly hazardous substances (e.g. nonylphenolethoxylates) is also to be
encouraged to assist with PP source control.
Other options for reducing the quantity of sludge produced and/or improving sludge quality also exist.
For example, the implementation of a dirt removal/grease recovery loop in the wool scouring process
can substantially reduce the volume of water used and hence the volume requiring treatment (and
leading to the production of sludge). This approach can even be combined with evaporation of the
effluent and incineration of resulting sludge so that together this system can be considered as BAT.
However, it is noted to be a complex and expensive process to establish. An alternative option for the
disposal of wool scour sludge is for recycling for use in the brick making industry. This is also
considered BAT. Wool scour sludge has been noted to have excellent technical properties for this
purpose when mixed with clay, and recycling as a raw material for brick making may also potentially
work out cheaper than landfilling, composting, or incineration (depending on the deal struck with the
brick-maker).
In general, sludge and residue from this industry may be disposed of by incineration (with heat
recovery), pyrolysis/gasification, brick manufacturing, composting or co-composting, or landfill. Solid
wastes from thermal disposal options (i.e. incineration, pyolysis etc.) are subsequently disposed of to
landfill. Wool scour sludges cannot be composted alone, and thus require the addition of carbon-rich
organic material (e.g. green waste) for this to be a viable measure. Landfill is the simplest method of
sludge disposal, and often the cheapest as well, although new regulations may potentially change this
as landfill is considered to be of limited economic and environmental sustainability in the long-term.
Special care should be taken when disposing of waste sludges/residues containing halogenated
compounds as treatment at high temperature (e.g. incineration) can lead to the emission of dioxins and
furans. Incineration should therefore only be carried out in properly constituted incinerators, running
under consistently optimal conditions.
96
Table B42: Summary of sludge production and use by the textiles industry and relevant PPs potentially
present in sludge from this sector.
Sludge is
produced
Wastewater
treatment sludge
is used
Requires
management of PP
YES
NO
YES
Relevant PPs
Biocides (including organochlorine

insecticides, hexaclorocyclohexane
(lindane), dieldrin, DDT,
chlorfenvinphos, chlorpyrifos), PAHs,
nonylphenols, trichloromethane, metals
(e.g. Ni), pentachlorophenol, and
polybrominated diphenylethers.
2.26 Slaughterhouses and animal by-products industries
Reference:
Best Available Techniques in the Slaughterhouse and Animal By-products Industries. Accessible via:
http://eippcb.jrc.es/reference/sa.html
This BREF addresses the slaughter of all animals that might contribute to a significant output for an
installation. The 'slaughter' activity is considered to end with the making of standard cuts for large animals and
the production of a clean whole saleable carcass for poultry. Directly associated activities of the slaughter
process are also included.
The disposal and recycling of animal carcasses and animal waste is also addressed in this BREF. The animal
by-products activities covered include treatments for entire bodies or parts of animals and those for products of
animal origin. These activities include treatments of animal by-products both intended and not intended for
human consumption. A wide range of by-products activities are covered. These include fat melting; rendering;
fish-meal and fish-oil production; bone processing; blood processing associated with slaughterhouses and to the
degree where the blood becomes a material for use in the preparation of another product. The dedicated
incineration of carcasses, parts thereof, meat, bond-meat and burning of tallow, are covered principally as
routes for disposal. Land spreading; land injection; biogas production; composting; preservation of hides and
skins for tannery use in slaughterhouses; and gelatine manufacture are also covered. Landfill is not covered,
except when mentioned as a route for disposal.
As indicated in the above summary a wide range of activities are covered in the BREF pertaining to
the slaughterhouse and animal by-products industries, including slaughtering and carcass processing,
fat melting, rendering, fish-meal and fish-oil production, blood processing, and associated waste
disposal activities. The industry is quite diverse, spread throughout Europe, and typically varyies
depending on the national characteristics and associated range of end-products (e.g. cured meats).
Important environmental issues associated with this industry include the large volume of water used
and the characteristically high strength organic waste liquors produced (e.g. from blood contaminated
effluents). Food and veterinary legislation require that potable water is used as process water in this
97
sector, hence there are virtually no opportunities for direct reuse of water in these installations and
large quantities of wastewater are thus virtually unavoidable.
Wastewater from the processing of carcasses and by-products is sent to a wastewater treatment plant
(often incorporating dissolved air flotation and/or activated sludge treatment), with the resulting
sludge being disposed of by incineration, landfill, land injection, land spreading, or used for biogas
production (digestion). Non-aqueous waste from the fat melting and rendering stages of by-product
processing are generally disposed of by incineration or landfill, but may also be reused to some extent
in the manufacturing of fertiliser or in the burning of tallow as fuel.
It appears that there is potential for the combined composting of waste from animal by-products (e.g.
stomach contents, wastewater sludge, blood processing sludge, grease trap fat etc.) to increase,
although requirements for pre-treatment of animal waste from this sector prior to composting and
restrictions on subsequent usage may limit this development. For example, regulation 1774/2002/EC
bans the application of compost derived from animal by-products on pasture lands. Nevertheless,
opportunities may remain for the reuse of composted by-product waste in landscaping, forestry,
horticulture and land restoration. Waste sludge and composted waste containing more than 4 % fat or
oil content is deemed unsuitable for land spreading as detrimental effects on plant growth may result.
The application of sludge on agricultural land may be restricted after flocculation due to the presence
of metals. In general, limitations on land spreading and land injection has prompted an increasing
trend towards the incineration of sludge in some parts of Europe.
There are many processing stages in this industry where the build-up of sludge and sediment may
arise. These are not all covered in the following text however some key examples are given. Much of
the sludge from processing tanks may be passed directly to wastewater treatment facilities on a regular
basis. For example, the sludge from the scalding tanks used for pig scalding is typically emptied
together with the used water directly into the waste water drainage system at the end of the working
day. Some of the sludge like by-products produced may be valorised and sold. For example, separated
red blood cell fractions contain 30% solids and are generally spray dried and used as a natural pigment
in the meat industry, in pet food, animal feed and for fertilisers. Meanwhile the biological waste
produced during the spray drying process (from filtration, osmosis and cleaning) is generally filtered
and then sent to wastewater treatment, with the protein rich sludge thus produced typically being
landfilled or incinerated although it could potentially be composted with other materials. Wastewater
treatment sludge produced after both the pretreatment of bones and gelatine production is reported to
be an excellent fertiliser and soil improver and is frequently used for land injection, but may need to
be mixed with other substrates first, and must be applied in accordance with land requirements and
local and European regulations.
With regards to BAT recommendations likely to affect sludge quality and/or quantity it is
recommended that a fat trap is used to remove fat from wastewater, that a flotation plant is used to
remove additional solids, that the effluent is further subjected to biological wastewater treatment prior
to discharge, and finally that increased efforts be made to use sludges for further beneficial uses. For
example, the increased use of composting procedures for mixed animal by-products waste from
slaughterhouses and wastewater treatment may help reduce the disposal of slaughterhouse byproducts as waste (e.g. in landfill).
98
Table B43: Summary of sludge production and use by the slaughterhouses and animal by-products
industries and relevant PPs potentially present in sludge from these sectors.
Sludge is
produced
Wastewater
treatment sludge
is used
Relevant PPs
YES
NO
POSSIBLY
Metals, biocides
99
3. Conclusions
Key information presented in this section on the production, treatment and disposal/reuse of PP
contaminated industrial sludge is summarised in Table B44, showing whether sludge is produced
and/or used by each of the reviewed industrial sectors and whether this sludge is likely to contain
specific PPs.
It is clear that the production of PP contaminated sludges is a management issue for many of the
industrial sectors covered in this review. Aside from the formation of process sludges there is also the
general problem (as noted also in the section on municipal wastewater treatment sludge) that action to
reduce pollutant discharges to surface waters (i.e. by improving/introducing wastewater treatment)
inadvertently leads to the increasing production of wastewater treatment sludge. By its very nature the
wastewater treatment process is designed to concentrate recalcitrant contaminants in the sludge to
prevent their release to surface waters, thus sludge from the treatment of wastewaters containing
recalcitrant organic substances and metals is contaminated by these substances and may require
additional pre-treatment before disposal. Aside from endeavours to recycle as much sludge as possible
(whether this be internally within the facility or externally by working with other industries), often the
only other available option is to pre-treat the sludge to remove problematic contaminants such as
mercury so that the sludge can be disposed of in a regular landfill and is not classed as hazardous
waste. Clearly the recovery of value through sludge reuse is desirable but this is not always a feasible
option in all manufacturing and process situations and must also be considered in the light of potential
economic constraints.
In all industrial sectors, process management can potentially play a central role in protecting the
quality of wastewater sludge produced and minimising waste production and subsequent
environmental emissions. For example, by practicing source control and modifying products, inputs,
and procedures wherever possible in order to minimise waste production and maximise the recycling
and reuse of waste streams, it is possible to considerably reduce the emissions from specific pathways
(including sludge disposal). New installations may be particularly well placed to implement and
demonstrate improved environmental performance through the use of alternative technologies to
prevent waste water arising, by closing production loops and by using dry processes rather than wet
processes wherever possible.
100
YES
YES
Industrial cooling
systems
Ferrous metals
processing industry
POSSIBLY
NO
NO
YES
POSSIBLY
YES
YES
Requires
management of
PP contaminated
sludges
YES
Pb, Cd and Ni, PAHs (from

oils), organic degreasing
agents (solvents)
Metals, biocides
101
Both process and wastewater treatment sludges potentially

produced; most sludge is currently disposed to landfill; BAT
is to recycle sludges (e.g. oily sludge, metal rich sludge) if
Sludge production likely to increase in response to pressure to

change to recirculating cooling systems; disposal according to
local (or national) legislation and sludge quality. BAT not
specified.
Major issue associated with Hg contaminated process sludge;

Hg recovery should be practiced as far as practicable prior to
disposal.
Wide variety of process sludges produced; wastewater sludge

also produced; BAT is to recycle/reuse sludge as much as
possible within the production process
Cd, Pb, Ni
Hg, Ni, chloroform,

dichloromethane, carbon
tetrachloride,
tetrachloroethylene
No significant sludge produced by this industry. However,

some industrial sludge may be used as raw material in cement
production (e.g. paper sludge) and sludge can also be used as
combustion fuel. BAT is to fit activated carbon filters to dry
kiln systems using sewage sludge or other metal contaminated
sludge as fuel.
Summary of relevant sludge treatment/disposal options
Metals
PAHs
Halogenated organic
compounds
PPs likely to be found in

sludge from this sector
YES
Chlor-alkali
industry
YES - Some
recycling/reuse of
sludge from
ceramics process
wastewater
treatment is
possible
YES Use of
sewage sludge for
fuel and raw
materials is possible
NO
YES
Wastewater
treatment sludge is
used
Sludge is
produced
Ceramics
manufacturing
industry
Cement and lime

manufacturing
industries
Industry
Table B44: Summary of sludge production and use by major EU industrial sectors and PPs potentially present in sludge from these sectors.
YES
YES
YES
YES
YES
Food, drink and

milk industries
Storage activities
Glass
manufacturing
industry
Intensive poultry
and pig rearing
industries
Large combustion
plants
POSSIBLY
NO
NO
NO
NO
POSSIBLY
YES
POSSIBLY
YES, especially
Pb crystal
production sites
POSSIBLY
POSSIBLY
YES
Cd, Ni, Hg, Pb, PAHs
Cd, Ni, Pb, biocides
Pb
Multiple
Metals (e.g. Ni), PAHs,

biocides, solvents (e.g.
dichloromethane)
Pb, Ni. Cd, Hg, PAHs,

Solvents
YES
Non-ferrous metals
processing industry
102
Use and produce wastewater treatment sludge; wastewater

sludge typically disposed of to landfill or landspreading; some
sludge products may be reused (e.g. lime sludge reused in the
cement industry); BAT is to recover products from sludge for
Pig slurry produced; management depends on national

regulations; may be separated into solid/liquid fractions in
some places; land spreading is common practice; anaerobic
digestion and stabilization may also be applied prior to land
spreading.
Wastewater sludge from the glass industry has generally been

disposed of to landfill; BAT is recover and valorise relevant
waste streams (e.g. lead crystal cutting sludge; etching sludge
etc.)
Sludges from storage tank cleaning etc. are often landfilled or

incinerated; BAT is to minimise sludge production during
storage by appropriate mixing and/or resuspension; Air
mixing is not BAT due to potential for stripping of volatile
components.
Numerous different types of sludge produced; some recycled

into production processes, some used for land spreading and
some sent to landfill. BAT is to valorise and recover useful
materials from sludge (e.g. food processing sludge may be
used in animal feeds).
Metal contaminated sludge produced; many waste streams are

already recycled in this sector (e.g. metal rich sludge); BAT is
to maximise recycling of sludge wastes.
possible and to minimise the production of wastewater and

associated sludge. BAT also includes dewatering of sludge to
minimise volume for landfilling.
YES
YES
YES
YES
Tanneries
Polymer
production industry
Surface treatment
with organic
solvents industry
Surface treatment
of metals and
plastics
YES
NO
NO
NO
NO
YES
YES
YES
YES
YES
Cd, Pb, Ni,

nonylphenols, octyphenols,
trichloroethylene,
tetrachloroethylene, methylene
Solvents, metals (e.g. Cd, Pb,

Ni), organotin compounds (e.g.
TBT), biocides
Solvents
Biocides, organic solvents,

surfactants (e.g. NPs), metals
(e.g. Cd, Pb), PBDEs
Metals, nonylphenols,
solvents, biocides, other
YES
Pulp and paper

industry
103
Sludge wastes are mainly derived through treatment of waste

process solutions and wastewater and are typically classed as
hazardous; Careful process management can minimise
dragout losses and improve sludge quality; Metals from
BAT is to optimize processes to minimise paint sludge buildup and to minimise process water use and hence wastewater
treatment sludge production; Distillation and ultrafiltration of
wastes for solvent, paint and ink recovery can minimise
sludge production; BAT is to dewater and/or recycle sludge.
Wastewater treatment sludge produced; Sludge is typically

dewatered then incinerated; Ashes from incineration must be
used as secondary material in the cement industry etc.
BAT is to segregate waste streams as far as possible to allow

maximum recycling of waste products; Landfilling is not
considered BAT for sludge from this sector but may in many
cases be the only option available.
Several types of sludge formed, mostly landfilled or

incinerated; Fibrous sludge may be re-used as fuel for heating
processes (energy recovery); Wastewater treatment sludge
may be used as secondary material in the brick industry and
can also be recycled back into the paper production process
(as can paper residue sludge); Paper industry sludges can
often be used for co-incineration by other industries; BAT is
to thicken and dewater sludge prior to disposal.
use in other industrial sectors and to recycle as much as

possible; where sludge is used for combustion (e.g. cocombustion of sewage sludge) BAT is to install appropriate
pollution prevention devices to limit emissions (e.g. scrubbers
for Hg production).
YES
YES
YES
Large volume
organic chemical
industry
Large volume
inorganic chemical
(ammonia, acids
and fertilisers)
industries
Organic fine
chemicals
manufacturing
industry
NO
NO
NO
YES
YES
YES
YES
YES
It is assumed that most PPs

still produced or used in the
EU will be relevant here
Metals
Pb, benzene, ethylene

dichloride, carbon
tetrachloride,
hexachlorobenzene,
pentachlorobenzene,
hexachlorobutadiene,
Hg, Ni, Cd, Pb, PAHs,

chlorobenzenes, halogenated
organic compounds
YES
Waste incineration
industry
chloride
104
Improvements in sludge quality to be achieved through

improvements in process and plant design; Wastewater
streams should be segregated and treated appropriately to
ensure that the biological treatment process is not impacted
by toxic shock.
BAT is to minimise production of wastewater and hence

sludge; BAT for sludge disposal is not specified.
Most process sludges produced by this sector are either

landfilled or incinerated however process residues (e.g. tars,
waxes from distillation columns) may also have value as a byproduct, as feedstock for another process, or as fuel; BAT is
to treat each waste material on a case by case basis and to aim
for recycling, reclamation or post treatment of waste sludge.
Sludge may be produced and may also be combusted (e.g. cocombustion of sewage sludge); Sludge pretreatment (e.g.
neutralization, drainage, thickening, drying) may be required
prior to incineration; BAT is to ensure high combustion
efficiency and to limit the release of metal pollutants
including Hg in the flue gas; Wastewater from scrubbers can
potentially be treated to recover both gypsum and table salt
and thus reduce sludge volume; Ash materials can potentially
be recycled as construction materials.
process sludges may be recovered and reused (e.g. metals

from electroplating sludges reused in non-ferrous metal
refining); BAT is to dewater and dry sludge and to reuse,
recover and recycle materials as far as possible.
YES
YES
YES
Management of
tailings and wasterock in mining
activities
Mineral oil and gas

refineries
YES
YES
YES
YES
Various sludge products produced and highly fluid tailings

also require management; Backfilling, management on heaps,
and thickening are relevant activities; Sewage sludge and
paper sludge may be used as oxygen consuming covers for
long term management of tailings dams with acid drainage
potential; Sewage sludge may also be used to assist with
revegetation.
Cd, Pb, Hg, Ni
105
Both oily and non-oily sludge produced; Oil from oily

sludges should be recovered if possible; Oily sludges and
wastewater sludges may be used as feedstock in the coking
process and this is commonly practiced; Land farming,
landfilling and incineration of sludge is practiced; Sludge may
also be incinerated at cement kilns, coal fired power plants,
and dedicated sludge incinerators or municipal waste
incinerators.
Both process and wastewater treatment sludges are produced;

BAT is to reduce the amount of sludge produced through the
use of high purity feedstock, improving process efficiency,
and improving catalyst systems; Recycling of constituents
from some sludges is possible (e.g. recycling of cadmium
pigment filtration residues and precipitation sludges); Metal
sludges may also be recycled externally in some cases (e.g. by
zinc and copper smelters); Sludges generally either
incinerated, landfilled or sent to off-site metal recovery plants
for further processing.
Cd, Pb, Ni, Hg, various

organic PPs
PAHs (e.g. benzene,

naphthalene, phenanthrene,
anthracene, benzo(a)pyrene),
and metals (including Pb, Ni
and Hg).
Many sources of wastewater and hence sludge production;

Sludge quality can be improved through the selection of high
quality raw materials for process input; Metal contaminated
sludge (e.g. from inorganic phosphate production) is not
considered recyclable and is generally landfilled.
Metals
NO
NO
YES
Specialty inorganic
chemicals industry
NO
YES
Large volume
inorganic
chemicals (solids
and other industry)
YES
Slaughterhouse and
animal by-products
industries
NO
NO
POSSIBLY
YES
Metals, biocides
Biocides (including
organochlorine insecticides,
hexaclorocyclohexane
(lindane), dieldrin, DDT,
chlorfenvinphos, chlorpyrifos),
PAHs, nonylphenols,
trichloromethane, metals (e.g.
Ni), pentachlorophenol, and
polybrominated
diphenylethers.
YES
Textiles industry
106
Large volumes of wastewater produced and reuse of water

generally not possible; Sludge disposed of by incineration,
landfill, land injection, land spreading, or used for biogas
production; Composting of sludge is possible but subject to
regulatory restrictions; Some sludge like by-products may be
valorized and sold (e.g. red blood cell fractions); BAT is to
use sludges for further beneficial reuse wherever practical and
allowed.
Process and wastewater sludge produced; Landfill is the

simplest method of sludge disposal; Wool scour sludge can
also be recycled for use in the brick making industry (BAT)
and this may prove cheaper than landfilling, composting or
incineration; BAT includes process amendment to reduce
wastewater production, for example the inclusion of a dirt
removal/ grease recovery loop in the wool scouring process.

1. Greywater treatment systems as sources of PP contaminated
sludge and sediments and implications of sludge disposal methods
for PP fate
A variety of potential treatment options are available for greywater treatment and reuse. Currently,
these treatment systems show a wide range of design and sophistication, from simple single-household
soil filter systems to community-scale multi-stage rotating biological contactors (RBC) and membrane
bioreactors (MBR), but all are based on chemical, physical, and biological processes such as settling,
filtration, adsorption, aeration, precipitation, aerobic/anaerobic digestion, and disinfection (see
ScorePP Deliverable 5.1 for a review). As such, the majority of these systems build up sludge or
sediment as a normal part of the process.
Whilst greywater treatment and reuse is becoming increasingly popular in water stressed countries
(including EU Member States such as Cyprus) the uptake of this technology must still be considered
as being at an early stage and most research to date has been focused on the monitoring of
conventional water quality parameters such as pH, biological oxygen demand (BOD), total suspended
solids (TSS), and pathogen content. There is very little measured data reported in the literature
regarding the presence and/or removal of PPs during greywater treatment and to our knowledge, no
data has previously been published in the literature documenting the concentrations of PPs in
greywater sludge. Yet despite the limited number of studies investigating the presence of PPs in
European greywater a considerable number of PPs have been detected at measurable concentrations,
including substances such as Cd, Pb, Ni, Hg, chloroform, octylphenols, nonylphenols, DEHP, PBDEs,
and TBT. Moreover, recent work by members of the ScorePP consortium has documented the
presence of both organic and inorganic PPs in greywater as well as key inorganic PPs (i.e. Cd, Hg, Ni,
and Pb) in Danish greywater sludge (Donner et al. (2010a); Donner et al (2010b). Many greywater
systems are used only to recycle the bathroom greywater fraction and therefore it is unlikely that all of
the listed PPs will be present in greywater from a particular site. However, numerous household
sources of PPs have been documented in WP3 of the SccorePP project so that it may certainly be
expected that some of these substances could be present in greywater and the literature data, although
limited, further supports this proposition.
Earlier work on the topic of greywater for the ScorePP project (see Deliverable 5.2) used simple
geochemical modelling applications within EPI SuiteTM v3.20 (US EPA, 2007) to assess the likely
partitioning and fate of PPs during greywater treatment. Although not relating directly to greywater
treatment as no specific greywater treatment models were available, two fugacity based approaches
were applied, one focused on an aquatic (river/lake) environment (LEVEL3NT - Mackay Level III
Fugacity model) (i.e. simulating a land based treatment system such as a reedbed or constructed
wetland) and the other based on a conventional activated sludge sewage treatment plant (STPWIN)
(i.e. assumed analogous to a more technical treatment system incorporating biological treatment such
as a rotating biological contactor). The results obtained from the pollutant partitioning and fate
modelling are presented in Table C1. Although these models are not tailored specifically to match
greywater composition and treatment conditions, they do allow some preliminary insights into the
potential partitioning behaviour of PPs during greywater treatment. Both the LEVEL3NT results and
STPWIN results indicate that PP removal during water treatment is likely to be predominantly due to
partitioning to the solid/sludge phase. The only substances investigated which appear likely to differ
from this trend are benzene, chloroform, ethylene chloride, and dichloromethane, with STPWIN
results for these substances predicting 718% partitioning to the solid phase and the remainder being
relatively equally distributed between the aqueous and gaseous phases. As biodegradation data
107
collected within WP3 of the ScorePP project indicated many of the PPs to be recalcitrant to
biodegradation (see Deliverable 3.1) it is feasible to conclude that in cases where PPs are present in
greywater the majority are likely to become at least partially entrained in the greywater treatment
sludge fraction. The role of biodegradation will certainly be restricted in the case of technical
treatment systems with relatively short hydraulic retention times and/or systems with young
sludge/biofilm that has not yet adapted to the presence of these recalcitrant substances.
Table C1. Phase distribution modelling results (EPI Suite v3.20, US EPA, 2007) for selected PPs.
Substance name
Alachlor
Anthracene
Atrazine
Benzene
Benzo(a)pyrene
Chlorfenvinphos
Chloroform
Chlorpyrifos
DEHP
Diuron
Endosulfan
Ethylene chloride
Fluoranthene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclohexane
Isoproturon
Dichloromethane
Naphthalene
4-nonylphenol
para-tert-octylphenol
Pentabromodiphenylether
Pentachlorobenzene
Pentachlorophenol
Simazine
Tributyltin cation
1,2,4-trichlorobenzene
Trifluralin
C10-13-chloroalkanes
1
STPWIN:
% adsorbed to
sludge
(Total %
removed)
13.3 (13.5)
52.5 (54.2)
3.3 (3.5)
1.1 (68.9)
91.9 (92.6)
90.2 (90.9)
92.8 (93.6)
91.8 (92.6)
21.9 (22.2)
1.1 (59.8)
75.7 (76.4)
93.2 (94.0)
3.6 (3.7)
22.4 (25.2)
1.4 (34.0)
81.4 (82.2)
88.0 (91.1)
51.9 (88.9)
36.4 (37.0)
4.6 (4.7)
1.0 (56.9)
8.3 (23.6)
90.0 (90.8)
84.0 (84.8)
93.0 (93.8)
79.5 (83.6)
80.5 (81.2)
2.4 (2.5)
74.6 (97.3)
26.4 (53.1)
84.9 (86.0)
92.9 (93.7)
59.2 (98.2)
Level III fugacity model:

Phase distribution (%)
Air
0.0
0.2
0.0
37.6
0.0
0.1
0.0
0.0
0.0
42.8
0.0
0.3
0.0
0.3
37.0
0.4
0.5
2.7
0.6
0.0
46.0
1.0
0.3
0.2
0.2
1.0
0.0
0.0
0.4
4.0
0.1
0.0
2.8
Water
10.2
9.7
13.7
48.1
2.5
3.6
1.8
2.6
10.7
43.2
4.5
3.8
14.6
5.0
44.5
7.6
1.3
3.5
6.1
13.4
47.1
12.8
9.5
9.1
0.9
2.2
2.8
19.6
6.0
7.3
2.6
1.7
11.0
Solid1
89.7
90.1
86.2
14.3
97.5
96.2
98.2
97.4
89.3
14.0
95.5
95.9
85.5
94.7
18.4
92.1
98.1
93.8
93.2
86.6
7.0
86.2
90.3
90.8
98.9
96.7
97.2
80.4
93.6
88.8
97.3
98.2
86.2
Solid phase = soil and sediment;
108
As noted earlier, the majority of technology-based greywater treatment systems incorporate the use of
one or more settling tanks, to retain the sludge produced as part of the treatment process. Currently
these systems do not usually include any additional sludge treatment but rely instead on the periodic
discharge/transfer of sludge to a municipal WWTP (either by backflushing to sewer or by pumping
and transferring by tanker) for further processing and disposal. Preliminary calculations have shown
that if greywater treatment sludge were to be removed from the wider municipal WWTP load this
could potentially improve the sludge quality and hence help meet the requirements of the various
national and European sludge regulations, particularly in relation to the stringent requirements for key
metal contaminants such as Cd (Donner et al, 2010a). The separate treatment and disposal of
greywater sludge is an attractive prospect because it is unlikely to contain a significant nutrient
content, and yet does effectively concentrate recalcitrant substances such as metals and nonylphenols.
The separation of the greywater treatment sludge from community scale treatment and reuse systems
is feasible and could effectively reduce WWTP sludge metal loads without significantly impacting on
sludge nutrient value. In contrast, sludge separation from single household system designs is unlikely
to be practical and these systems will most probably continue to be designed to periodically backwash
or flush particulate matter to the sewerage system in order to minimise the system maintenance
requirements.
The tendency for PPs to partition to solids (e.g. soils and sediments) also indicates that land-based
greywater treatment systems (e.g. reedbeds) and the reuse of untreated greywater for garden irrigation
and/or infiltration should be carefully monitored to ensure that hazardous substances that are not
readily biodegradable in the soil environment are properly managed and the risks of residual
contamination remaining in sediments/soils are appropriately addressed.
Further details relating to the presence and fate of PPs during greywater sludge treatment can be found
in Deliverable 5.2 of the ScorePP project and associated publications.
109
Section D Stormwater sludge and treatment

1. Stormwater Best Management Practices as sources of PP
contaminated sludge and sediments
Stormwater Best Management Practices (BMPs) are increasingly used by both the private and public
sectors in an effort to alleviate flood risk and improve stormwater quality. Although both structural
and non-structural BMPs exist, this report focuses on structural BMPs as these are of immediate
relevance when it comes to the issue of contaminated sludge and sediment management. Nonstructural BMPs refer to practices such as street sweeping which help reduce the spread of diffuse
pollution but do not involve the construction of physical containment/retention structures. Structural
stormwater BMPs include a wide range of structures, from filter drains and swales to porous paving
and constructed wetlands (See Table D1). These facilities are frequently used to collect, withhold and
treat runoff from large areas of impermeable surfaces such as highways and roads, as well as carparks
and other urban surfaces. For example, they are sometimes installed on industrial sites in an effort to
limit the release of pollutants to surface waters and the wider environment. It is also particularly
common for BMPs to be located adjacent to roads (e.g. swales, filter strips etc.) and traffic sources
may therefore be a major factor determining the key contaminants of concern. BMPs can be used
either individually or in combination with each other (as a treatment train), both as an alternative to or
in combination with conventional piped stormwater drainage systems.
Table D1. Relative importance of direct removal processes in BMPs.

BMPs
Filter drain
Porous asphalt
Porous paving
Filter strip
Swales
Soakaways
Infiltration trench
Infiltration basin
Sedimentation tank
Retention ponds
Detention basins
Extended detention basin
Lagoons
SSF constructed wetlands
SF constructed wetlands
Adsorption
to substrate
Settling
Microbial
degradation
Filtration
Plant
uptake
Volatilisation
Photolysis
M/H
L/M
H
M
M
M/H
M/H
H
L
L/M
M
M
L/M
M/H
M
L/M
L
L/M
L
L/M
L/M
L/M
H
M/H
H
M/H
H
M/H
M
M
M
L
M
L/M
L/M
M
M
H
L
M
L/M
M
L
H
M
M
H
H
L/M
M
M/H
M/H
M/H
NA
L
L
L
L
M/H
M
L
NA
L
M
M
L
L
L/M
NA
L
L
L
L
M/H
M
L
L
L
L/M
M
L
L
M
L
M
M
M
L/M
L/M
M
NA
L
NA
L/M
L/M
NA
NA
L/M
L
L/M
L/M
L/M
L
L
L
Key: H = high (considered to be a dominant removal process), M= medium (process contributes significantly to
overall pollutant removal capability), L= low (process which makes only a small contribution), NA = not
applicable (process not relevant); SSF = sub-surface flow; SF = surface flow
A notable proportion of the PPs covered by the ScorePP project are used in activities of relevance to
stormwater pollution. For example, TBT in stormwater may be sourced from runoff from
contaminated shipyards and surface treatment sites; roads are a major source of metal contaminants
due to their presence in vehicle parts, tyres, brakes and road materials (as well as the previous use of
110
leaded petrol); biocides are commonly used alongside roads and railways as well as in external
building materials such as roofing materials; and traffic is a major source of PAH emissions. Another
potential source of stormwater pollutants in areas with combined sewer systems is from combined
sewer overflows during storm events when the capacity of wastewater treatment plants is exceeded. In
such cases a wide variety of contaminants may be present, together with high total suspended solids.
Reviews by Makepeace et al (1995) and Eriksson et al (2007) have documented the
detection/quantification of over 450 inorganic and organic pollutants in stormwater including many of
those listed under the WFD. So although there has been limited research specifically measuring the
presence of PPs in stormwater sediments, it is clearly evident that a range of different PPs are likely be
present in stormwater. Furthermore, on the basis of both the physico-chemical characteristics of the
target PPs and of the fugacity modeling results presented in the previous section on greywater, it
appears that many of these substances have the propensity to build up in stormwater sediments during
the deposition of particulate matter. In Table D1 a list of different types of BMPs is given together
with an indication of the importance of different pollutant removal processes for each category of
BMP. This table is derived from work completed in ScorePP Task 5.1 and is based on a combination
of experimental data and expert judgement (see Deliverable 5.1). The table shows the key role of
adsorption and settling as pollutant removal processes in a wide range of BMPs, further highlighting
the likelihood that PP contaminated sediments are likely to build-up in urban stormwater BMPs.
In a study of 4 stormwater management ponds on a multiple use (i.e. housing, industrial, commercial)
development site in Scotland, annual surveys of sediment depth and quality between 1999 and 2003
indicated varying sedimentation rates up to 1.0 cm/yr (Heal et al. 2006). Other studies of this nature in
a variety of different types of BMPs have found sedimentation rates of 3.2 cm/yr in a detention pond
adjacent to a highway (Frm, 2002), 2.0 cm/yr in a stormwater pond located in a predominantly
commercial area (Marsalek et al., 1997), 0.46 cm/yr in an artificial lake in a residential area (Rowney
et al., 1986), and 2.26 cm/yr in 9 different detention ponds constructed in an urban area in the vicinity
of a highway (Yousef et al., 1994). It is important to recognise that where sedimentation rates are
measured over the long-term (i.e. based on the quantity of sediment excavated since the structure was
built) the calculated rates will also be affected by any resuspension and transport of sediment that may
have occurred during the lifetime of the pond. It should also be noted that the volume of infill
represented by a particular sedimentation rate varies depending on the size of the BMP and that the
associated sediment characteristics may also vary in terms of the percentage organic/inorganic
material present.
Sediment characteristics in BMPs can be expected to differ in pollutant content depending on the
surrounding watershed and predominant activities carried out in that area. For example, BMPs
installed on industrial sites may contain relatively high levels of chemicals handled and stored on-site,
whilst BMPs at airports or other transport facilities may have relatively high contents of hydrocarbons,
detergents, deicing chemicals etc. in their sediments. As mentioned previously, measured data focused
specifically on sediment quality in stormwater BMPs is far less extensive than measured data relating
to stormwater quality. Nevertheless, by considering the pollutants commonly found in stormwater and
their removal during stormwater treatment it is easy to see that one of the major groups of stormwater
pollutants is that of metals, including those listed as PPs under the WFD. Their removal during
treatment cannot be through biodegradation or other biological processes, so aside from some
possibility for volatilization, removal is assumed to be related to the adsorption, sedimentation and
settling of metals on suspended sediments. This indicates a potential for build-up of metals in BMP
sediments over time, which has indeed been observed in those studies investigating the chemical
characteristics of BMP sediments. Analysis of metal contents in pond sediments sampled by Heal et
al. (2006), Frm (2002), Marsalek et al (1997), Rowney et al. (1986) and others has indicated
deposition of metal contaminated sediment over time. This research has also indicated that sediment
quality can be highly variable within individual stormwater management facilities. For example, Heal
111
et al. (2006) showed that concentrations of metals tended to be higher near the pond inlet. Although
the relevant results are still somewhat limited research has indicated that in most cases it will be the
rate of sediment infilling and subsequent reduction in the retention time for stormwater that determines
the timing of sediment removal for BMP maintenance, rather than the build-up of contaminants in
BMP sediments to unacceptable levels.
At the present time there is still considerable uncertainty as to the required maintenance hours and
costs for maintaining stormwater BMP facilities, with previous experience mostly focusing on the
installation of BMP structures and less on the ongoing maintenance. The tendency for sedimentation
must however be realised as an issue requiring ongoing maintenance for not only does sedimentation
reduce the available stormwater storage volume of BMP structures it may also be of concern from a
water quality perspective. For where there is a buildup of contaminated sediments there is also the
potential for their resuspension and transport to downstream environments, meaning that stormwater
BMPs may potentially act both as pollutant sinks and sources. In any case, regardless of whether the
timing is based on the reduction in stormwater storage volume or key sediment contaminant
concentrations, sediment removal is a necessary, albeit occasional, BMP management requirement,
and the potential disposal pathways following removal will be heavily dependent on the degree of
contamination.
2. Treatment and/or disposal of stormwater sludge/sediments

The installation of BMPs throughout Europe has increased considerably over the past few decades and
it is only relatively recently that the removal of built-up sediment has increasingly been required. In
most cases there are no specific guidelines detailing acceptable BMP sediment contaminant limits for
disposal purposes, but testing has in some cases resulted in disposal to landfill as hazardous waste (e.g.
in parts of Scandinavia). At the present time it is common in many EU Member States where BMPs
are in place to compare BMP sediment quality to contaminated soil guidelines when considering the
possibilities for disposal. In cases where these guideline limits are exceeded, excavated sediments may
be indeed be classified as hazardous waste and this will influence the choice of appropriate disposal
pathways. Furthermore, with EU regulations increasingly designed to limit the disposal of waste to
landfills, it is important to note that the options for hazardous waste disposal are both increasingly
limited and increasingly expensive. For example, there are only 3 landfill sites in the UK which can
currently accept sediments classified as hazardous waste.
In a recent study of BMP maintenance and related whole-life costs, the results from the chemical
analysis of 565 BMP sediment samples (from the USA, Canada and UK) were reviewed (WERF,
2005). BMP locations discussed in the review included sites receiving runoff from highways, town
centres, industrial areas, large housing areas and a canal alongside old foundries with extensive ground
contamination issues. A summary of the results is reproduced in Table D2 and also includes the EU
threshold values for the definition of hazardous waste. It is clear that with respect to the four metals,
which are listed as PPs (Cd, Pb, Ni and Hg), that the vast majority of samples (with the exception of
one canal sediment sample from Scotland) fell below the guideline limit and thus did not need to be
classified as hazardous waste. In the UK, this means that the dredged sediment can be disposed of on
the banks surrounding the BMP structure, which has the benefit of being a relatively low cost option.
However, it should be noted that this practice may not be allowed in all member states and was also
not the option chosen during the actual maintenance activities. In fact, the dredged sediments from two
of the sites were disposed of to landfill (due to lack of space at the sites) and the sediments from two
further sites were not removed at all (due to insufficient budget at one site and concerns regarding the
smell and potential to attract flies at the other).
112
Table D2. Maximum concentrations of metals in sediments from various BMP/SUDS sites.
Overall, the possible options for BMP sediment disposal are as follows:
On the bank adjacent to the BMP
For beneficial reuse in agriculture (if uncontaminated and of benefit to soil quality)
As non-hazardous waste to a licensed disposal site or facility
As hazardous waste to a special waste disposal site or facility
As part of a construction, e.g. for an embankment or other minor landfill use close to the BMP.
113
The level of pollution of sediments and presence and concentration of other PPs other than metals is
an area of current research and information and management experience surrounding this issue can be
expected to grow in the coming years as more and more stormwater BMPs reach an age where
sediment removal is necessary to maintain the system efficacy.
114
General Conclusions
There are a vast range of activities which lead to the production of sludge-like waste materials that
may potentially be contaminated with PPs. Many of these activities are industrial activities where
process sludge is produced. However, huge quantities of PP contaminated sludge are also produced
specifically as a result of wastewater treatment, including the treatment of combined municipal
wastewater as well as industrial wastewater, greywater, and stormwater. Generally speaking, sludge
treatment has been designed primarily to reduce the volume, odour and pathogenic risk associated
with sludge handling and disposal/reuse but the reduction of key inorganic and organic
micropollutants is increasingly becoming an area of concern. This development has largely been
driven by scepticism regarding the sustainability of large-scale agricultural land application practices,
particularly given the increasing quantities of sewage sludge being generated as a direct result of
increasingly stringent water quality regulations.
Many of the PPs listed under the WFD have been or are likely to be included in future guideline limits
for sludge quality measures to control disposal pathways. Aside from the major disposal pathways
such as sea dumping (now banned throughout Europe but previously widely practiced), land spreading
and agricultural reuse, incineration, and landfilling (increasingly discouraged) there are also numerous
potential reuse options whereby sludge may be valorised and/or incorporated in useful products.
Examples include the use of sewage sludge in the production of Portland cement and other building
materials, and the reclamation of valuable constituents (e.g. metals from electroplating sludge for use
in non-ferrous metals refining) and/or reuse of sludge produced as a by-product of industry (e.g. reuse
of wool scour sludge in the brick making industry).
From a sustainability perspective it is clear that reuse/recycling of sludge products should be practiced
as far as is possible and practicable, although care needs to be taken to ensure that reuse is indeed
beneficial and does not result in environmental degradation. The agricultural reuse and land
application pathway remains of key concern in this respect. The human food chain and wider
environment must be afforded adequate protection, and it appears that further research is needed to
ensure that this is the case under current practices. Many EU member states are sceptical of the
sustainability of the agricultural reuse pathway and permissible contaminant limits are tending to be
lowered as a result. This is likely to further encourage the development of new sludge treatment
techniques capable of lowering sludge PP contents and/or the refinement of existing techniques to
further improve their PP removal efficiencies.
115
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Production, treatment and disposal of

priority pollutant contaminated sludge.

Erica Donner1, Kemi Seriki2, Mike Revitt1.

Urban Pollution Research Centre, Middlesex University, UK.

Source Control Options for Reducing Emissions of Priority Pollutants (ScorePP)

Duration: 1 October 2006 31 March 2010

D5.5 Production, treatment and disposal of PP contaminated sludge

Production, treatment and disposal of priority pollutant

Erica Donner, Kemi Seriki, Mike Revitt

Review and assessment

Luis Castillo, Anjou Recherche

Date submitted to project coordinator:

Approved by Work package leader:

Approved by Project Coordinator:

D5.5 Production, treatment and disposal of PP contaminated sludge

Section A Municipal wastewater treatment sludge

2. The production of municipal sewage sludge

3. Sludge treatment and disposal options

3.1 Overview of sludge treatment and disposal options

4.1 Literature data

4.2 Case city monitoring data

5. Treatment of PP contaminated sewage sludge

Section B: Industrial Sludge Production and Treatment

2.Sludge production and management in key European industrial sectors

2.1 Cement and Lime Manufacturing Industries

2.2 Ceramic Manufacturing Industry

2.3 Chlor-alkali manufacturing industry

2.4 Industrial cooling systems

2.5 Ferrous Metals Processing Industry

2.6 Non-ferrous metals industry

2.7 Food, drink and milk industries

2.8 Storage activities

2.9 Glass manufacturing industry

2.10 Intensive rearing of poultry and pigs

2.11 Large combustion plants

2.12 Pulp and paper industry

2.13 The tanning of hides and skins

2.14 The production of polymers

2.15 Surface treatment using organic solvents

2.16 Surface treatment of metals and plastics

2.17 Waste incineration

2.18 Large volume organic chemical industry

D5.5 Production, treatment and disposal of PP contaminated sludge

2.20 Manufacture of organic fine chemicals

2.22 Production of specialty inorganic chemicals.

2.23 Management of tailings and waste-rock in mining activities

2.24 Mineral oil and gas refineries

2.25 Textiles industry

2.26 Slaughterhouses and animal by-products industries

Section C Greywater treatment sludge

1.Stormwater Best Management Practices as sources of PP contaminated sludge and sediments

D5.5 Production, treatment and disposal of PP contaminated sludge

Overview and general introduction

the likelihood of PP contaminated sludges being produced

the compositional characteristics of such sludges and extent of PP contamination

potential sludge treatment and disposal/reuse options

the applicability of such options.

D5.5 Production, treatment and disposal of PP contaminated sludge

Section A Municipal wastewater treatment sludge

2. The production of municipal sewage sludge

D5.5 Production, treatment and disposal of PP contaminated sludge

3. Sludge treatment and disposal options