General aspects of industrial waste

water

Maria Fürhacker

Universität für Bodenkultur Wien

April 2014
Content

• Industrial sectors in Peru

• Problems of industrial wastewater
• Negative effects
• Risk assessment
• Cases of lead and mercury

• Conclusions

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Peruvian industry

• Large numbers of poultry, cattle, sheep, llamas,

alpacas and guinea pigs
• Fishing industry
• Logging is also an important economic activity.
• Mining industry: copper, silver, gold, iron ore,
coal, and phosphate rock
• Petroleum and gas
• Manufacture of steel and other metals, textiles,
and clothing.
• Peru: Economy | Infoplease.com http://www.infoplease.com/encyclopedia/world/peru-country-
south-america-economy.html#ixzz2vvvSMZzU
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Top 10 export commodities 2009
to 2011

• Mining products
• Agricultural products
http://data.un.org/CountryProfile.aspx?crName=PERU
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Industrial wastewater - definition

• The water or liquid carried waste

from an industrial process
• The term includes contaminated
storm water and leachate from solid
waste facilities
• Waste material (solid, gas or liquid)
generated by a commercial,
industrial or nonresidential activity

These wastes may result from any process or activity of industry, manufacture,
trade or business, from the development of any natural resource, or from
animal operations such as feedlots, poultry houses, or dairies

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Contaminants in industrial WW
• Conventional pollutants can include
– Organic pollution: COD, TOC, BOD
– Nutrients: nitrogen, phosphorous
– Total suspended solids
– pH (acid or alkaline equivalents)
– Fats, oil and grease (FOG)
• Toxic pollutants can include
– Metals (arsenic, cadmium, chromium, copper, lead, mercury, nickel,
silver, zinc)
– Toxic organics (e.g.)
• Solvents (1,1,1-trichloroethane, benzene, ethylbenzene, methylene chloride,
toluene, and trichloroethylene)
• Semi-volatile organics (di-n-butyl phthalate, naphthalene, p-chloro-m-cresol,
and phenols)
• Pesticides
• Hygienic pollutants can include
– Fecal coliforms
– All types of pathogens e.g. viruses, parasites, bacteria

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Problems of industrial emissions

depend on the dedicated use or disposal of the

wastewater

Required treatment

Human health environmental

health

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Acute impacts of wastewater on
surface water
spills, releases, deposition
and/or runoff events

Oxygen depletion and toxicity

Example: high concentrations of organic matter or

ammonia may cause:
• Rapid increase Biochemical Oxygen Demand (BOD)
• Fish kills
• Disrupts aquatic ecosystem balance

• Contamination with pathogens

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Chronic impacts of wastewater
on surface water
long-term loadings due to
erosion, runoff, etc.

Eutrophication due to long-term phosphorus and nitrogen loading

• cause algal blooms
• reduce water clarity
• lead to increased BOD
• lead to fish stress and fish kills
• reduce biodiversity
• increase rooted plant growth

• toxins of cyanobacteria
http://chemistry.tutorvista.com/biochemistry/eutrophication.html

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Pathogens and emerging
pathogens
Improved methods of surveillance,
epidemiological studies and the In 2001, a review of the scientific
continuous development of more
literature identified
advanced methods of diagnosis have
allowed to detect new pathogenic species 1415 species of infectious organisms known
of micro-organism or to associate a to be pathogenic to humans, including
known micro-organism with a new or 217 viruses and prions,
atypical set of disease symptoms. 538 bacteria and rickettsiae,
307 fungi,
66 protozoa and
Photo: HDA Lindquist, USEPA
287 helminths.
Of these, 61% were zoonotic and
12% were associated with
diseases considered to be
emerging (Taylor, Latham &
Woolhouse, 2001).
Cryptosporidium and Giardia

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Micropollutants and emerging
chemicals and effects

Pesticides Hormons

Industrial
chemicals Endocrine Drugs
effects

Metals Personal care

products

cyto- geno- immuno neuro- organo-

mutagenicity -toxicity
toxicity toxicity toxicity toxicity

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 Basic approaches for standard
setting
Risk assessment (RA)
Predicted Predicted no
environmental effect conc. Precautionary principle (PP)
concentration
(PNEC) Drinking water
(PEC)
DW-value for pesticides and
metabolites (DWD, 1998)
0.1 µg/l

European Medicines Agency

Groundwater EMEA, 2006
PEC/PNEC > 1 GWvalue 0.01 µg/l
0.01 µg/l

In case the knowledge for RA is not available at a

proper time, no action is taken.
Take action PP acts in advance // RA is lacking behind
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 STEPS IN TOXICOLOGICAL RISK
Scientific Level ASSESSMENT
1. Exposure assessment
chemical analysis, model calculation

2. Hazard assessment
- identification of effect / type of disease (qualitative)
- dose-response relationship (quantitative, threshold)
3. Risk assessment
risk= propability of manifestion of disease as well as
type and size of affected population (man)
or environmental compartment, resp.
interconnection of exposure and effect

Sociopolitical Level
Risk-Benefit-Analysis
Risk Management
Risk Communication
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EU-Guidelines

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Case of metals - dose response relationship
– essential metals
Essential Non-essential

Cr, Co, Cu, Fe, Mn, Mo, Ni, Se, Zn As, Sb, Cd, Pb, Hg, Tl, Ag, Sn

death Dose-Response death

Increasing adverse

irreversible Relationships irreversible

effects effects
response

reversible effects

homoestasis

Increasing dose
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Case of metals
Essential
Cr, Co, Cu, Fe, Mn, Mo, Ni, Se, Zn
Member States may, take into
account:
• (a) natural background
concentrations for metals and
their compounds, and
• (b) hardness, pH or other
water quality parameters that
affect the bioavailability of
metals.
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Non-essential
As, Sb, Cd, Pb, Hg, Tl, Ag, Sn
 In a TRA (total risk approach), no
explicit account is taken of natural
background levels; this approach
accounts for the total dissolved amount
of a metal in a waterbody.
 The added risk approach accounts for
natural background concentrations and
avoids setting regulatory standards
below this background level in a simple
manner: a maximum permissible
addition (MPA) to the background level
of a certain metal is calculated.
- Case of metal mining
Regulated but especially unregulated mining has the potential to release
harmful substances into the soil, air, and water.

• Oxidation of sulfidic ores but also in-situ-

leaching cause acidification
• Release of radioactive elements, asbestos-like
minerals, and metallic dust
• Toxic concentrations of heavy metals: gold ores
often contain other metals, including iron,
copper, zinc, nickel and silver as well as other
elements such as arsenic or lead.
• Mercury releases when used as an
amalgamating agent
• Cyanide spills can cause significant wildlife
mortality
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Solubility of metals

• Depend on pH
• ORP
• Complex forming agents

• complexed form - break up and

transform to "free" form amenable to
chemical precipitation

• Examples of complexing molecules

are ammonia, citrates, and ethylene
diamine tetra acetic acid (EDTA).

Solubility of Metal Hydroxides and Sulfides as a Function of

pH. (Source: EPA publication, EPA-600/2-82-011C, 1981)
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 General Principles of Metal Toxicity
 The most prominent property of heavy metals is their potential
to form complexes with functional groups of cellular molecules:
R-SH R-OH R1-NH2 R1-NH-R2

 Displacement of essential, regulatory metal ions

Ca2+, Mg2+ and Zn2+ of their complexes

 ROS (reactive oxygen species) formation, catalyzed by Fe,

Cr, Cu, V (redox cycling) (superoxide anion radical and
hydroxyl radicals)
 Binding and decrease of glutathion and protein-SH
(e.g. Cd, Hg, Ni, Pb) with the consequence of ROS-formation

 Disturbance of signaling pathways and inhibition of DNA-repair

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General Principles of Metal Toxicity

 Toxic effects are highly variable

 Neurotoxicity (e.g. Pb2+, Hg0 )

 Kidney toxicity (e.g. Hg2+ )
 Carcinogenicity (e.g. As3+ )

 Metals in organic bonding (e.g. methylmercury)

altered toxicokinetic properties: increased
lipophilicity
 toxicity in else “protected” organs: CNS

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Cases Pb and Hg

local to global issue

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 Lead (Pb)

 Soft blue-gray metal

 Found in the
natural environment
 Was added to paint
and gasoline in past
 Still used in consumer products
e.g. automotive batteries
 Water pipes and tightenings
 Lead-containing pipes
 Brass faucets
 Solder

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Biological effects

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 Biological effects
No known threshold for effects of lead
Affects all organ systems
Developmental neurologic effects of
greatest concern

Research has shown that blood lead levels below

those considered safe by the World Health
Organization (WHO) in 2004 (<10 µg/dl) can cause
significant cognitive and intellectual impairment in
children. (*)
The Centers for Disease Control (US) has set the
standard elevated blood lead level for adults to be
10 (µg/dl) of the whole blood. For children the
number is set much lower at 5 (µg/dl) of blood as of
2012

April 2014 (*) Tong et al., 2000

Pb standards in water

WHO GDWQ (2011) and WFD (2012)

Drinking water EU (1998)  AA-EQS: 7.2 µg/L Pb
• 10 µg/L Pb  MAC-EQS: not applicable

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Mercury

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 Mercury
Mercury is a naturally-occurring element in soil and rocks
and also exists in lakes, streams and oceans.

Mercury exists in three forms:

Hg0 (1) elemental mercury,
Hg++ (2) inorganic mercury
compounds (primarily in the aquatic environment,
mercuric chloride),
CH3Hg (3) organic mercury compounds
(primarily methyl mercury). in fish

All forms of mercury are quite

toxic, and each form exhibits
different health effects.

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Geochemical circuit of mercury-
compounds (Fent, 1998)

volatilization volatilization
input output

bacteria
bacteria

algae ground-
water
bacteria

* organic carbon

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Global Transport of gaseous elemental
mercury

Global Mercury Assessment 2013

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 Relative contributions to estimated
emissions to air from anthropogenic
sources in 2010

Global Mercury Assessment 2013

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Global distribution of anthropogenic
mercury emissions to air in 2010.

Global Mercury Assessment 2013

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 Mercury: toxikokinetics
primary target organs: kidney, central nerve system
excretion: feaces, urine, saliva,
sweat, expir. air
Half-life:
metallic Hg ca 60 days
in CNS 1 to 18 years
bivalent Hg ca 40 days
Methylmercury ca. 50 days

methylmercury has a half-life of about 72 days in aquatic organisms

bioaccumulation
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 Teratogenicity of methylmercury
Mouse: 15-days embryo Exposure to methylmercury for: day 10-13

18 day embryo:
malformation of
lips and palate
control methylmercury
growth deficit
exencephalie
encephalocele

Effects of methylmercury on prenatal development in mice.

Spyker,-J-M; Smithberg,-M; Teratology 5, 181-190, (1972)

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 Mercury: limit values
WHO GDWQ (2011): 6 µg/L based on inorganic Hg

FOOD
The EFSA Panel established a TWI (tolerable
weekly intake) for methylmercury of 1.3 µg/kg
b.w., expressed as mercury in 2012.
Surface water
WFD 2008/105/EC: Hg and compounds : 0.07 µg/L MAC-EQS and
20 µg/kg wet weight in biota

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 Mercury (Haskoning, 2002)

The production, storage and sale or supply of pesticides containing mercury

was banned in 1992. The following applications of mercury based compounds have
been addressed:
 use in paints, cosmetics, agriculture

Council directive 89/677/EEC regulates the following applications of mercury

compounds:
 marine anti-fouling paints;
 wood preservation;
 textile treatment;
 industrial wastewater treatment.
Contaminants:
• Mercury is a contaminant in fertilisers (originating from phosphate rocks and
sulphuric acid), lime and sewage sludge.
• Fossil fuel combustion and industrial production involving the use of raw
materials containing mercury (ex. zinc and copper production). [Bjornstad &
Havenstrom, 1992]
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How to assess the
ecotoxicological risk?
WFD: Assessing the impacts of pressures on water
bodies in terms of ecological and chemical impacts

Biomarkers,bioassays,bioindicators

Biological parameters have been proposed to

complement the information given by chemical
analyses.
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Sampling
Determine the goal – select criteria for a comparison
• aqueous or solid samples (filtered or total)
• time and location - contaminated site, background
• extrapolate with care - to include the whole area under
investigation
• indicate - maximum, minimum and average values for
process control or environmental criteria (include mass
flow)

The results of analysis can be no better than the

sample on which it was performed.

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In-situ biological monitoring

Surveys are carried out to investigate the aquatic

ecological status in addition to the water chemistry.

Surface water flora and macroinvertebrate fauna

• Selected plant and macroinvertebrate species may be
utilised as indicators of the surface water quality (existence
and/or lack of existence).
Fisheries, fish population and spawning
• A fish stock assessment in representative sections of the
main watercourses within the survey area is part of this
section.

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Water Status

• Surface water status assessed • Groundwater status assessed

using: using:
Ecological status Quantitative aspects

Chemical status Chemical aspects

Priority substances (PS) and
priority hazardous substances (PHS) Nitrate, ..

• Objective is “good surface water / groundwater status”

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Conclusions

• Emissions from industry - but also other sources

- cause environmental pollution threatning
human and environmental health
• A holisitc approach needs
- health based targets
- measures based on these objectives
- key points and audit procedures
- Define analytical verification (including health status)

April 2014
Thank you for your attention

maria.fuerhacker@boku.ac.at
www.boku.ac.at

April 2014