Professional Documents
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14
KH-40-01-448-EN-N
Pollutants in urban waste
water and sewage sludge
ISBN 92-894-1735-8
OFFICE FOR OFFICIAL PUBLICATIONS
OF THE EUROPEAN COMMUNITIES
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ISBN 92-894-1735-8
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1
Executive Summary
Authors
(scientific co-ordinator)
Dr David Butler
Paul Docx
Martin Hession
Christos Makropoulos
Madeleine McMullen
Dr Mark Nieuwenhuijsen
Adrienne Pitman
Dr Radu Rautiu
Richard Sawyer
Dr Steve Smith
Dr David White
Stefania Paris
IRSA Rome
Dr Dario Marani
Dr Camilla Braguglia
ECA Barcelona
Dr Juan Palerm
Table of Contents
EXECUTIVE SUMMARY 5
1. INTRODUCTION 9
APPENDICES 232
APPENDIX A - URBAN WASTEWATER TREATMENT SYSTEMS (WWTS) AND SEWAGE SLUDGE
TREATMENT (SST) - EU AND REGIONAL ASPECTS
APPENDIX B - PHYSICO-CHEMICAL PROPERTIES OF SELECTED POLLUTANTS
DATABASES, REFERENCES
EXECUTIVE SUMMARY
Water policy in the European Union is aiming to promote sustainable water use and a major
objective of the new Water Framework Directive (2000/60/EC) is the long-term progressive
reduction of contaminant discharges to the aquatic environment in urban wastewater
(UWW). Sewage sludge is also a product of wastewater treatment and the Urban Waste
Water Treatment Directive (91/271/EEC) aims to encourage the use of sludge whenever
appropriate. Potentially toxic elements and hydrophobic organic contaminants largely
transfer to the sewage sludge during waste water treatment with potential implications for the
use of sludge although some may be emitted with the effluent water.
Inputs of metals and organic contaminants to the urban wastewater system (WWTS) occur
from three generic sources: domestic, commercial and urban runoff. A review of available
literature has quantified the extent and importance of these various sources and the inputs
from different sectors. In general, urban runoff is not a major contributor of potentially toxic
elements to UWW. Inputs from paved surfaces due to vehicle road abrasion and tyre and
brake-lining wear have been identified and losses from Pb painted surfaces and Pb and Zn
from roofing materials represent localised sources of these elements.
Platinum and Pd are components of vehicle catalytic converters and emissions occur as the
autocatalyst deteriorates. Catalytic converters are the main source of these metals emitted
to the environment and releases have increased with the expansion in use of autocatalysts.
Platinum group metals (PGMs) potentially enter UWW in runoff and transfer to sewage
sludge in a similar way to other potentially toxic elements. The Pt content in sludge is
typically in the range 0.1 – 0.3 mg kg-1 (ds) and the background value for soil is 1 µg kg-1.
PGMs are inactive and immobile in soil.
In contrast to potentially toxic elements, inputs of the main persistent organic pollutants of
concern, including: PAHs, PCBs and PCDD/Fs, to UWW are principally from atmospheric
deposition onto paved surfaces and runoff. Combustion from traffic and commercial sources
accounts for the major PAH release to the environment, although inputs from food
preparation sources also represent an important and often under-estimated contribution of
certain PAH congeners. PCDD/Fs are released during waste incineration and also by coal
combustion. Soil acts as a long-term repository for these contaminant types and
remobilisation by volatilisation from soil is an important mechanism responsible for recycling
and redistributing them in the environment. For example, the industrial use of PCBs was
phased out in Europe during the 1980s-1990s, but 90 % of the contemporary emissions of
PCBs are volatilised from soil. Since emission controls are already in place for the main
point sources and PAHs, PCDD/Fs or PCBs enter UWW principally from diffuse atmospheric
deposition and environmental cycling, there is probably little scope, from source control, to
further reduce inputs and concentrations of these persistent organic substances in UWW or
sewage sludge.
Being strongly hydrophobic these organic pollutants are efficiently removed during urban
wastewater treatment (WWTS) and bind to the sludge solids. However, the increasing body
of scientific evidence has not identified a potential harmful impact of these substances on the
environment in the context of the urban wastewater system. Therefore, on balance, the
importance of these contaminants in UWW and sewage sludge has significantly diminished
and there may be little practical or environmental benefit gained from adopting limits or
controls for PAHs, PCBs or PCDD/Fs in UWW or sewage sludge. This is emphasised further
by the high cost and specialist analytical requirements of quantifying these compounds in
sludge and effluent.
5
Executive Summary
Potentially toxic element contamination of urban wastewater and sewage sludge is usually
attributed to discharges from major commercial premises. However, significant progress has
occurred in eliminating these sources and this is reflected in the significant reductions in
potentially toxic element concentration in sewage sludge and surface waters reported in all
European countries where temporal data on sludge and water quality have been collected.
However, potentially toxic element concentrations remain higher in sludge from large urban
wastewater treatment plant (WWTP) compared with small WWTP and they are also greater
in sludges from industrial catchments compared with rural locations. These patterns in
sludge metal content suggest that commercial sources may still contribute significantly to the
total metal load entering UWW. Indeed, recent regional surveys of metal emissions from
commercial premises confirm that further reductions in most elements could be achieved
from this sector. The primary targets for source control include health establishments, small
manufacturing industries (particularly metal and vehicle related activities) and hotel/catering
enterprises, as 30 % of medical centres and 20 % of the other types of activity could be
discharging significant amounts of potentially toxic elements in UWW. Mercury is a specific
case where compulsory use of dental amalgam separators, and substituting Hg with
alternative thermoreactive materials in thermometers, may be effective in reducing
discharges of this element to the WWTS wastewater treatment system .
Faeces contribute 60 – 70 % of the load of Cd, Zn, Cu and Ni in domestic wastewater and
>20 % of the input of these elements in mixed wastewater from domestic and industrial
premises. Faecal matter typically contains 250 mg Zn kg-1, 70 mg Cu kg-1, 5 mg Ni kg-1, 2 mg
Cd kg-1 and 10 mg Pb kg-1 (ds). The other principal sources of metals in domestic
wastewater are body care products, pharmaceuticals, cleaning products and liquid wastes.
Plumbing is the main source of Cu in hard water areas, contributing >50 % of the Cu load
and Pb inputs equivalent to 25 % of the total load of this element have been reported in
districts with extensive networks of Pb pipework for water conveyance. Adjusting water
hardness in order to reduce metal solubilisation from plumbing is technically feasible, but is
likely to be impractical at the regional scale necessary to significantly reduce metal
concentrations in UWW and sludge and may be unpopular with consumers in hard water
areas. The gradual replacement of Pb water pipes can be achieved during building renewal
and renovation programmes.
Detergent residues (e.g.nonyl phenol, NP), surfactants (e.g. linear alkyl benzene
sulphonates, LAS), plasticising agents (e.g. di-(2-ethylhexyl)phthalate, DEHP) and
polyacrylamide compounds, added to sludge to aid dewatering, are quantitatively amongst
the most abundant organic contaminants present in UWW and/or sewage sludge.
Dewatering agents based on polyacrylamide may contain traces of the potentially toxic
acrylamide monomer, but this is rapidly degraded and polyacrylamide itself is biologically
inactive. Detergent residues and DEHP are primarily of domestic origin and they are
effectively degraded during aerobic wastewater treatment and are not considered to
represent a potential environmental problem from the discharge of treated effluents to
surface waters. Anaerobic digestion is the principal method employed for stabilising sewage
sludge, but NP accumulates during anaerobic digestion, DEHP is not removed by this
conventional process and, although a significant amount of LAS is biodegraded, residues of
this substance remain because of the large concentrations initially present in raw sludge.
The inability to degrade detergent residues anaerobically and the large concentrations
present in sludge and UWW have prompted ecolabelling initiatives in a number of European
countries to influence consumer choice away from detergents containing these surfactants to
alternative products. This has been successful when supported by extensive public
awareness campaigning. For example, the market share for ecolabelled detergents in
Sweden increased to 95 % and the consumption of LAS has decreased to a similar extent.
Surfactant residues and plasticisers degrade quickly when added to aerobic soils. The
oestrogenic activity of NP is however, a principal concern and measures are proposed to
eliminate the discharge of this substance to UWW.
Natural and synthetic oestrogens are degraded in WWT, but trace amounts remain and
represent the main source of oestrogenic activity in treated effluents. Further work is
necessary to link these substances to oestrogenic responses in aquatic life, but it may be
necessary in future to consider the requirement for tertiary treatment processes (e.g.
ozonation) to eliminate these substances from treated effluents.
A number of other groups of organic compound are identified as being potentially resistant to
wastewater and sewage sludge treatment and the most significant of these are brominated
diphenyl ethers (PBDEs) and chlorinated paraffins. Further research is warranted, in
particular to assess the persistence and potential environmental significance of these
compounds. Synthetic nitro musks are used in perfumed products and traces may be
present in UWW and sludge. Little is known about the environmental fate of these
compounds, but effects on human health from this route seem unlikely given that the main
exposure route is through direct contact.
A general recommendation to protect the water and soil environment is that a hazard,
biodegradability and fate assessment should be required for all new synthetic chemicals,
irrespective of their purpose or end-use, to determine the potential from them to transfer to
UWW or sewage sludge and the subsequent implications for the environment. Specified
criteria regarding toxicity and biodegradation could be set for compounds that exhibit a
propensity to enter the WWTS and restrictions could be enforced regarding production and
use if these were not met. These decisions would need to balanced against the potential
benefits to health derived from the administration of pharmaceutical drugs.
Strategies aimed at controlling pollutant discharges can only focus on those sources that can
be identified and quantified. Published mass balance calculations indicate there is a high
degree of uncertainty regarding inputs of potentially toxic elements entering the WWTS.
Indeed, unidentified sources may contribute as much as 30 - 60 % of the total metal load
entering the WWTS, although more than 80 % of the Cd discharged is from identified inputs.
This apparent discrepancy could be related to difficulties in measuring the highly variable
inputs of metals in urban runoff and the underestimation of discharges from commercial
premises that have not been subjected to trade effluent control.
The European Commission has proposed a list of 32 priority and 11 hazardous substances
(COM/2001/17) with the aim of progressively reducing emissions and discharges of these
chemicals to the environment. Current developments also suggest that Zn, Cu and LAS may
be the most limiting constituents in sludge if the proposed maximum permissible
concentrations for these substances in soil (Zn and Cu) and sludge (LAS) are carried
through in the revised of Directive 86/278/EEC, but they are not listed as priority substances.
Consideration should be given to designating Zn, Cu and LAS as priority substances to
minimise their to UWW as far as is practicable and to ensure there is a consistent link and
approach to defining the environmental quality standards for sludge with those for
sustainable water use and contaminant discharge reduction.
The main identified priorities for future research relating to contaminant sources, fate and
behaviour in the WWTS are:
• To establish the extent and variability of contaminant entry into UWW by catchment
investigations in relation to precipitation frequency and changes in sludge quality;
• To critically and independently review the fate, behaviour, degradability, toxicity and
environmental consequences of alternative surfactant and plasticing compounds, in
collaboration with the related chemical manufacturing industries, to inform decisions of
the benefits and disadvantages of product substitution in detergent formulations and
plastics manufacture;
1. INTRODUCTION
The primary objective of this study is to determine the sources of pollution in urban
wastewater (UWW) treated in wastewater treatment systems (WWTS). This includes the
pollutants introduced into the UWW collecting system with run-off rainwater, from domestic
and small commercial sources. The pollutant contents in urban wastewater and sewage
sludge has been evaluated by review of the existing literature, in order that measures may
be proposed to reduce pollution at source.
• potentially toxic elements (PTEs) including cadmium (Cd), chromium (Cr III and Cr
VI), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn),
• organic pollutants including PAHs, PCBs, DEHP, LAS, NPE, dioxins (PCDD) and
furans (PCDF). Over 6,000 organic compounds have been detected in raw water
sources most of which are due to human activities. While some of these are highly
persistent, others are easily biodegradable in WWTS.
Other pollutants of interest are the metalloids, arsenic and selenium and the metal silver.
Platinum group metals (PGMs), and pharmaceuticals are covered in detail in case studies.
The sources of metal pollution in the wastewater system can be classified into three main
categories:
• Domestic,
• Light industrial (connected to the WWTS) and commercial,
• Urban runoff (which also encompass lithospheric and atmospheric sources).
Lithosphere
INDUSTRY
products
WASTEWATER
TREATMENT WORKS
Receiving
Water
A summary of the various inputs, outputs and pathways followed by water and associated
contaminants from both natural and anthropogenic sources encountered in urban
environments is shown in Figure 1.1. It depicts the drainage area as an open system [Ellis,
1986]. A more detailed urban catchment figure is included in Appendix A.
Wastewater contains many constituents and impurities arising from diffuse and point
sources. Large point sources are easily quantifiable and result from specific activities in the
area that are connected to UWW collecting systems. The contribution from small point
sources, such as households and small businesses, is much more difficult to identify and
quantify, compared to point sources which are usually regulated. UWW is also vulnerable to
illegal discharges of pollutants.
Diffuse sources, such as atmospheric deposition and road runoff have also been
characterised and this study will attempt to present an overview of the available information
in this area. Different methods have been used to estimate point sources and diffuse (non-
point) sources contributions to the pollution load [Vink, 1999]. Inventories of point and diffuse
sources, can link observed water quality trends to changes in socio-economic activities.
The type of pollutants and the magnitude of the outfall loadings are a complex function of:
A review of the sources and pathways of potentially toxic element pollutants in urban
wastewater is presented in Section 2.1 and for organic pollutants in Section 3.1
This report presents a thorough literature review and is primarily based on the analysis and
presentation of case studies from a wide variety of sources and test catchments across
Europe, covering a time range from 1975 to date. Databases used during this project are
listed in the reference section. As theoretical approaches, such as modelling of pollutant
sources and predicted concentrations, are scarce the report attempts to summarise the
monitoring, sampling and measurement of numerous studies, thus providing a concise
overview of pollution source types and concentration ranges. The reader must keep in mind
that there are significant differences between the experiments (in duration, location,
measurement methods, measurement targets and initial conditions), and thus conclusions
on mean or extreme values of pollutants will have to be drawn carefully.
The aim is to reduce inputs of pollutants entering the wastewater system to background
levels because this represents the minimum potential extent of contamination that can be
achieved. Potentially toxic elements are of concern because of their potential for long-term
accumulation in soils and sediments.
The majority of metals transfer to sewage sludge (see Fig 2.1). However, 20% may be lost in
the treated effluent, depending on the solubility and this may be as high as 40% - 60% for
the most soluble metal, Ni. Although the use of sludge on agricultural land is largely dictated
by nutrient content (nitrogen and phosphorus), the accumulation of potentially toxic elements
in sewage sludge is an important aspect of sludge quality, which should be considered in
terms of the long-term sustainable use sludge on land. Application of sludge to agricultural
land is the largest outlet for its beneficial use and this is consistent with EC policy of waste
recycling, recovery and use. This is a critical issue due to the increasing amount of sludge
produced, the increasingly stringent controls on landfilling, the public opposition to
incineration (a potential source of further atmospheric pollution), and the ban on disposal at
sea. Consequently sludge quality must be protected and improved in order to secure the
agricultural outlet as the most cost effective and sustainable option.
Figure 2.1: Origin and fate of metals during treatment of wastewater [from ADEME,
1995]
Pb 0.1 ≤ 13
Cu 0.2 0.04-26
Zn 0.1-1.0 0.03-133
Cd <0.03 0.003-1.3
Cr 0.03 ≤20
Ni 0.04 ≤7.3
Cd distribution Cu distribution
Domestic Domestic
Storm events Storm events
Commercial Commercial
Non Identified
Non Identified
Cr distribution Hg distribution
Domestic Domestic
Storm events Storm events
Commercial Commercial
Non Identified
Non Identified
Pb distribution Ni distribution
Domestic Domestic
Storm events Storm events
Commercial Commercial
Non Identified
Non Identified
Zn distribution
Domestic
Storm events
Commercial
Non Identified
Figure 2.2 Pie charts showing the breakdown of potentially toxic elements entering
UWW from different sources in France (ADEME 1995) This uses the French data in Table
2.2 but is included to give a clearer visual representation of the source breakdown for the
different metals.
The data in Table 2.2 and Figure 2.2 show that for some elements over 50% of the
potentially toxic elements in wastewater are unaccounted for. This is in line with findings by
Critchley & Agy [1994] Better source inventory data is essential in order to effectively target
reductions in emissions from all the different sources. It may be that identification of some of
the industrial sources will require increased trade effluent discharge controls if
concentrations of pollutants are to be reduced. Domestic and urban run-off sources may
require different types of action, such as changes in products used.
Emissions of potentially toxic elements from industrial point sources were the major sources
of pollution to urban wastewater. However, stringent and more widespread limits applied to
industrial users has reduced the levels of potentially toxic elements emitted by industry into
urban wastewater considerably. This continues a general decline of potentially toxic
elements from industrial sources since the 1960s, due to factors such as cleaner industrial
processes, trade effluent controls and heavy industry recession. For example, the liquids
used in metal finishing typically contain 3-5 mg.l-1 of copper, 5-10 mg.l-1 of chromium, 3-5
mg.l-1 of zinc, 5-10 mg.l-1 of zinc, 1-5 mg.l-1 of cyanide, and 10-50 mg.l-1 of suspended solids
[Barnes, 1987]. However, metal finishing industries are now required to pre-treat these
liquids before disposal, reducing toxic discharges by 80-90%.
In the Netherlands, a survey of potentially toxic element load in UWW influent [SPEED,
1993], also made estimations for 1995 and forecasts up to 2010. The overall prevalence of
potentially toxic elements in the UWW system is expected to decrease, mainly due to a
decrease in runoff and industrial sources, while the potentially toxic elements share in
WWTS loads from households was expected to increase. As industrial sources of potentially
toxic elements in UWW decline, the relevant importance of diffuse sources will increase.
Wiart and Reveillere [1995] carried out studies at the Achères WWTS in France. Their
studies showed a significant decrease (50-90%) in the potentially toxic element content of
sewage sludge since 1978, following the application of the "at-source discharge reduction"
policy [Bebin, 1997]. However, the main concern is now with organic pollutants, and current
regulations require monitoring of the influent, in order to set up a baseline database from
which limits may then be devised.
Domestic sources of potentially toxic elements in wastewater are rarely quantified due to the
difficulty in isolating them. Domestic sources include the potentially toxic elements
discharged from the household to UWW collecting systems and, in addition, corrosion from
materials used in distribution and plumbing networks, tap water and detergents.
A study by RIVM (Dutch Institute of Public Health and the Environment) in the Netherlands
[SPEED, 1993], quantified the waterborne emissions of potentially toxic elements from
household sources, dentistry and utility buildings in the urban environment. Table 2.3 shows
the data of waterborne potentially toxic elements emissions in tonnes per annum.
Domestic products containing potentially toxic elements used on a regular basis at home
and/or at work, are also reviewed by Lewis [1999]. The following lists the principal PTEs and
products containing them that may enter urban wastewater;
Copper: comes mainly from corrosion and leaching of plumbing, fungicides (cuprous
chloride), pigments, wood preservatives, larvicides (copper acetoarsenite) and antifouling
paints.
Mercury: most mercury compounds and uses are now banned or about to be banned,
however, mercury is still used in thermometers (in some EU countries) and dental
amalgams. Also, mercury can still be found as an additive in old paints for water proofing
and marine antifouling (mercuric arsenate), in old pesticides (mercuric chloride in fungicides,
insecticides), in wood preservatives (mercuric chloride), in embalming fluids (mercuric
chloride), in germicidal soaps and antibacterial products (mercuric chloride and mercuric
cyanide), as mercury-silver-tin alloys and for "silver mirrors".
Nickel: can be found in alloys used in food processing and sanitary installations; in
rechargeable batteries (Ni-Cd), and protective coatings.
Lead: The main source of lead is from old lead piping in the water distribution system. It can
be found in old paint pigments (as oxides, carbonates), solder, pool cue chalk (as
carbonate), in certain cosmetics, glazes on ceramic dishes and porcelain (it is banned now
for uses in glazes), also in "crystal glass". Lead has also been found in wines, possibly from
the lead-tin capsules used on bottles and from old wine processing installations.
Zinc: comes from corrosion and leaching of plumbing, water-proofing products (zinc
formate, zinc oxide), anti-pest products (zinc arsenate - in insecticides, zinc dithioamine as
fungicide, rat poison, rabbit and deer repellents, zinc fluorosilicate as anti-moth agent), wood
preservatives (as zinc arsenate), deodorants and cosmetics (as zinc chloride and zinc
oxide), medicines and ointments (zinc chloride and oxide as astringent and antiseptic, zinc
formate as antiseptic), paints and pigments (zinc oxide, zinc carbonate, zinc sulphide),
printing inks and artists paints (zinc oxide and carbonate), colouring agent in various
formulations (zinc oxide), a UV absorbent agent in various formulations (zinc oxide), "health
supplements" (as zinc ascorbate or zinc oxide).
Silver: originates mainly from small scale photography, household products such as
polishes, domestic water treatment devices, etc. [Shafer, et.al, 1998, Adams and Kramer,
1999]
Arsenic and Selenium: are among the potentially toxic metalloids found in urban
wastewaters. These are of importance due to their potential effects on human/animal health.
Only a limited number of studies have taken these into account. Arsenic inputs come from
natural background sources and from household products such as washing products,
medicines, garden products, wood preservatives, old paints and pigments. Selenium comes
from food products and food supplements, shampoos and other cosmetics, old paints and
pigments. Arsenic is present mainly as DMAA (dimethylarsinic acid) and as As (III) (arsenite)
in urban effluents and sewage sludge [Carbonell-Barrachina et.al., 2000].
Household products
Household products were investigated as potential sources of PTE pollution entering the
WWTS. Table 2.4 shows metal concentrations in various household products in UK
Table 2.4 Metal concentrations in household products
[Comber and Gunn, 1996, WRc report, 1994].
As can be seen from Table 2.4 there is a great deal of variability between products and also
between types of the same products in terms of potentially toxic element content.
The high variability of cadmium concentrations found in the big box washing powders can be
explained by the differences in the composition of phosphate ores used in their production.
Cadmium impurities in these phosphate ores have been shown to vary greatly depending on
mining source [Hutton et al reported in WRc report 1994]. Reducing the amount of
phosphate in washing powders, or choosing phosphate ores with low Cd concentration could
lead to a reduction in Cd in wastewater from diffuse sources. In Sweden the amount of
cadmium in sewage sludge was reduced from 2 mg kg-1 ds to 0.75 mg kg-1 ds [Ulmgren,
1999], and cadmium discharges from households in the Netherlands have been substantially
reduced due to the switch to phosphate-free detergents [SPEED, 1993]. The 'Ultra' washing
powders, usually phosphate-free, have smaller potentially toxic element contents than the
traditional powders, and are designed to be used in smaller quantities. A shift to these newer
products will reduce the overall metal load from this source.
The products with the highest metal contents are shown in bold in Table 2.4. The medicated
(anti-dandruff) shampoos contain zinc pyrithione and the high zinc concentrations will thus
raise the zinc inputs to the UWW collecting system. In 1991 these shampoos were estimated
to represent 26% of the market [*BLA Group 1991- reported in Comber and Gunn 1996 and
WRc 1994]. Cosmetics are not included here but they may also contain high levels of zinc
and several of these products are likely, at least in part, to enter in the waste water system.
One study in France [ADEME, 1995a] identified that the main sources of potentially toxic
elements in domestic wastewater came from cosmetic products, medicines, cleaning
products and liquid wastes (including paint), which were directly discharged from the
household sink.
Table 2.5 provides a general picture of some of the potentially toxic elements in various
domestic products including food products [after Lester, 1987 and WRc report 1994].
Sources for each metal are marked with a tick. In addition to the main metals considered in
this study, cadmium, chromium (III and VI), copper, mercury, nickel, lead and zinc, silver,
arsenic, selenium and cobalt are also included. Other metals and metalloids for which more
information is necessary include manganese, molybdenum, vanadium, antimony and tin.
Washing powders √ √ √
Wood- √ √ √
preservatives
Other sources
Faeces and Urine √ √ √ √ √ √ √ √ √
Tap Water √ √ √ √ √
Water treatment √ √ √ √ √
and heating
systems
Domestic activities
The main domestic sources of potentially toxic elements in wastewater were estimated by
WRc [1994] to be (in order of importance):
cadmium: faeces > bath water > laundry > tap water > kitchen
chromium: laundry > kitchen > faeces > bath water > tap water
copper: faeces > plumbing >tap water > laundry > kitchen
lead: plumbing > bath water > tap water > laundry > faeces > kitchen
nickel: faeces > bath water > laundry > tap water > kitchen
zinc: faeces > plumbing > tap water > laundry > kitchen.
Estimates of the mean potentially toxic element inputs to UWW collecting systems from
domestic activities are presented in Table 2.6. The results show that for the particular UK
(hard water) catchment studied in 1994, the domestic inputs of copper and zinc are major
contributors to the overall level of potentially toxic elements reaching the WWTS. Most of the
zinc is derived from faeces and household activities such as washing and cleaning.
Chromium, lead and cadmium were also found to be mainly from domestic activities rather
than from plumbing.
Table 2.6 Potentially toxic element loads to the UWW collecting systems from
domestic activities [adapted from Comber and Gunn, 1996]
Based on the above results, changes in population behaviour, such as a shift to dishwasher
use rather than washing up by hand, would reduce potentially toxic element input into the
WWTS.
It is noted that, while the quantities of potentially toxic elements dissolved in water from
plumbing will vary across the Europe they will make up a significant proportion of the
potentially toxic element loading going to any WWTS.
Table 2.7 summarises the percentages of the domestic inputs at the Shrewsbury WWTS, in
the UK. As can be seen over a fifth of the copper, zinc, cadmium and nickel entering the
wastewater treatment plant from domestic sources are from faeces. This emphasises the
fact that faeces are an important source of potentially toxic elements pollution. This source is
also very difficult to reduce. The percentage inputs of chromium and lead from this source
are much lower.
Table 2.7 Potentially toxic elements entering wastewater, breakdown by source [WRc,
1994]
Cu Zn Cd Ni Pb Cr
Percentages of total load
Break down of domestic sources as percentage of total metal entering WWTS
Plumbing Input Bathing 12.4 1.2 0.3 1.6 4.4 0.1
(% of total entering WWTS) Toilet 8.9 2.1 0.5 4.3 8.1 0.2
Washing 8.0 0.7 0.2 0.9 3.2 0.1
Machine
Miscellaneous 8.0 1.2 0.3 2.4 6.1 0.2
Dishwashing 7.1 0.6 0.2 0.8 2.7 0.1
Activities Faeces 20.6 28.0 20.0 23.6 3.1 2.1
(% of total metal entering Washing 9.53 10.8 4.6 4.4 18.6 9.3
WWTS) Machine
Bathing 0.2 2.6 0.9 0.8 1.1 0.3
Dishwashing 2.6 4.6 11.2 1.1 5.1
Human faeces contain high concentrations of potentially toxic elements from normal dietary
sources and this represents a principal input of metals to domestic wastewater and sludge of
domestic origin. The normal dietary contribution of metals represents the background metal
concentration represents the background metal concentration and is the minimum
achievable in waste water and sludge.
Concentrations are expected to vary with the intake of metals in the diet, drinking water and
medication and may also be influenced by the increasing prevalence of mineral
supplementation of food, for example with zinc, iron, selenium, and manganese. One study
in France (ADEME 1997) found the following concentrations of potentially toxic elements in
faeces (as dry matter): Zn: 250mg kg-1, Cu: 68mg kg-1, Pb: 11mg kg-1, Ni: 4.7mg kg-1, and
Cd: 2mg kg-1. Differences can also occur due to geographical variations in the dietary habits.
For some elements, such as Cd, the weighted average concentration in sludge (e.g. 3.3 mg
kg-1 in the UK) is typical of the amount originating naturally in faeces from the normal trace
amounts of this element ingested in food (typically 18.8 µg d-1). Other differences in reported
concentrations of Cd in different EU member states is discussed in section 2.3.
Studies in the USA [Isaac et.al, 1997], and Europe [WRc 1994] show that corrosion of the
distribution-plumbing-heating networks contribute major inputs of Pb, Cu and Zn. Lead
concentration for instance can vary between 14 µg.l-1 at the household input and 150 µg.l-1 at
the output.
It has been found that concentrations of copper in sewage sludge are directly proportional to
water hardness [Comber et al 1996]. Hard water (high pH) is potentially more aggressive to
copper and zinc plumbing, increasing leaching. However, the opposite is true for lead in that
it dissolves more readily in than soft, acidic water. The high lead levels in drinking water in
Scotland due to its soft waters are a major concern.
Reductions in the amounts of copper and lead in wastewater have been reported by pH
adjustment of tap water and addition of sodium silicate. The addition of alkali agents to water
at the treatment stage and the replacement of much lead piping has led to reductions in lead
concentration [Comber et al., 1996]. Adjusting the pH of tap water may be limited by
practical and economic factors.
Zinc in domestic plumbing comes from galvanised iron used in hot water tanks but is less
problematic than lead and copper because the amount decreases with the ageing of the
installations. Copper corrosion and dissolution is also greater in hot water than in cold water
supplies [Comber et al 1996]. The 'first draw' (initial flow of water in the morning) has higher
amounts of copper and lead compared to subsequent draws [Isaac et.al., 1997]. The Cu
content was found to be between 73.7 and 1430 µg l-1, and Pb content between 8.3 and
22.3 µg l-1, much greater than in the average effluent from households. Water treatment
would be recommended for certain water domestic uses, such as boilers and heating
systems, in order to reduce the metal corrosion.
The type of housing was also found to be important by the WRc report [1994]. Table 2.8
gives an average concentration of effluent from two types of estates, "1960s residential" and
"1990s residential" from daily bulk- and flow-weighted samples. The larger copper levels
from the "modern estate" can be explained by the newer plumbing system. In many
countries copper is the major element used in plumbing. In the UK it has been estimated that
leaching from copper plumbing accounts for over 80% of the copper entering domestic
wastewater [Comber et al 1996]. The higher lead level found in the newer housing did not
correlate with similar studies comparing old and new housing and could not be explained
satisfactorily; as in general older houses in the UK contain more lead plumbing. Lead from
solders in the piping system may also be an important source. In other regions of the EU
steel and zinc galvanised iron are used widely. This may explain why zinc in sludge is
proportionally greater than Cu in other member states compared with the UK.
Table 2.8 Mean concentration of potentially toxic elements in the effluent from
households in two types of residential areas [WRc Report, 1994]
Potentially toxic Zn Cu Ni Cd Pb Cr Hg
element concentration µg.l-1
" 1960s residential" 74.3 219.4 5.2 0.71 9.02 5.65 0.114
" 1990s residential" 147.0 458.3 7.56 0.34 90.61 3.3 0.088
In summary, potentially toxic elements entering UWW collecting systems from domestic
sources are related to:
Limited data is available for the potentially toxic element contribution from commercial
sources and health care inputs (such as hospital and clinical wastes). Inputs from artisanal
sources are looked at in more detail in a separate Case Study in Section 6.
Cadmium could originate from laundrettes, small electroplating and coating shops, plastic
manufacture, and also used in alloys, solders, pigments, enamels, paints, photography,
batteries, glazes, artisanal shops, engraving, and car repair shops. Data from ADEME
[1995], estimated that worldwide, 16000 tonnes of cadmium were consumed each year; 50-
60% of this in the manufacture of batteries and 20-25% in the production of coloured
pigments.
Chromium is present in alloys and is discharged from diffuse sources and products such as
preservatives, dying, and tanning activities. Chromium III is widely used as a tanning agent
in leather processing. Chromium VI uses are now restricted and there are few commercial
sources.
Copper is used in electronics, plating, paper, textile, rubber, fungicides, printing, plastic, and
brass and other alloy industries and it can also be emitted from various small commercial
activities and warehouses, as well as buildings with commercial heating systems.
Lead, as well as being used as a fuel additive (now greatly reduced or banned in the EU) it
is also used in batteries, pigments, solder, roofing, cable covering, lead jointed waste pipes
and PVC pipes (as an impurity), ammunition, chimney cases, fishing weights (in some
countries), yacht keels and other sources.
Mercury is used in the production of electrical equipment and is also used as a catalyst in
chlor-alkali processes for chlorine and caustic soda production. The main sources in effluent
are from dental practices, clinical thermometers, glass mirrors, electrical equipment and
traces in disinfectant products (bleach) and caustic soda solutions.
Zinc is used in galvanisation processes, brass and bronze alloy production, tyres, batteries,
paints, plastics, rubber, fungicides, paper, textiles, taxidermy (zinc chloride), embalming fluid
(zinc chloride), building materials and special cements (zinc oxide, zinc fluorosilicate),
dentistry (zinc oxide), and also in cosmetics and pharmaceuticals. The current trend towards
electrolytic production of zinc which, in contrast to thermally produced zinc, has virtually no
cadmium contamination. This means that cadmium pollution to UWW due to the corrosion of
galvanised steel will in time become negligible. [SPEED 1993].
Platinum and platinum group metals (PGMs) such as palladium and osmium can enter
UWW from medical and clinical uses, mainly as anti-neoplastic drugs. The amount in
hospital/clinical effluent has been estimated to be between 115 and 125 ng l-1 [Kümmerer
and Helmers, 1997, Kümmerer et.al., 1999] giving a total emission of 84-99 kg per annum
from hospitals in Germany. Other sources of platinum metals in the environment related to
commercial activities come from catalysts used in petroleum/ammonia processing and
wastewaters, from the small electronic shops, jewellery shops, laboratories and glass
manufacturing. Section 6 contains a detailed Case Study (a) on PGMs in urban waste water
and sewage sludge.
Silver could potentially be emitted from photographic and printing shops, from jewellery
manufacturers and repairers, plating and craft shops, glass mirror producers and small-
scale water filters.
Studies in Spain showed the presence of elevated concentrations of Cd, Cu, Hg, Pb and Zn
in urban wastewater and in the coastal environment [Castro, et.al., 1996], with large
concentrations of copper and zinc possibly due to the use of fungicides in glass-houses.
Table 2.9 Summary of potentially toxic elements in UWW from commercial sources
( g l-1)
Element Country Industry Industrial Effluent Reference
-1
(µg l )
Cd Germany All sectors 3-1,250 Wilderer et al 1997
Greece Petroleum industries 300-400 NTUA, 1985
Cu Germany All sectors 37-26,000 Wilderer et al 1997
Greece Metal and electrical industries 5,000-10,000 NTUA, 1985
Italy Artisanal galvanic shops 20,500 EBAV, 1996
Goldsmiths and jewellery 700-1,900
shops (max.13,300)
Cr Germany All sectors <10-20,100 Wilderer et al 1997
Greece Metal and electrical industries 500-13,000 NTUA, 1985
Tanneries 100-7,000,000
Italy Artisanal galvanic shops 16,000 EBAV, 1996
Pb Germany All sectors <50-13,400 Wilderer et al 1997
Greece Metal and electrical industries 500 NTUA, 1985
Italy Ceramics and photoceramics 6,000 EBAV, 1996
shops
Ni Germany All sectors <10-7,300 Wilderer et al 1997
Greece Metal and electrical industries 500-14,500 NTUA, 1985
Italy Artisanal galvanic shops 19,700 EBAV, 1996
Zn Germany All sectors 30-133,000 Wilderer et al 1997
Greece Metal and electrical industries 60-2,830 NTUA, 1985
Italy Goldsmiths and jewellery 1,000 (max. 7,000) EBAV, 1996
shops
As Spain Paper mills 3.4 Navarro, et.al
1993
In 1999, a project carried out by Anjou Recherche [LIFE, 1999], attempted to classify all
commercial sources of wastewater pollution based on a matrix of 73 main pollutants
including many potentially toxic elements and certain organic pollutants. The UWW
collecting system of Louviers, for example, had listed 1054 establishments of which 39%
were capable of emitting at least one of these pollutants. Ten classes of activities were
recorded, of which health and social action (33.5%), manufacturing industry (20%), hotels
and restaurants (17.8%), and collection services (10%) appeared most often as potential
polluters. It was found on average, that between a third and a half of the activities emitted
pollutants. In the Louviers area, it was found that 53 urban businesses and institutions could
potentially emit cadmium, 168 chromium, 147 copper, 35 nickel, 167 mercury, 50 lead, and
63 zinc. This suggests that more can be done to reduce trade effluent discharges.
Between 1990 and 1992, Stockholm Water Company investigated measures to reduce
discharges of potentially toxic elements into the UWW collecting system. This programme
involved the following groups: the city council, neighbouring municipalities, small businesses
and industry, professional associations and NGOs as well as local households. Efforts to
reduce pollution entering the wastewater system were divided among all the major sources
i.e., small businesses and industry, wastewater from urban runoff, household wastewater
and storm water.
Collaborative projects were developed both for research, product development and
educational programmes. Local commercial organisations (particularly the Swedish Dental
Federation) co-operated in the project; new technologies were developed and an evaluation
of alternative products was carried out. Pollution limits were imposed that were determined
to be appropriate to encourage the purchase of the endorsed environmental products. This
programme of research, and earlier work during the 1980s led to a reduction of between 50
and 80% of potentially toxic elements in sewage sludge [Ulmgren 2000a].
The results of some more specific investigations into sources of potentially toxic elements in
UWW are outlined below.
Scandinavian studies [SFT-1997a, 1997b, 1999] showed that the motor industry, followed by
vehicle workshops contribute most to the potentially toxic element load in UWW. Vehicle
washing, particularly heavy goods vehicles (HGVs), was found to be an important source of
potentially toxic element contamination.
In Sweden, oil separators are commonly used in vehicle washing and motor industries
before discharging effluent to UWW collecting systems. Most facilities in Sweden are
reported to be equipped with combined oil separators and sludge traps where the dispersed
oil and sludge should be retained. However, tests at one of the light vehicle (LV) washing
facilities showed that this equipment was ineffective with practically no difference between
the influent (before the separator) and the effluent (after the separator). This was due to the
formation of stable emulsions in the wastewater caused by the detergents in the
microemulsion formulations used for vehicle washing [Paxéus, 1996b].
A study by the Norwegian Pollution Control Authority [SFT, 1999] examining potentially toxic
element pollutants in Norway found that out of six petrol stations investigated, only one had
an oil separator/sand trap that worked effectively. Although designed to reduce the
contamination of urban wastewater, oil separating devices are generally ineffective at
reducing pollutant emissions from vehicle washing and motor industry facilities.
In the late 1980s, the high concentration of mercury in sewage sludge (SS) at Henrikdal
WWTS, Stockholm, prompted an investigation to identify potential sources (Table 2.10). It
was concluded that the high mercury content of sludge was attributable to dental practices
and the use of mercury in dental amalgams. Amalgam separators were ineffective at
retaining mercury and new legislation was introduced to combat this [Ulmgren, 2000a].
Recent reduction or bans on the use of mercury in various products, such as batteries and
thermometers, has led to a reduction of mercury input into UWW [Ulmgren, 2000a and
Ulmgren, 2000b]. Mercury recycling schemes have also proved to be successful, and could
be extended to other countries and activities.
Other discharges from dental technicians shops are covered in detail in Section 6, Case
Studies.
Source Comments
Heavy Industry no Ruled out as a source of mercury to UWW and SS as these were
not connected to the UWW collecting system
Small and no Ruled out as they were operated in such a way that no
Medium contamination of the wastewater was likely
Enterprises
(18 Companies)
Storm Drains yes 20% of the total mercury load came from storm drains. This was
largely traced to the deposition of particulates emitted from
crematoria which are estimated to be about 50 kg of mercury a year
Household yes About 15% of the mercury entered the waste water system through
Wastewater the use of mercury thermometers in the home, and also from small
amounts of mercury in food and amalgam fillings in teeth
Dentists and yes High mercury content of sludge was largely attributable to dental
Dental practices and the use of mercury in dental amalgams
Technicians
Hospitals yes Samples indicated that hospitals emit 10% of the mercury loading
Old Sewage yes Investigations in the last few years have found many sources of
Pipes mercury in old pipes
Similar findings have been reported in other countries. A WRc report [1994] established that
in the UK mercury emissions are much higher from commercial, rather than domestic
sources, mainly due to dental practices. In France, it is estimated [Agence de l'Eau, 1992]
that between 73 and 80 % of the mercury in UWW is from dental practices and amalgam
fillings corrosion. In the Louviers area of France, the analysis of wastewater and sewage
sludge showed that out of the total load of mercury, 50% was lost from medical practices,
13% from dentistry practices, 28% from medical auxiliaries (nurses etc.), 4% from hospital
activities, 4% from veterinary activities, and 1% from ambulance activities. Thus, in this
instance, targeting medical/dental practices may help reduce pollution from mercury [LIFE,
1999].
Table 2.11 highlights the amount of mercury waste produced by zinc/lead metallurgy and
chlorine production. In Galicia, north-western Spain, high mercury levels in UWW and
sewage sludge are attributed to chlor-alkali production in the Pontevedra area [Cela et.al.
1992]. In Portugal too, the presence of mercury in treated wastewater, sewage sludge and
the lagoons of Aveira is linked with chlor-alkali production [Lucas et.al, 1986 and Pereira
et.al, 1998]. There appears to be potential for improved control and recycling of mercury
waste associated with these activities.
Sources of chromium
Mine production of chromium in Finland has increased from 348 thousand tonnes to just
over a million tonnes in 1990 [Mukherjee 1998], representing just under 10% of world
production. The main sources of chromium in wastewater are from the metal, chemical and
leather industries (Table 2.12). As can be seen, the chemical industry contributes over half
of the total emissions to UWW and surface waters in this region.
Table 2.12 Chromium emissions to water in Finland [adapted from Mukherjee, 1998]
Source Category Emissions to water (not exclusively UWW)
tonnes per annum % of total contribution
Chemical Industry 14.3 58.1
Paint Manufacture 0.01 <0.1
Electroplating 0.1 0.4
Ferro-chrome and Stainless Steel 4.6 18.7
Plants
Leather Processing 5.5 22.5
Total 24.6 100.0
Mukherjee [1998] reports that in Scandinavia, chromium compounds are also used in wood
preservatives, along with arsenic compounds (As2O5) and an oily mixture of organic
chemicals (phenol and creosol).
All wet-textile processing in Finland discharges its wastewater, containing chromium and
other metals, to the WWTS. The textile companies studied [Kalliala, 2000] produced
between 50 and 500 litres of wastewater per kg of textile produced. Wastewater analyses
were carried out at six major Finnish textile companies (two of these include analysis for
potentially toxic elements (Table 2.13)):
Table 2.13 Potentially toxic elements in wastewater from textile processing in Finland
[Kalliala, 2000]
Wastewater analysis (µg l-1)
Company 2 Company 4
Lead 0.11 -
Chromium 0.03 60
Copper 0.4 80
Zinc - 20
There is a very high variation in the process emissions between these two plants. Company
2 was noted to use cellulose blends while company 4 was noted to have mainly polyester
and polyester blends.
Sources of lead
Data from ADEME [1995] showed that worldwide consumption of lead is around 5.4 million
tonnes per year. In a Swedish study [Palm, Östlund, 1996] in the Stockholm area the total
amount of lead used in products such as those listed previously, was estimated at between
44,000 and 47,000 tonnes per annum. Clearly the potential for lead entering UWW from
these sources will vary greatly. The largest amount of lead that finds its way to the WWTS is
likely to be contributed by piping. Estimates for the amount of lead used are 8,000 tonnes in
lead jointed water pipes used inside buildings, followed by 2,000 tonnes used in lead jointed
water pipes used outdoors (higher replacing rate), and 120 tonnes used in PVC piping.
In the case of Finland, the Ministry of the Environment report that the drinking water
pipelines are predominantly plastic (85% PVC and PEH), with 11% cast iron; no lead is used
for pipes conveying water. The wastewater pipes for the UWW collecting system are 57%
concrete and 41% plastic.
Runoff to UWW collecting systems and waterways has been intensely studied due to its
potentially high loading of potentially toxic elements [WRc, 1994]. Atmospheric inputs to the
urban runoff depend on the nature of surrounding industries, on the proximity of major
emission sources such as smelters and coal fired power stations and the direction of the
prevailing wind. Potentially toxic element loads can be five fold greater in runoff near
commercial activities, than in residential areas far from industrial emitters. Roof runoff and
building runoff also contribute to the total runoff loading and may be a source of considerable
amounts of potentially toxic elements such as zinc, lead, copper and cadmium. Road and
roof runoff sources are particularly important during storm events, which will allow flushing of
potentially toxic elements and other pollutants from surfaces. Furthermore, it is important to
note that the metal species released are usually in a freely dissolved, bioavailable form.
Nevertheless, these sources are very variable, as every event is different and depends on
traffic, material and age of roofs and other surfaces, and meteorological and environmental
conditions.
Although a number of studies had focused on the effects of urban land use in the
quantification of precipitation runoff, it was not until the 1950s that the first qualitative1
studies were undertaken [Palmer, 1950 and 1963; Wilkinson, 1956]. Table 2.14 provides
concentrations for a number of potentially toxic elements in urban runoff, as a summary of
various investigations from 1975 to 1978. It is important to note that the measured
concentrations differ considerably. The main sources of pollution in urban precipitation runoff
can be summarised as follows [based on Mitchell, 1985]:
Table 2.14 Maximum and mean concentrations of potentially toxic elements (mg l-1)
in urban precipitation runoff pollutants [after Mitchell, 1985]
1
Focusing on pollutant loads in rainfall runoff
Site Cd Cu Pb Zn Reference
Urban (Netherlands) 0.9 8 20 31 Van Daalen, 1991
Central Paris 2.4 60 140 Granier, 1991
Central Paris 0.11 6 13.7 38.8 Garnaud et al., 1996-1997
Garnaud et.al., [1999] attempted a comparative study between the main sources of pollution
in urban precipitation in Paris. In this recent study of individual rain events, bulk samples
were collected within four gutter pipes (roof runoff), three yard-drainage pipes (yard runoff),
six gullies (street runoff) and one combined UWW collecting system, at the catchment outlet.
The results can be seen in Figure 2.3. The values are median values.
Differences in potentially toxic elements concentration in precipitation water and runoff from
roofs and streets have also been found in a German study (Table 2.16). In this case it can
be seen that runoff from streets has the highest potentially toxic element content.
A study carried out by Rougemaille (1994) analysed the wastewaters of the treatment plant
in Achères in the Paris region and found that lead concentrations varied between 0.05 and
0.5mg l -1 and that the average concentration was 0.1mg l-1. These wastewaters come from
four different urban areas. The study showed that lead concentrations were 3 times larger
during wet weather than during dry weather, hence proving the importance of the runoff
sources.
A study carried out around the region of Nantes in France in 1999, analysed road runoff from
a major highway for a year showing that lead and zinc are the main pollutants present in
runoff waters (Table 2.17).
PAH Pb Cu Cd Zn
(ng l-1) ( g l-1) ( g l-1) ( g l-1) ( g l-1)
Mean <96 58 45 1 356
Median <74 43 33 0.74 254
Range <11-474 14-188 11-146 0.2-4.2 104-1544
SD 76 44 27 0.86 288
The Swedish study mentioned in previous sections [Palm, Östlund, 1996], estimated the
total amount of zinc passing into wastewater at 6,300 tonnes per annum. Most of the zinc
present in the urban environment was generated by urban runoff and rain; from roofs and
building surfaces (1,600 tonnes), from cars excluding tyres (1,500 tonnes), from tyres (200
tonnes), and from lampposts and street furniture (an estimated 1,142 tonnes). Zinc was also
attributed to water pipe couplings (1,000 tonnes).
Roads are a major source of pollution in urban environments and contribute to wastewater
pollution both directly and indirectly (airborne pollutants generation). Sartor and Boyd
[USEPA, 1972] determined the major constituents of road related runoff to be inorganic
matter, but the total mass of inorganic matter present seemed to increase as the antecedent
dry period (ADP) increased. Sources of the organic and inorganic fraction of road-produced
pollutants are summarised as follows:
Potentially toxic elements in runoff occur from motor fuel combustion, brake linings, tyre
wear and road surface wear. Motor fuel combustion was the largest source of lead to runoff
but it is on the decrease due to the gradual phasing out of leaded fuel in the EU. Other
metals emitted from exhausts are zinc, chromium and more recently tin from the
replacement anti-knock compounds in petrol. The presence of Zn and Cd in road surface
sediments can also be explained by the addition of Zn dithiophosphate in the manufacturing
of lubricating oil, Cd being present as an impurity of the original Zn. Brake lining wear
contributes copper, nickel, chromium and lead to runoff. Tyre abrasion contributes to the
load of zinc, lead, chromium and nickel due to the soot and metal oxides constituents.
Cadmium in car tyres is attributed to zinc-diethylcarbonate, which is used during the
vulcanisation process. Road surface wear contributes to emissions of nickel, chromium,
lead, zinc and copper.
Legret and Pagotto (1999) produced estimates of potentially toxic element content from
vehicle related pollution sources (Table 2.18), and contributions to road runoff (Table 2.19).
Table 2.18 Potentially toxic element contents in vehicle and road materials (mg kg-1)
[after Legret and Pagotto, 1999]
Sources Pb Cu Cd Zn
Leaded petrol 200 - - -
Unleaded petrol 17 - - -
Brake linings 3900 142000 2.7 21800
Tyre rubber 6.3 1.8 2.6 10250
De-icing agent 3.3 0.5 0.2 0.5
Table 2.19 Emissions fluxes in precipitation runoff (kg km-1 annum) and percentage
removed in drainage waters [after Legret and Pagotto, 1999]
Sources Solids Pb Cu Cd Zn
Vehicles Tyre wear 314 0.002 0.0006 0.0008 3.22
Brake 100 0.390 14.2 0.0003 2.17
linings
Petrol - 13.0 - - -
Road Safety - 0.002 0.0002 0.0002 0.95
fence
De-icing 130 0.015 0.002 0.0007 0.002
agent
Air deposition 86 0.014 0.015 0.0009 0.21
Drainage water %2 235 5 2 313 37
The percentages of these potentially toxic elements entering the drainage systems show that
a large proportion of the pollutants released do not end up in the runoff waters but are
probably emitted into the atmosphere. The Zn content in urban runoff remains highly variable
depending on the use of safety barriers made from galvanized steel or from an alternative
material. All parameters are affected by traffic and by variables connected to the
meteorological and environmental conditions of the sites concerned, which make the
comparison highly uncertain (Montrejaud-Vignoles et al., 1996).
The following mechanisms summarise the way the pollutants are transported (pathways)
from the catchment over the roads and finally in the drainage network:
Note that the first two mechanisms above result in pollutants being transferred ultimately into
receiving waters or sewage sludge, while the last mechanism removes pollutants prior to
their ultimate disposal. The general conclusion, however, is that the majority of road surface
runoff contamination is sediment associated. In particular, the prime transport mechanisms
and pathways with respect to road-runoff sediment transport are [Sartor and Boyd, 1972]:
- Particle entrapment
- Cross surface transport by overland sheet-like flow to the gutter as turbulent
heavy fluid transport process
- Linear transport of the particle material parallel to the kerb line into the road gully.
The transportation of surface particulates is sporadic in nature [Mitchell, 1985]. Metal levels
tend to fall after periods of rain, whilst elevated concentrations have been recorded after
prolonged dry periods. Also introduced in the movement patterns are local storage and
residence effects due to the intrinsic configurations and micro-topography of the road
surface [Harrop, 1983]. The fact that contaminants move through this sequence is well
known, however, the relationship between the contaminants and the various mechanisms
involved are poorly understood. Comparison of metal distribution during particle transport,
2
For value >100% the research identified larger concentrations in the samples than expected from the sources that were
taken into account. This is particularly true for Cd concentrations. Additional sources of Cd (such as lubricating oils, as
discussed earlier) may account for this underestimation.
from atmosphere to receiving water body, clearly demonstrates a metal mobility evolution
(Garnaud et al., 1999). Extremely labile (i.e. hydrosoluble or exchangeable), within dry
atmospheric deposits Cd, Pb and Zn, become bio-available within street runoff and stable
within UWW collecting system or river sediment. In conclusion particulate metal mobility may
be classified as: Cu<<Cd<Pb<Zn<Fe.
Potentially toxic elements are predominantly associated with inorganic particles and
research indicates that potentially toxic element concentrations increase as particle size
decreases (Sansalone and Buchberger, 1997; Lloyd and Wong, 1999). In particular
Colandini and Legret (1997), found a bimodal distribution with the highest concentrations of
Cd, Cu, Pb and Zn being associated with particles of less than 40 µm in size. Table 2.18
indicates the potentially toxic elements distribution across the particle size distribution for a
number of potentially toxic elements.
Table 2.21 Summary of pollutant loads in urban runoff caused by road related sources
from 1975 to 1982 [after Klein, 1982]
Vehicle emissions:
Prior to the lead ban in fuel3, research had identified exhaust lead emissions to account for
more than 90% of atmospheric lead pollution. Although the main source of lead in the
average urban atmosphere is lead from fuel additives, it appears that only 5% of the lead
can be traced in runoff water. The greatest part may, therefore, disperse in the atmosphere
or settle on the soil by the roadside (Hewitt and Rashed, 1990). The actual rate and form of
lead emission is crucially dependent on driving conditions. High engines speeds and rapid
acceleration can increase emission levels due to reactivation of particles deposited on the
exhaust system. Total lead emissions can double if the engine and/or weather is cold. The
deposition from petrol to the road surface was estimated to be 0.049g Pb.vehicle-1. km -1. In
the case of lead-containing fuel, approximately 75% of lead is discharged to the atmosphere
(Hewitt and Rashed, 1990) and a further 20% is retained in engine sump oil (Wilson, 1982).
Concentration of lead added to petrol has rapidly declined in the EU during the 1980s due to
legislation. In Austria for example, the lead emissions between 1985 and 1995 have been
reduced by approximately 88 % [UBA, 1999]. Figure 2.4 is indicative of this period of policy
change (between 1972 and 1992). Note the high correlation between lead in petrol and lead
air pollution despite the large rise in traffic flow experienced in the same period.
Figure 2.4 Reduction in lead concentrations in air and petrol between 1972-1992
in the EU [after Montague and Luker, 1994]
Platinum group metals4 (PGMs) are increasingly used in vehicle exhaust catalysts (VECs)
and can be traced in the urban environment [Farago et al., 1995]. These are covered in
detail in Section 6, case studies.
3
Amid mounting concern that the lead dispersed in the environment was causing damage to humans and the
environment, a series of regulations and directives have been adopted in Europe since the 1980s, in order to phase out
the use of leaded petrol. Lead content of petrol has been reduced from 0.4g l-1 to 0.15gl -1, following the Lead In Petrol
Directive 85/210/EEC. Further regulations on air quality have now come into force limiting the levels of lead in air, with an
attainment date of 2005. Some countries, namely: Austria, Denmark, Finland, Germany, the Netherlands, Norway,
Sweden, and the UK have already phased out its use.
However, in some countries in Eastern Europe, higher levels of lead are permitted, up to 0.4g l-1. In most of the newly
independent states and the Russian Federation, permitted lead levels are 0.15-0.37 g l -1. Various strategies for reduction
of lead in petrol have been made in these countries, though it is expected that some will have difficulty in achieving these
targets.
4
Platinum, palladium in vehicle exhaust catalysts and rhodium in three-way catalysts
Vehicle degradation:
Tyre wear releases lead, zinc and hydrocarbons, either in particulate form or in larger pieces
as a result of tyre failure. The deposition of Zn on the road surface from tyres has been
determined to be 0.03g vehicle km-1 (Mitchell, 1985). Metal particles, especially copper and
nickel, are released by wear of clutch and brake linings. Additionally, the presence of Ni and
Cr in storm runoff can result from the degradation of car bumpers and window sealings
where both metals are used in the manufacture of chrome plating. Copper is a common
constituent of piping and other components of the engine and chassis work. The contribution
to road surface material of vehicle tyres and brake linings from different road types has been
summarised in Table 2.22.
Table 2.22 Input from tyre wear and brake lining degradation for each road category
[after Muschack, 1990]
Type Total Individual elements
of street Abrasion (g ha of road-1 annum-1)
(kg ha of
road-1) Pb Cr Cu Ni Zn
Tyre Brake Tyre Brake Tyre Brake Tyre Brake Tyre Brake Tyre Brake
wear lining wear lining wear lining wear lining wear lining wear lining
Residential
way 137 6.8 60 7.3 10 13.7 12 210 10 51 35 0.9
Residential
street 62 8.5 76 9.0 13 17.0 17 260 12 63 43 1.7
Distributor
72 12.4 112 16.6 19 24.9 26 381 18 93 63 2.4
road
Main
distributor 109 19.1 172 20.4 29 38.3 39 586 27 143 96 2.6
road
Main road 127 30.3 266 32.2 44 60.5 60 926 42 226 149 2.1
Dual
carriageway
120 43.4 382 46.3 64 86.9 72 1329 61 324 214 5.8
Motorway 328 82.1 572 87.6 120 164 164 2513 115 613 405 11.0
These findings are also supported by evidence in non-EU countries. Drapper et al. (2000) in
an experimental site in Australia concluded that brake pad and tyre wear, caused by rapid
vehicle deceleration, contributes to the concentrations of copper and zinc in road runoff.
Laser particle sizing indicated that the median size (by volume) of the sediment found was
100 µm, but have settling times of around 24 hours under laboratory conditions. The
explanation offered to this unexpected behaviour is the presence of potentially toxic
elements. One of the most important findings of this study (which took into account both
Australian and US research), was that traffic volume cannot account for more than 20-30%
of the variability of pollutant load variations and therefore a traffic volume criterion on
whether or not the precipitation runoff should be treated may not be acceptable. Drapper et
al. (2000) also stated that precipitation intensity and preceding dry days could be a
significant factor influencing actual pollutant concentrations. It can be argued that a more
suitable criterion for treatment need assessment would be the environmental significance of
the receiving waters.
De-icing agents include large amounts of sodium chloride, and may also contain smaller
concentrations of iron, nickel, lead, zinc chromium and cyanide as contaminants. Their use
can greatly increase corrosion rates in vehicles and metal structures leading to increased
metal deposition. Salt in solution can also create conditions that allow the release of toxic
metals such as mercury from silts and sludge [WRc, 1993]. It is likely that de-icing is a major
source (at least in the winter) of bromide, nickel and chromium [Hedley and Lockley, 1975]
and it is suggested it may affect the solubility and mobility of other metals, notably of lead,
which may precipitate more readily in the presence of sodium [Laxen and Harrison, 1977].
The use of NaCl as a de-icing agent may change the behaviour of the accumulated
contaminants in roadside soils. In soils exposed to high Na concentrations with a
subsequent supply of lower salinity water, as in snowmelt periods and storm flow events,
there is a risk of colloid dispersion and mobilization [Norrstrom and Jacks, 1998]. Soil
column leaching experiments with NaCl and low-electrolyte water have provided evidence
for the mobilisation of organic colloids and Fe-oxides, suggesting that potentially toxic
elements may reach the groundwater via colloid-assisted transport [Amrhein et al., 1992,
1993]. Moreover, the use of road-salt may result in the increased mobilisation of potentially
toxic elements due to complexation with chloride ions [Doner, 1978; Lumsdon et al., 1995].
Complexed cyanide ion (in the form of sodium ferrocyanide) is added as anti-caking
agent to de-icing agents, and compounds containing phosphorus may also be added as
rust inhibitors. Novotny et al. (1998) argue that although ferrocyanide is non-toxic in its
original form, its instability under predominant natural surface waters conditions, results in
decomposition to free cyanide which is toxic (free cyanide↔HCN(aq)+CN-(aq)). The initial
cyanide form is only stable within the pH range 8 to 14 and zero to –600mV redox potential
(Eh). The rate of decomposition is estimated around 10.2µg l-1 h -1 in salt water. Meeusen et
al. (1992) estimated similar rates of decomposition.
Road surface degradation is likely to release various substances: bitumen and aromatic
hydrocarbons, tar and emulsifiers, carbonate and metals depending on the road construction
techniques and materials used. The following table provides some indication of the
concentrations of potentially toxic elements released from road surface abrasion, classified
by type of road encountered in urban areas.
Accidental discharges:
Although spillages can be considered a minor add-in in terms of total pollutant loading, they
can be one of the most serious sources of contaminants in urban areas. They can range
from minor losses of fuel to major losses from fractured tanker vehicles. The resulting impact
on wastewater treatment plants or directly to water receptors is hard to estimate due to the
random nature and the unpredictability to both the extent of the spill and its position relative
to the precipitation runoff system.
In the case of chemical accidents, water or foam medium are used for road cleaning
purposes or for fire fighting. The compositions of a typical and unusual load of the surface
run-off are compared in Table 2.24.
Table 2.24 Example of a typical and unusual load in run-off water from a German
motorway [Ascherl, 1997, Krauth and Klein, 1982]
Parameter Run-off rain water- mean value Water for firefighting- [mg l-1]
[mg l-1]
Cd 0.0059 0.057
Cr 0.0096 0.053
Cu 0.097 0.203
Fe 3.42 4.0
Pb 0.202 0.439
Zn 0.36 4.7
B Roof runoff
Runoff from roof surfaces constitutes a significant fraction of the total sealed surface runoff
and is often regarded as unpolluted. Assessment of roof runoff quality found in literature
gives rather contradictory results. Some authors conclude that rain runoff from roof surfaces
is polluted (e.g. Zillich 1991; Good 1993); others found that there is a low pollution potential
associated with roof runoff (Shinoda 1990). For the specific case of potentially toxic
elements pollution however, the literature seems to agree that roof runoff can be at least as
polluted as road runoff (Herrmann et al., 1994; Förster, 1999). The pollution effect is much
greater when the source of pollutants is the roof material itself. Förster (1999) found that zinc
concentrations in runoff from zinc sheet roof were actually two or three orders of magnitude
above those measured in runoff from roofs without any metal components (i.e. fibrous
cement roof).
A study in Calais, France, and its surrounding area found that concentrations of cadmium,
mercury, and lead in roof sludge were: 34.5 mg kg-1, 4.4 mg kg-1, and 4mg kg-1 respectively
in the urban areas [ADEME, 1997]. A study carried out in Nancy in 1996 analysed wet
weather runoff and determined the main metal-contributing sources. For zinc, roof runoff was
the largest source as it contributed 72%, and road runoff only contributed 12%. For lead, the
main source was again roof runoff with 33% contribution and then road runoff with 32%
[Autugelle et al., AGHTM, 1996]. However, these data may not be typical, as they represent
one storm event.
Relationships between rooftop material and runoff pollutant load can be observed in Figure
2.5 and Table 2.27
Figure 2.5 and Table 2.27 Rooftop material and runoff pollutant load [after Gromaire-
Mertz et al., 1999]
Roof Name Covering Gutter
Material Material
Table 2.28 provides some indicative ranges of potentially toxic element pollution
concentrations from roof runoff. For comparison purposes the ranges of concentrations of
the same pollutants from other sources in the same study, are also included. The median
value is used, instead of the mean, to filter out the effect of isolated extreme events.
Table 2.28 Potentially toxic element pollution concentrations from roof runoff
[after Gromaire – Mertz et al., 1999]
In conclusion it can be said that roof runoff pollution is influenced by roof material, air
pollution, the precipitation event (intensity, antecedent dry period), the meteorology (season,
wind speed and direction) and the pollutants’ physico-chemical properties. It can under
certain conditions by far exceed threshold toxicity values. The following suggestions
(Förster, 1999) summarise a number of research areas that should be considered to
minimise roof runoff pollution.
Rainwater can add its own absorbed and dissolved pollutants to the loads generated from
other sources. This was shown in Figure 2.3, which shows the initial potentially toxic element
loading of precipitation and the subsequent additional loading from roof, pavement and road
surfaces. Both traffic density and location of industry have a strong influence on the
deposition of potentially toxic elements in precipitation.
Table 2.29 Composition of atmospheric loaded run-off water in German urban regions
[Freitag et al. 1987, Göttle 1988, Hahn 1995].
Currently, vehicle traffic, steel and glass production, and combustion processes represent
the main sources of lead in the atmosphere. Data by ADEME studies have shown that
atmospheric fallout contributes 87-536 g ha-1year-1 of lead, and is particularly high in urban
areas. These studies determined that 70-80% of lead present in UWW comes from runoff,
15-20% from commercial sources and 5% from domestic sources. The main cadmium
sources are from combustion processes (vehicle traffic, waste combustion in incineration
plants). Combustion processes and chlorine and steel production represent the main
sources of the atmospheric mercury emissions in the Central Region. Table 2.30 shows the
reduction in Cd, Hg and Pb emissions in Austria between 1985 and 1995 as a result of
legislative controls.
Table 2.30 Emissions and predicted yearly emissions of potentially toxic elements in
Austria, 1985-2010 [UBA, 1999].
PTEs 1985 1990 1995 Prediction Prediction
[t y-1] [t y-1] [t y-1] 2005 2010
[t y-1] [t y-1]
Cadmium 4.80 3.10 1.80 1.20 1.30
Mercury 4.30 2.70 1.50 1.20 1.10
Lead 320.00 202.00 39.00 24.00 21.00
The presence of impermeable surfaces in urban areas prevents natural filtration processes
in the soil zone from removing the pollution. The actual quality of the rain can vary
dependent on pollution sources other than urban traffic. In coastal areas the increased
concentrations of sodium and chloride in precipitation will increase the susceptibility of
vehicles to corrosion. A road drainage study in Sweden noted precipitation pH of between
3.8 and 4.9 [Morrison et al. 1988].
The second of the two atmospheric sources of contamination is dry deposition in the period
between storm events. For dry deposition, removal by stormwater runoff is not the sole
mechanism responsible for depletion of the contaminant store, which is developed on the
catchment surface. As well as removal by storm events, removal also can occur through
street sweeping, through the local turbulence arising from the motion of vehicles on roads,
and through wind events where the wind has sufficient capacity to entrain the contaminant
and to move it from the surface of the urban catchment [Ball et al., 2000].
Dry atmospheric fallout can be responsible for large proportions of road dust but estimates
vary according to atmospheric and weather patterns, as well as with different sampling and
estimation methods. Nevertheless, atmospheric deposition can be very significant proportion
of the total particulate/sediment input to a highway and since much of it is inert, inorganic
and often calcareous in nature (depending upon local geology and building stone), it can
prove beneficial in neutralising acid emissions, reducing potentially toxic element solubility
and assisting in the binding of organic and other pollutants [Luker and Montague, 1994].
Snowfall has an increased pollutant scavenging efficiency because of the large snowflake
surface area and the increased ionic strength of the melt water provides enhanced metal
exchange capabilities. Trees in urban settings are also effective scavengers of metals, which
are deposited on surfaces at leaf fall.
Atmospheric contaminants are deposited during the early stages of a precipitation event and
therefore the resulting impermeable surface loading tends to be independent of both
precipitation volume and intensity, with the pollutant load tending to increase with the length
of antecedent dry period and with local traffic density.
E Sewer cleaning
Sewer cleaning is carried out for a number of reasons, but principally to deal with blockages
or to remove sediment in order to restore hydraulic capacity and limit pollutant accumulation.
A number of cleaning techniques and methods is in use, depending particularly on location
and severity, including rodding, winching, jetting, flushing and hand excavation (Lester &
Gale, 1979). A combination of more than one method may well be used in any particular
locality.
The frequency with which sewers are cleaned will depend on the maintenance strategy in
operation. If reactive maintenance is used, problems are dealt with on a corrective basis as
they arise (i.e. after failure). This approach will always be required to a certain extent, as
problems and emergencies occur from time-to-time in every system. However, its frequency
cannot be predicted. In planned maintenance, potential problems are dealt with prior to
failure. Unlike reactive maintenance, planned maintenance is proactive and has the objective
of reducing the frequency or risk of failure (Butler & Davies, 2000). Planned maintenance
differs from routine maintenance (operations at standard intervals, regardless of need), and
involves identifying elements that require maintenance and then determining the optimum
frequency of attention. Frequency of cleaning will thus vary from place to place but is usually
less than once per year even in heavily affected sewers.
Sediment removed from sewers during cleaning is normally classified as a controlled waste,
and is therefore disposed of to licensed landfill sites.
2.2 Influence of various treatment processes on the fate of potentially toxic elements
through WWTS and SST
The removal of metals during secondary wastewater treatment is dependent upon the
uptake of metals by the microbial biomass and the separation of the biomass during
secondary sedimentation. Several mechanisms control metal removal during biological
secondary treatment including:
In general; the patterns in metal removal from settled sewage by secondary treatment are
similar to those recorded for primary sedimentation. However, the general survey of removal
efficiencies listed in Table 2.32 suggests that secondary treatment (by the activated sludge
process) is more efficient at removing Cr than the primary stage. Operational experience and
metal removals measured by experimental pilot plant systems provide guidance on the
overall likely removal and transfers to sludge of potentially toxic elements from raw sewage
during conventional primary and secondary wastewater treatment. This shows that
approximately 70 – 75 % of the Zn, Cu, Cd, Cr, Hg, Se, As and Mo in raw sewage is
removed and transferred to the sludge (Blake, 1979) and concentrations of these elements
in the final effluent would be expected to decrease by the same amount compared with the
influent to the works. Lead may achieve a removal of 80 %, whereas the smallest overall
reductions are obtained for Ni and approximately 40 % of this metal may be transferred to
the sludge.
The majority of potentially toxic elements in raw sewage are partitioned during wastewater
treatment into the sewage sludge or the treated effluent. However, atmospheric volatilisation
of Hg as methylmercury, formed by aerobic methylation biotransformation processes, is also
suggested as a possible mechanism contributing to the removal of this element during
secondary wastewater treatment by the activated sludge system (Yamada et al., 1959).
Whilst some of the Hg removal observed in activated sludge may be attributed to bacterially
mediated volatilisation, it is unlikely that this is a major route of Hg loss because of the
significant quantities of Hg recovered in surplus activated sludge (Lester, 1981).
Table 2.32 PTE removals and transfer to sewage sludge during conventional
urban wastewater treatment [Lester, 1981]
PTE Removal (%)
Primary(1) Secondary(2) Primary + Primary +
secondary secondary(3)
Zn 50 56 78 70
Cu 52 57 79 75
Ni 24 26 44 40
Cd 40 40 64 75
Pb 56 60 70 80
Cr 40 64 78 75
Hg 55 55 80 70
Se 70
As 70
Mo 70
(1)
Mean removal (n = 5) from raw sewage and transfer to sludge during primary sedimentation
(2)
Mean removal (n = 9) in activated sludge from settled sewage, (3)Blake (1979)
Predicting the fate of potentially toxic elements during WWT and sludge treatment
Chemical contaminants present in UWW are associated principally with the organic and
mineral fractions in sewage. The microbial biomass in secondary treatment is also effective
at scavenging potentially toxic elements from the settled sewage transferring metals to the
activated sludge. About 60 - 80 % of the wastewater load of potentially toxic elements such
as Cu and Pb is transferred into sludge (Table 2.32) and the sludge contains approximately
1000 times (mg kg-1 ds basis) the concentration of these metals present in the wastewater
(mg l -1). The relationship between metal concentrations in wastewater and in sludge can be
determined empirically as follows (after Blake 1979):
For example, a wastewater containing 1.3 mg l-1 of Zn (P) and 450 mg l-1 of dry solids (Ws)
would produce sludge with a Zn concentration of 2000 mg kg-1, assuming a transfer factor of
70 % (T):
This relationship can also be used to estimate the concentrations of metals in the raw
sewage effluent, based on analytical data for the metal content in sludge and the dry solids
in the raw wastewater:
The concentration in the final effluent, F mg l-1, can therefore be estimated from:
Based on the above assumptions, the Zn content in the final effluent in this example is
estimated to be:
= 0.4 mg l-1
A more mechanistic approach to predicting the fate of metals during wastewater treatment is
described by Monteith et al. (1993) using a computer-based mathematical model. The
mechanistic model, TOXCHEM (Bell et al., 1989), includes both steady state and dynamic
models to simulate operation of a conventional activated sludge plant, incorporating grit
removal, primary clarification, aeration and secondary clarification unit processes.
Biodegradation, surface volatilisation, air stripping, precipitation and sorption removal
mechanisms are determined for trace metallic and organic contaminants in the model’s
database. A sensitivity analysis feature allows the user to investigate the impact of design
and operating conditions and the contaminant’s physical/chemical properties on removal by
unit process and by mechanism.
Inputs to the TOXCHEM model include influent wastewater flow rate, influent metals
concentrations, dimensions of individual process units, plant operation conditions (e.g. mixed
liquor suspended solids concentration), and raw wastewater, primary effluent, and
secondary effluent suspended solids concentrations. The model then predicts metal
concentrations in primary sludge, return activated sludge, surplus activated sludge, and
secondary settler effluent, based on mass balance calculations and removals through
precipitation and sorption. The steady-state model accounts for removal by sorption of
soluble metals onto settleable solids and precipitation of the metals into a settleable form.
The following assumptions were used to develop the model equations:
In both the primary settlement and aeration tanks, the model calculates the metal
concentrations in the soluble and solid phases:
Ct = C s + Cx
Cx = Cp + KpXCs
Where:
The values of Kp and metal solubilities are experimentally defined. Solubility was determined
from dosing studies in which metal concentrations were measured in filtered and unfiltered
wastewater samples at equilibrium.
The soluble, sorbed and precipitated metal fractions are calculated by the expression:
Fractional removal of metals in the primary and secondary settlers is calculated by:
FRm = (FRsolidsCx)/CT,0
Where
FRm = fractional removal of metal in settler, and
FRsolid = fractional removal of solids in settler.
Fractional removal of the solids is input by the user based on site-specific experience. The
output for the primary and secondary settlers is calculated by:
The TOXCHEM model was validated against operational data on effluent metal contents
collected from a full-scale wastewater treatment plant (Table 2.33). The predictions were
compared to observed values in the final effluent using linear regression analysis and the r2
statistic. Copper exhibited the highest correlation between predicted and observed effluent
concentrations of the elements tested and the r2 value for this metal was 0.96. The model
predicted that 70 % of this element would be transferred to the sewage sludge. Zinc also
gave relatively good agreement between predicted and observed effluent concentrations and
the results showed that 50 – 60 % of Zn in wastewater would be recovered in the sludge.
The poorest correlation of modelled and actual values was obtained for Ni and the r2 was
0.41 in this case. The model underestimated the removal of Ni by the wastewater treatment
plant and the predicted value was 26 % compared with the observed removal of 37 %. Lead
and Cr have low solubilities and in both cases, the TOXCHEM model predicted much larger
removals of approximately 70 % for these metals than was observed in practice at the
sewage treatment works. However, the model predictions for Pb and Cr were comparable
with operational experience at other wastewater treatment plant (Table 2.32). The slopes of
the regressions lines fell within the range 0.58 – 1.96 bracketing the ideal slope of 1.0. The
model provided good representations of the concentrations of Cu, Ni and Zn in the final
effluent, but was less satisfactory for Pb or Cr. Cadmium was not subject to the verification
exercise because concentrations in the effluent were below the analytical limit of detection.
The modelling and experimental studies showed that Cd and Ni were the most soluble
metals, and the most poorly removed, while Pb and Cr were the least soluble. The majority
of metals, with the exception of Ni, were maintained in the mixed liquor, and the mass
collected in effluent was small in comparison to the total influent mass. At low metal
concentrations (0.02 – 0.1 mg l-1), the soluble fraction is controlled by sorption to solids. At
larger influent metal concentrations, precipitation is the main process controlling soluble
metal fractions. In consequence of this differential fate of metals in WWTS, nickel may need
tighter regulation at source to reduce the amount in the effluent.
The mechanistic approach to model development incorporates the main chemical and
physical processes that are recognised as being important in removing metals from
wastewater. However, in some circumstances, there may be specific properties of a
wastewater at a particular treatment works that influence metal behaviour and removal
efficiency that are not accounted for by these basic assumptions. For example, recoveries of
insoluble elements such as Cr or Pb in sewage sludge are usually relatively high and of the
order >75 % (Table 2.33). This contrasts with the recoveries of these elements measured by
Monteith et al. (1993), which were much lower than those normally observed in practice.
Operational and mechanistic models have the capability to predict partitioning and
distribution of potentially toxic elements from raw sewage during conventional wastewater
treatment. They provide insights into the physico-chemical processes controlling metal
removal in terms of solubility, sorption and precipitation mechanisms, and calculate the mass
balance and partitioning of metals into sewage sludge and the final effluent. The metal
concentration in sludge can be calculated using the estimated partitioning coefficients and
the mass of primary and biological sludge produced by primary sedimentation and
secondary wastewater treatment.
Volatile matter is also lost during aerobic composting of sewage sludge (Figure 2.6).
Composting dewatered sewage sludge cake requires a bulking agent, such as straw or
woodchips, to increase porosity and reduce moisture content to values that will support
aerobic microbial decomposition processes. Straw is often used for this purpose and may be
mixed with sludge cake at 25 % ds at a rate of 5 – 10 % on a fresh weight basis (Smith and
Hall, 1991). The addition of bulking agent to sludge reduces the initial metal concentration.
However, metal concentrations in the composting material increase proportionally in linear
relation to the extent of volatile matter destruction by microbial activity. In windrow
composting trials (Smith and Hall, 1991), for example, the volatile solids concentration of
composting sewage sludge and straw decreased by 21 % during a period of 100 days
(Figure 2.6). During that period, the metal concentration in the composted product was
increased above the value in the original sludge (Figure 2.7).
Figure 2.6 Volatile solids content of sludge-straw compost at different rates of straw
addition (fresh weight) to sludge cake (25 % ds) over time (Smith and Hall, 1991)
75
70
Volatile
Solids
65 5.0%
Content (%)
7.0%
60 8.5%
55
50
0 20 40 60 80 100 120
Time (days)
Sludge stabilisation processes reduce the fermentability of the sludge and the potential
odour nuisance and health hazards associated with its use on agricultural land. However,
the loss of volatile matter during microbial decomposition also significantly increases its
metal content by as much as 40 % compared with material that has not been subject to a
biological stabilisation process. More than 75 % of the sludge produced in the EU is treated
by anaerobic or aerobic digestion. Despite the wide adoption of biological stabilisation
processes for sludge throughout the EU, which generally increase the metal content of
sludge, reported potentially toxic element concentrations in sewage sludge continue to
decline (e.g. Figure 2.7).
This further emphasizes the major and significant improvements in sludge quality, in terms of
potentially toxic element content, that have been achieved in the past 20 years through
improved industrial practices and the successful and effective implementation of trade
effluent controls.
1300
1200
1600
Zn (mg kg-1 ds)
1400
1200
1000
800
600
400
200
0
50 55 60 65 70 75
1.6
1600
1.4
1400 1.2
1200 1
0.8
1000
0.6
800
0.4
600 0.2
400 0
1978 1983 1988 1993 1998 1978 1983 1988 1993 1998
Year Year
Figure 2.8 Reduction in (a) zinc and (b) cadmium concentrations (untransformed and
log10 transformed data, respectively) in sewage sludge from Nottingham STW, UK
during the period 1978 – 1999
There is limited information available on pollutant concentrations in influent and effluent from
WWTS. Concentrations may also be less than the detection limit of the analytical techniques
used. It must be noted that the variability of influent concentrations within a WWTS can be
very high due to season, precipitation, and levels of industrial and domestic activities. This
means that comparisons based on small numbers of samples must be made with caution.
Organotin compounds were the subject of monitoring in Switzerland by Fent and Müller
[1991], and Fent [1996]. Monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were
monitored in raw wastewater (influent), effluent and sewage sludge (Table 2.35). Phenyltin
compounds were also investigated.
The potentially toxic element loading per inhabitant, per year has been determined in two
German studies (Table 2.36). There is a good correlation between these studies for zinc,
copper, lead and cadmium concentrations in the influent and effluent of WWTS.
Table 2.36 Potentially toxic element loading per member of population in two German
towns [Raach et al.,1999; DAF, 1995]
In Norway and Sweden; emissions of potentially toxic elements from WWTS serving more
than 20,000 persons account for almost 80 percent of the wastewater. The discharges of
metals from these WWTS in Sweden and Norway are summarised in Table 2.37. This shows
that, for Sweden, the amount of potentially toxic elements discharged with urban wastewater
decreased over the period 1992 to 1998 for all metals, except for copper. The statistical data
do not take into account the WWTS size and also the potentially toxic elements reported are
for the treated sewage sludge. There is only limited data available on potentially toxic
element content in the treated wastewater (effluent), due to the low concentration, often
below detection limits.
Table 2.37 Emissions of potentially toxic elements from WWTS in Sweden and Norway
1998
Power et al. [1999] monitored water in the Thames, UK and found statistically significant
reductions in the concentrations of Cd, Cu, Hg, Ni and Zn over the period 1980 to 1997. For
lead, the initial improvements were reversed by drought in the period 1990-1997 resulting in
a slight, though statistically significant rise in Pb concentrations. However; Pb had fallen prior
to this and was still found to have a statistically significant decrease overall in the period
1980-1996 (Table 2.38).
The overall reductions in most metal concentrations in the Thames was greater than 50
percent over the years 1986-1995, with lower reductions being experienced for lead and
cadmium. This complements evidence for sludge quality that overall PTE emissions have
markedly improved.
In spite of the reductions achieved by 1995 in the River Thames, potentially toxic element
concentrations are still high compared to the levels found in the 1980s in the other rivers in
the study. It is concluded that while much progress has been made in reducing the
anthropogenic sources of potentially toxic element pollution discharged into the Thames,
improvements are still needed if water is to approximate to background levels. For cadmium
and mercury; the year 2000 levels are forecast to be about twice estimated background
levels [Power et al 1999].
A study carried out in the Rhine region in France [Commission Internationale pour la
Protection du Rhin, 1999] examined all pollutant sources entering the river over a period of
10 years. The study showed that the decrease in certain pollutants was due to pre-
treatment, cleaner technologies and more care in the handling of the priority substances.
Nevertheless, in 1996, the study showed that diffuse and domestic (communal) sources are
important contributors, particularly storm runoff for mercury, lead, and copper.
The study further divided the sources for each metal and other pollutants into greater detail
for each of the riverine countries in the region (France, Switzerland, Belgium, Luxembourg,
Netherlands, Germany). An estimate into the source breakdown of metal pollution into the
Rhine is included in Figure 2.9.
Percentage contribution of heavy metals for the different sources in the Rhine
100%
90%
80% Diffuse
70%
60%
50% Communal
40%
30%
Industrial
20%
10%
0%
Hg Cd Cu Zn Pb Cr Ni
Figure 2.9 The percentage of potentially toxic elements in the Rhine from different
sources (France, 1999)
The communal sources of wastewater into the river Rhine (in France), include wastewater
from the UWW collecting system, hence showing the widespread presence of these
pollutants (Table 2.39). For mercury, lead, and copper more than half is due to storm runoff.
Erosion and drainage are also important sources, contributing 18% of the mercury and 55%
of the chromium. Atmospheric deposition generally tends to contribute around 8% of the total
diffuse metal contribution, particularly for cadmium and zinc.
Diffuse sources Hg Cd Cr Cu Zn Pb Ni
kg.annum-1
Erosion 18 53 5144 3547 10642 4789 5853
Surface runoff 1 10 474 229 1013 67 62
Drainage 7 286 429 2145 28600 2145 1430
Atmospheric deposition 8 75 189 1131 9425 1508 566
Separating system 8 57 475 1900 7600 1520 855
Storm discharge 32 126 630 3780 17640 3780 1890
Untreated wastewater 16 62 310 1860 8680 1860 930
Houses not connected to 2 7 36 216 1008 216 108
UWW collecting systems
Point sources
Industry 74 242 5548 11190 41100 3120 14300
Communal sources 40 200 1400 12470 30000 2700 3500
Table 2.41 Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Cadmium
Table 2.41b Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Chromium
CHROMIUM Country Mean Median Min. Max. Survey Year/s
Austria 62 54 25 130 1994/95 (11)
Germany 50 52 46 52 1995-97 (4)
Denmark 33 34 24.8 40.3 1995-97 (4)
France 69.4 58.8 80 1995/97 (4)
Finland 85.7 84 82 91 1995-97 (4)
Greece (a) 885.8 1996 (6)
(b) 43.8 1997 (1)
Italy 14.8 1400 1998/99 (10)
Ireland 165 1997 (4)
Luxembourg 51 1997 (4)
Netherlands 64 1990 (16)
Sweden 38.4 37.7 39 1995/96 (4)
UK 159.5 157 162 1995/96 (4)
Norway 28.5 1998 (12)
Poland 144.2 136.5 6.8 289.0 1999 (3)
EU 145 1992 (9)
74 1994-98
USA 589 150 1988 (13)
178 1992 (2)
Table 2.41c Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Copper
COPPER Country Mean Median Min. Max. Survey Year/s
Austria 264 240 170 540 1994/95 (11)
Germany 275 1995-97 (4)
Denmark 284 1995-97 (4)
France 322 1995/97 (4)
Finland 288 1995-97 (4)
Greece (a) 302 1996 (6)
(b) 103 1997 (1)
Italy 160 373 1998/99 (10)
Ireland 641 1997 (4)
Luxembourg 206 1997 (4)
Netherlands 190 1990 (16)
Sweden 522 1995/96 (4)
UK 562 1995/96 (4)
Norway 287.1 1998 (12)
Poland 237.5 183.4 24.1 592.0 1999 (3)
EU 380 1992 (9)
365 1994-98
USA 639 444 1988 (13)
616 1992 (2)
Table 2.41d Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Mercury
Table 2.41e Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Nickel
Table 2.41f Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Lead
Table 2.41g Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Zinc
Table 2.41h Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Arsenic
Table 2.41i Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Selenium
Table 2.41j Survey of potentially toxic elements in sewage sludge: values in mg.kg-1
DS-Silver
References
In the particular case of Greece, Voutsa et al. [1996] have compared the potentially toxic
element content of municipal and industrial sludge for Thessaloniki. The results are
illustrated in Figure 2.10. Sludge A is municipal sludge from Thessaloniki’s main WWTS and
sludge B is from a WWTS treating partially treated industrial wastes from the greater
Thessaloniki region.
Figure 2.10. Potentially toxic element concentrations in sewage sludge from biological
treatment of municipal and industrial wastewater (Municipal sludge: Dark, Industrial
sludge: Light Grey)
As shown concentrations of most metals are 2-9 fold higher in municipal sludge than in
industrial (except for Cd and Cu where the contents are similar). This interesting fact, due
possibly to pre-treatment of the most toxic industrial wastewater on site, is not adequately
explained by the authors.
63
3. Organic Pollutants
There are a large number of organic pollutants from a wide range of sources which may
enter UWW. Paxéus (1996a) identified over 137 organic compounds in the influent of the
municipal wastewater plants in Stockholm. The physical and chemical properties of some of
these organic pollutants are outlined in Appendix B. The main categories of organic
pollutants detailed in this report are:
The most frequent anthropogenic sources of PAHs are: house fires, heat and energy power
stations, vehicle traffic, waste incineration and industrial plants (cement works, metal
smelting, aluminium production). Forest fires represent natural sources. PAHs concentrate in
sewage sludge due to their low biodegradability.
Di-(2-ethyhexyl)phthalate (DEHP):
DEHP is used as emollient in synthetic materials. In Germany, 90 % of DEHP is used in
PVC and about 10% in laquers and paints. It is common to use DEHP as antifoaming agent
in paper production, as an emulsifier for cosmetics, in perfumes and pesticides, they aid in
the production of different synthetic materials such as dielectric in condensers, and
substitute for substances such as PCBs and pump oil. DEHP specific emissions from
various human activities have been identified by Bürgermann [1988] as follows:
• cellulose/paper production
• DEHP production
• plastisol-coating process
• PVC production and processing, leaching from PVC products
• leaching from waste in landfills
• waste incineration and uncontrolled combustion
64
3. Organic Pollutants
DEHP is found regularly in municipal wastewater and, because of its lipophilic properties, it
concentrates in sewage sludge.
Surfactants are contained as the main active agents in all washing and cleaning agents.
These compounds are covered in detail in Case Study (f).
The generic term "dioxins" represents a mixture of 219 different polychlorinated dibenzo-p-
dioxins and furans. The most well known and hazardous dioxin, is the tetrachlorodibenzo-p-
dioxin (TCDD). Dioxin concentrations are calculated as sum of the toxicity equivalents (TEQ)
relevative to the most toxic dioxin [TCDD].
Dioxins speciation in household wastewater and laundry wastewater is similar to those in the
sediments of UWW collecting systems and sewage sludge. A mass balance indicates that 2-
7 times more dioxins in sewage sludge originates from households than from urban runoff.
Washing machine effluent is a major source of dioxins in household wastewater. Dioxins
were also detected in shower water, and in urban run-off from various human activities
[Horstmann 1993, 1995]. These results suggest that the importance of household
wastewater as a dioxin source has been underestimated [Horstmann et.al., 1993,
Horstmann, 1995].
Organic pollutants can originate from food and household related products, such as long
chain fatty acids and their methyl and ethyl esters, originating from faeces, soaps and food
oils. Being relatively hydrophobic these compounds are attached to particles, the
concentration of fatty acids and esters in the unfiltered influent is more than 500 µg/l. Other
organic pollutants from domestic origin are the sterols from animal foods and faeces and
indol from faeces. Caffeine is also found from discharges from coffee processing.
65
3. Organic Pollutants
Plasticisers and flame retardants are still used in many products for household and
industrial applications. Among the organic pollutants present are benzenesulphonamides,
adipates (esthers of hexandioic acid), phthalates (esters of phthalic acid, among which
DEHP is the most common), and several phosphate esters. (2-chloroethanol phosphate) and
TBP (tri-n-butyl phosphate) are used in flame-retardant compositions in textiles, plastics as
well as in other products.
Preservatives and antioxidants are constituents of household and industrial products, and
among the organic pollutants linked with these compounds are parabens (esters of
hydroxybenzoic acid), and also substituted phenols and quinones are among the
constituents.
Solvents both chlorinated and non-chlorinated (alcohols, ethers, ketones) are present in a
large range of products such as car shampoos and degreasing products, household
cleaners and degreasing agents from vehicle maintenance and production. Chlorinated
solvents, such as trichloroethylene and trichloroethane, are in increasingly wide use: the
amounts consumed in France per year are 24,000 and 28,000 tonnes, respectively. The
principal sources of diffuse pollution from chlorinated solvents are due to artisanal activities
such as metal finishing activities and dry cleaners. Nevertheless, domestic sources from
aerosols and other agents are not negligible. Pollution by metal cleaning activities is usually
considered as diffuse discharges as they are usually from small firms with only few
employees. Garages consumed around 15,000 tonnes of solvents in 1988, about 60% of
which is lost to the atmosphere and the rest as waste. Of the 6,000 tonnes, of waste solvent
some will be discharged into the UWW collecting system [Agences de l'Eau, 1993]. Metal
finishing used 50,000 tonnes of solvents in 1991 and their aqueous wastes are discharged
into UWW collecting systems, although these are usually in low levels. Dry cleaning
consumed around 19,500 tonnes of solvents in 1988 and it has been determined that
0.3x10-3 kg of solvent/100 kg of clothes cleaned ended up in wastewater.
Pesticides and herbicides are also a common component of the urban wastewaters and
they result from road and rail weed treatment, and from gardens, parks and urban woodland
areas. They include the triazine group, the phenyl urea group (e.g. chlorotoluron, isoproturon
and diuron), the phenoxy acid group (eg. Mecoprop and 2,4-D) and glyphosate [Revitt et al.,
1999].
An enormous quantitiy of pharmaceutical products are prescribed every year: 100 tonnes
of human drugs were prescribed in 1995 in Germany [Ternes, 1998]. Pharmaceuticals in the
Urban Environment are discussed in Case Study (d), Section 6.
66
3. Organic Pollutants
A study carried out in France in 1995 by ADEME, showed the sources of the main organic
micropollutants in sludge from WWTS were mainly domestic and commercially related (see
Table 3.1). Another study, by SFT (in collaboration with the wider Norwegian government
environmental study programme and the A/S Sentralrenseanlegget RA-2 WWTS),
investigated sources of PAH, PCB, phthalates, LAS and NPE. This study found that sewage
from domestic sources, in this instance from an isolated housing estate with a separate
sewage and stormwater drainage system, does make a significant contribution of the above
organic pollutants to urban wastewater [SFT report 98/43].
Aliphatic Fuel ++ ++ ++
hydrocarbons
Monocyclic aromatic Solvents, phenols + + ++
hydrocarbons
PAHs By-products of petrol + + +
transformation and
insecticides
Halogens Solvents, plastics, ++ + ++
chlorination
Chlorophenols and Solvents, pesticides + + ++
Chlorobenzenes
Chlorinated PAHs PCB, hydraulic fluids (+) + ++
Pesticides + + ++
Phthalate esters Plastifier + + ++
Detergents ++ + ++
Nitrosamines Industrial by-products 0 + ++
(rubber)
Soil is also a major repository of organic matter and the soluble fractions can leach/run-off in
to water courses, especially in upland areas where measures to remove colour and
formation of trihalomethanes during drinking water treament is important.
Table 3.2 shows that the PAH concentration profiles for three Swedish WWTS varies. This
may in part be due to differences in the catchment areas, with the sources of the pollutants
coming from different local industries. Most of these PAHs are expected to derive from
diffuse commercial activities and traffic but PAHs such as pyrene, which is believed to be
derived from at least 50% domestic sources, is present in all the samples at more consistent
concentrations than some of the other compounds.
Mattson et al (1991) referenced in Paxéus (1996a) found that PAHs from food, an often
overlooked source of this pollutant, from households can reach 50-60 % of the total UWW
collecting system load for pyrene and phenanthrene. This is an important observation as
household sources of PAHs are likely to be more difficult to control than commercial
sources.
Another source of PAHs from domestic and commercial activities is the use of phenol and
creosol in products such as wood preservatives. In Finland, 430 tonnes of wood
preservatives were used in 1995 [Finnish Environmental Institute, 1997]. PAHs may enter
UWW as a result of spillages or as surface runoff from rainwater.
67
3. Organic Pollutants
Table 3.2 PAHs concentrations in urban waste waters in Sweden [Paxéus 1996a]
PAHs WWTS
HST GRYAAB SSW
µg/l µg/l µg/l
Naphthalene, dimethyl 1 0.5 <LOD
Naphthalene, methylpropyl 3 <LOD <LOD
1,1’- Biphenyl, dimethyl 2 0.5 <LOD
1,1’- Biphenyl, ethyl 1 <LOD <LOD
Anthracene/Phenanthrene 1 <LOD 0.5
Methyldibenzothiophene <LOD <LOD 0.5
2,8-Dimethyldibenzothioprene 5 <LOD <LOD
Anthracene/Phenanthrene methyl (different 2 <LOD 3
isomers)
Anthracene/Phenanthrene dimethyl (different 1 <LOD 1
isomers)
Retene <LOD <LOD 0.5
Pyrene 3 <0.5 2.5
Pyrene, methyl (different isomers) 2 <LOD 1
Pyrene, methyl, methylethyl or tetramethyl 1 <LOD 1
1,1-Diphenylethane <LOD 0.5 <LOD
1, (H)- Indene, 1-phenylmethylene 0.5 <LOD <LOD
9H-Flouren-9-one 0.5 <LOD <LOD
2-Anthracenaemine <LOD <LOD 9
Acridine, 9-methyl-Dibenz(b,f) azepine <LOD <LOD 0.5
Octahydrophenanthrene, dimethyl-, isopropyl 0.5 <LOD <LOD
Total PAH 23.5 <2 19.5
HST = Henriksdal Sewage Treatment Plant, GRYAAB = Gothenburg Regional Sewage
Works, SSW = Sjölunda Sewage Works (<LOD = below limit of detection)
A study carried out in the Rhine region of France, [Commission Internationale pour la
Protection du Rhin, 1999], showed that control of organic pollutants from point sources has
been effective at reducing levels of contamination in the Rhine. Between 1985 and 1996, the
pollution from PAHs and PCBs had decreased by over 90%. In 1985, 1,075 kg of PCBs were
discharged, which was reduced to 250 kg in 1992, and to 3 kg in 1996, all of which were
from industrial sources. For trichloromethane, 9,000 kg were discharged in 1985, 2,300 kg in
1992, and 2,210 kg in 1996; of these 600 kg were from industry and 1,610 kg from
communal sources.
68
3. Organic Pollutants
B. DEHP
The Danish Ministry of the Environment and Energy [Danish Report, 1999] have estimated
the annual consumption of phthalates in Denmark to be approximately
In Germany, the total production of DEHP in 1988 was 234,000 tonnes. Of this, 1% was
discharged to surface and groundwater [Brüggermann, 1988].
The vast majority of phthalate emissions to the environment occur, not during the
manufacture, but during the use of the finished products. While in some cases this is a
commercial setting (such as vehicle washing, which will be examined subsequently), there
are also major sources in the domestic environment. Mattson et al. (1991) mentioned
previously regarding domestic sources of PAHs, estimated the household contribution of
phthalates and adipates to the Gothenburg sewage works as 70% of the total load (this
figure emphasises the ubiquity of compounds and difficulty of control). Two major sources of
domestic releases to wastewater (shown in bold in Table 3.3) are floor and wall coverings
and textiles with PVC prints.
The Environment Agency of England and Wales [1998] estimates dioxin emissions from
industrial Part A processes to UWW collecting systems in the UK as 4.5 µg (TEQ), whereas
emissions to air from these processes was estimated to be 1.1kg. Routes of these pollutants
into wastewater via deposition or industrial process (i.e. washing of air pollution cleaning
equipment), are not discussed. Actions taken to reduce dioxin emissions continue to ensure
IPC authorisations are met.
Recent research at the University of California, Berkeley, reports that deposition of dioxins to
soil is 6 to 70 times greater than estimated emissions [Eduljee 1999]. This suggests that
either not all sources of dioxin are known and/or the contributions from these sources may
not be accurately characterised.
Table 3.4 shows the dioxin emissions for the years 1994-1998 in Austria. There was little or
no change in the dioxin emissions in Austria over this period, but slight reductions, were
achieved in some sectors. The main reason for the emission reduction in 1998 is due to the
air hold ordinance, which limited dioxin emissions from waste combustion as well as from
steam-boiler plants.
69
3. Organic Pollutants
In Spain, concentrations of dioxins are reported for recent samples (1999) of sewage sludge
and for archived samples (from 1979 to 1987) [Eljarrat, et.al., 1999]. Results are shown in
Table 3.5. It is estimated that the current concentrations of dioxin in sludge have dropped
since the 1970s-80s. This is expected to be due to the source reduction of pollutants, from
combustion and incineration processes, and from certain pesticides contamination and
emphasises the success that controls on use of compounds and trade effluent discharge in
reducing pollutant levels.
Table 3.5 Concentrations of PCDD/F in sewage sludge in Spain [Eljarrat, et.al., 1999]
Adsorbable organo-halogen compounds (AOX) resulting from bleach products and from
chlorine use, were reported in studies done in Portugal, in Ria Formosa lagooned sewage
[Bebianno, 1995] and in Italy in the city of Parma [Schowanek, et.al, 1996]. The average
AOX concentration in sewage was reported as 37 µg.l-1.
Sterols were reported in sewage sludge and around discharge wastewater points in
Portugal, in Faro, Tavira and Olhao [Mudge et al., 1997, 1998 and 1999]. Concentrations
ranged between 0.1 to 27.8 µg.g-1 sterols of dry weight of sludge. Hospital wastewater may
contain high phenol concentrations, up to 20,000 µg.l-1, plus other compounds such as LAS,
NPE, PCBs and pharmaceuticals.
F. Vehicle washing
o Actual cleaning, involving the removal of oily dirt, which, on a quantitative basis
would be expected to be similar to the type of oily dirt (asphalt and vehicle exhaust
particles) which is in road runoff. However, this would also involve the use of
degreasing solvents and surfactants which can enter the wastewater treatment
process.
o Vehicle Treatment, involves the use of protective treatments, often coatings using
different types of wax against corrosion, dust and dirt.
70
3. Organic Pollutants
The effluent is usually discharged to the UWW collecting system. Several studies of the
effluents from vehicle washing facilities have been undertaken [Paxéus 1996a, 1996b,
Paxéus and Schröder, 1996, Ulmgren 2000a]. In Sweden, an environmental standard for car
washing detergents was established in Göteborg in 1992 [EHPA, 1992], based on the
Precautionary Principle and Substitution Principle in the Chemical Products Act. In general
COD values found at the effluents of vehicle washes are in the range of typical untreated
industrial petrochemical wastewaters [Huber, 1988].
In Gothenburg, an important site for vehicle manufacture, vehicle washing was estimated to
correspond to 0.5 % of the total wastewater at the Gothenburg WWTS, which was concluded
to have a very small effect on the total load of organic pollutants at the plant. The major
components of the effluents were aliphatic hydrocarbons and alkylbenzenes, originating from
petroleum base degreasing solvents and the oily dirt on the vehicles themselves (asphalt,
vehicle exhaust particles). Low aromatic products reduce the potential environmental
associated with detergent use in car washing facilities. These are produced by
hydrogenation of petroleum-based solvents where substituted benzenes and naphthalenes
are converted to corresponding naphthenes and decalins. The formation and discharge of
polyaromatic compounds is negligible for detergents that come from low aromatic
microemulsions.
Table 3.6 summarises the results of a study on washing both of light vehicles (LV) and
heavy vehicles (HV) [Paxéus 1996]. As can be seen, HVs tend to contribute larger organic
pollutant loads than LVs.
71
3. Organic Pollutants
Conventional LV HV
parameters
Mean Median Range Mean Median Range
Total oil 291 242 10-1750 550 460 65-1200
COD 1263 1180 120-4200 4600 4500 1700-
7500
Aliphatic hydrocarbons
C8-C16 29 22 1-139 103.86 76.72 41-220
C17-C30 0.6 0.4 <0.001 1.84 1.87 0.9-3.0
Aromatic hydrocarbons
Benzene 0.01 0.01 <0.01-0.2 0.02 0.02 0.02-0.03
Toluene 0.08 0.05 <0.01-0.6 0.10 0.08 0.03-0.2
Naphthalene 0.17 0.13 <0.001- 1.1 0.75 0.3-3
0.7
Biphenyl 0.015 0.005 <0.001- 0.12 0.11 0.04-0.2
0.1
Dibenzofuran 0.001 0.002 <0.001- 0.011 0.011 0.009-
0.03 0.012
Phenathrene 0.005 <LOD <0.001- 0.021 <LOD 0.005-
0.03 0.03
Pyrene 0.003 <LOD <0.001- 0.009 <LOD 0.01-
0.01 0 .02
Fluoranthene 0.003 <LOD <0.001- 0.004 <LOD 0.002-
0.01 0.006
Plasticizers
Diethyl phthalate 0.005 0.01 2E-3-0.06 0.01 0.01 0.01-0.02
Dihexyl phthalate 0.05 0.03 <0.001- 0.3 0.21 <0.001-
0.15 0.7
DEHP 0.52 0.38 0.03 - 4.1 1.50 1.30 0.4 - 3
Washing agents
p-nonylphenol 0.60 0.26 0.01-4 0.43 0.41 0.1-0.8
2-Botoxyethanol 25 15 <0.001- 15 17 <0.001-
270 27
It is not known if this area is representative of the Scandinavian region as a whole in terms of
the car washing input. However, it does seem that car washing is also an important source
of pollutants in Norway [SFT, 1998a, 1998b]. In Norway 41 businesses were reported on as
sources of hazardous organic pollutants, PAHs, phthalates (DBP, BBP, DEHP),
nonylphenols (nonylphenol, nonylphenol mono- and di-ethoxylates). The studies found the
highest pollutant loads in the effluents from motor vehicle workshops to urban wastewater
came from petrol stations with car washes, long haul transport depots with ‘car washes’
commercial laundries, paint spraying workshop and chemical businesses [SFT, 1998a,
1998b].
There are two main types of washing agent available and the choice of these would result in
significant differences in wastewater quality:
• Water-based formulations (microemulsions) containing 10-30% hydrocarbons but
increased surfactants (10-30%);
• Petroleum-based degreasing formulations containing 95-99% of hydrocarbons and
3% surfactants.
Plasticisers found in the effluents from vehicle cleaning included phthalates, although
analysis of the cleaning and washing chemicals showed that they themselves contribute very
little to the discharge of plasticisers.
72
3. Organic Pollutants
A significant proportion of organic contaminants in wastewater are derived from urban runoff.
These organic compounds include aliphatic and aromatic hydrocarbons, PAHs, fatty acids,
ketones, phthalate esters, plasticisers and other polar compounds. Solvent extractable
organics are dominated by petroleum hydrocarbons, which arise from motor oil and tyres
from road surfaces. Organic pollutant sources have not received the extent of research
attention that potentially toxic element pollution has. For example, in the case of PAHs which
are combustion by-products and enter wastewater principally through atmospheric
deposition and urban runoff, the sources can be stationary (industrial sources, power and
heat generation, residential heating, incineration and open fires) and mobile (petrol and
diesel engine automobile) [Sharma et al.,1994]. Different PAH species are associated with
each one of these sources.
The main sources of road and vehicle related metals pollution have been outlined in Section
2.1.3. Table 3.7, shows some of the road and vehicle related sources of organic pollutants.
Table 3.8 summarises the results from three experimental catchments from 1975 to 1982 on
mean concentrations of PAH.
Table 3.8 Summary of pollutant concentrations in urban runoff caused by road related
sources [after Klein, 1982]
The necessary conditions for PAH formation is the presence of benzene and a high
concentration of radical intermediates, which then form stable compounds. Multiple ring
systems are autocatalytic and promote further ring condensations. Fuel aromatic content has
been shown to influence particle-associated PAH emissions almost linearly [Pedersen et al.,
1980; Nunnermann, 1983; Egeback and Bertilsson, 1983]. However, the relationship
between the aromatic content of petrol and PAH formation is not fully understood.
PAHs are produced by unburned fuel, exhaust gases and vapour, lead compounds (from
petrol additives) and hydrocarbon losses from fuel, lubrication and hydraulic systems.
Volatile solids will be added to the total suspended solids loading of rainfall runoff and can
also act as carriers for both potentially toxic elements and hydrocarbons. Some road dusts
have been found to contain 8.5 µg g-1 of PAHs [Colwill et al., 1984 as reported in Luker and
73
3. Organic Pollutants
Montague, 1994]. The introduction of the catalyst technology for motor vehicles lowered the
emissions of PCDD/F in Germany to about 98% [UBA, 1999].
Tyre wear releases hydrocarbons either in particulate form or in larger pieces as a result of
tyre failure. A tyre loses about 10 to 20 per cent of its weight in a lifetime. Annually it is
estimated an average of 140 g of tyre-derived particles are eroded per metre of road
[Environment Agency of England and Wales, 1999].
Plasticisers (such as diethyl phthalate and dihexyl phthalate) are also considered an
important parameter of organic pollution load in urban runoff. Cary et al. [1989], stated that
plasticisers, especially phthalates, represent the major pollutants found in urban storm water.
The concentrations found for 8 plasticisers were recorded. Of these DEHP was found in the
greater concentrations than the other seven plasticisers combined. The main sources of
plasticisers are traffic grime and dirt, associated with the degradation of plastic components
of the vehicles.
B. Roof Runoff
Regarding roof runoff as an interface between atmospheric boundary layer and the runoff
receiving system, Förster (1993) investigated the role of roofs as source and sink of organic
pollutants. The trace organics analysed included PAH, chlorinated hydrocarbons and nitro
phenols. The research indicated that the insecticide HCH was primarily introduced to the
roof runoff system by wet deposition, while the amount of adsorbed PAHs (pyrene;
benzo[a]pyrene=BaP) in roof runoff exceeded the input by rain with events during colder
times of the year where fossil fuel heating systems constitutes additional source for this
pollutant. The concentration profiles for a number of PAHs are illustrated in Figures 3.1 and
3.2 below.
Figure 3.1 PAH in runoff from zinc sheet roof [after Förster, 1993]
74
3. Organic Pollutants
Figure 3.2 PAH in runoff from tar roof [after Förster, 1993]
As can be seen, the concentrations of PAH in roof runoff from zinc roofs was found to be
about ten-fold higher than for tar roofs. There is a difference in the pattern of distribution for
PAH concentration at different precipitation flow rates. For tar roofs PAH concentration is
highest at the lower and higher precipitation flows and lower at intermediate events, whereas
for zinc roofs it tended to be higher at lower precipitation flows. Therefore, concentrations of
**pollutants in roof runoff can be considered variable depending on the characteristics of the
roof material itself as well as on the characteristics of the precipitation event.
A number of hydrocarbons are present in urban rainfall runoff, particularly those associated
with motor vehicles, such as petrol, fuel oils and lubricants. In an unmodified form these
liquids are insoluble in, and lighter than, water. Typically, 70-75% of hydrocarbon oils show a
strong attachment to suspended solids [Luker and Montague, 1994]. PAHs have an even
greater affinity. In contrast, Methyl-tertiary-butyl-ether (MTBEs) the new additive to unleaded
fuel is significantly more soluble in water than all other hydrocarbons in rainfall runoff.
Hydrocarbons, even in low concentrations, can give rise to surface sheens and thus
adversely affect surface waters. Most hydrocarbons eventually degrade by a combination of
microbial and oxidative processes; degradation though is slow, so the increase in oxygen
demand in watercourses and wastewater is likely to be marginal and not a principal
environmental impact.
Herbicides and pesticides are used in road maintenance operations to control weeds and
pests on the roadsides and verges. The triazine group of herbicides, including atrazine and
simazine, has been used extensively for roadside weed clearance and is more soluble and
mobile than their organo-chlorine predecessors. Combined levels of atrazine and simazine
above 1µg l-1 are not uncommon in watercourses near highways (Ellis, 1991). Collins and
Ridgeway (1980), report that half of pesticides in urban runoff are associated with particles
<63 µm, although these particles are less than 6% of the total suspended solids load.
In urban areas, pesticides in general, and herbicides in particular, are becoming an integral
part of the control of unwanted vegetation by local and municipal authorities, rail and airport
operators. The main herbicides used in the UK are of the triazine group, the phenyl urea
group (e.g. chlorotoluron, isoproturon and diuron), the phenoxy acid group (e.g. Mecoprop
and 2,4-D) and glyphosate (Revitt et al., 1999). Of the phenyl urea compounds, only diuron
75
3. Organic Pollutants
has been widely used in the urban environment and in 1989 this herbicide accounted for
13% of the total 550 tonnes of active ingredient used in the UK (Department of the
Environment, 1991). The comparable use of triazines was 39% but following the introduction
of restrictions for the non-agricultural use of these herbicides in 1992, many users converted
to the use of diuron and glyphosate for the control of vegetation in urban environments
(White and Pinkstone, 1995). The removal of herbicides by rainfall runoff is influenced by
rainfall characteristics, the time interval between herbicide application, the precipitation event
and the properties of the herbicide. However, the full range of factors that influence herbicide
release from sites of application and the mechanisms governing the transport to, and fate of
herbicides in the aquatic environment are not fully understood [Davies et al., 1995; Heather
and Carter, 1996]. The principal herbicide sources in urban catchments include [Revitt et al.,
1999]:
Concentrations in receiving waters, reported by Revitt et al., (1999) in the UK, were
consistently above the drinking water limit of 0.1 µg l-1 recommended for simazine and
diuron; the mean concentrations of which reached 0.34 and 0.45 µg l-1, respectively. In
France [Farrugia et al., 1999], the average application rates for pesticides on the most
consuming urban land uses are reported as 900 g ha-1 for roads and streets, 4000 g ha-1 for
cemeteries and 500 to 800 g ha-1 for parks and sport yards. Householders may also use
large amounts of herbicides and other pesticides but information on the quantities applied is
not available in published literature. However, there was considerable variation in the extent
of water contamination with herbicides between catchments. Farrugia et al, (1999), reported
the average concentration of diurons in water receiving urban runoff was 5 µg l-1, and
attributed this entirely to use in urban situations.
It is to be noted that the hydrological characteristics of hard urban surfaces provide the ideal
conditions for the efficient transport of herbicides (particularly diuron, see also Farrugia et al.,
1999) into UWW collecting systems. This, combined with the existence of inert physico-
chemical environments involving neutral pH, low nutrient and total organic carbon levels,
absence of absorption sites and low bacterial populations, allow the application of herbicides
in urban areas (although in low use), to be an important potential source of contamination of
waste water.
The main repository of PCBs, PAHs and PCCD/Fs is soil. Volatilisation from soil, then further
atmospheric transport and deposition of PAHs, PCBs and PCDD/Fs is considered to be one
of the main contemporary sources of these contaminants in the environment Wild et al.,.
[1995]. PAHs are difficult to control because they are a combustion product.
The Austrian Federal Environment Agency (UBA) analysed PAHs in several media (surface
and wastewater, sediment, soil, sewage sludge, compost, plants, street dusts and ambient
air) between 1989 and 1998 [Gans, et.al., 1999]. Only 10 % of samples were above the
detection limit for PAHs of between 2.6 and 20.3 ng l -1 and these were all taken during winter
and spring, suggesting that PAH originates from the emissions of heating systems during the
cold period.
Once released (by the sources mentioned in the previous paragraphs), airborne PAHs are
transported by the prevailing meteorology before being removed from the atmosphere
through various scavenging mechanisms. As with other airborne pollutants the major
mechanisms of removal of PAHs from the atmosphere are wet deposition, such as rain,
sleet, snow, hail, and dry deposition to the surface. The wet removal of gaseous compounds
is better understood than particulate PAH removal [Ligocki et al., 1985]. The extent of in-
76
3. Organic Pollutants
cloud or below cloud scavenging, collection efficiency of falling precipitation, solubility and
size particles has been examined in the literature [McVeety, 1986 as reported in Sharma et
al., 1994].
Dry removal is a function of atmospheric conditions and the surface level concentration of
PAHs. PAHs adsorbed to particles greater than 20 µm have higher settling velocities and
thus will settle in the vicinity of the source. However, this mechanism will only account for a
minor percentage of removal, as PAH are mostly adsorbed on particles less than 10 µm in
diameter.
77
3. Organic Pollutants
During the treatment cycle, some organic materials can degrade to a certain extent,
especially in aerobic environments and organic material of biological origin is easy to
degrade. Indeed, some common organic pollutants such as LAS, are specifically added to
detergents because they are aerobically biodegradable. A considerable body of literature
exists on this aspect and a variety of oxidants have been proposed. The main aim of this
type of work has concentrated on reducing the organic pollutant content in sewage sludge
prior to land disposal. Advanced oxidation processes might be used in tertiary treatment
especially if the final effluent is to be used for drinking water. However, use of these
processes; regardless of the power of the oxidant, cannot be expected, a priori, to degrade
all types of organic pollutants within a reasonably short time scale. Indeed, the presence of
organics in final effluents is an obstacle in expanding the recycling of wastewater.
Traditionally, wastewater treatment is supposed to begin at the head of a WWTS at the inlet
screens used to remove large objects such as wood plastics and paper. However, in reality
wastewater conditioning starts in the sewer, in large conurbations the wastewater can have
quite a significant residence time in a sewer. However, it is suggested that dilution of
sewage with runoff water is likely to have an adverse effect on the efficiencies of the
downstream treatment processes (Dorussen et al., 1997).
Primary treatment is installed to enable sedimentation of the feed wastewater. This process
is used to settle, retain and concentrate most of the particulate material to the bottom of the
tank as primary sludge. The process is affected by temperature and the solids content of the
supernatant or primary overflow is significantly higher if the temperature is low, as it is in
winter. Though simple, primary sedimentation is a widespread process in Europe, although
not practised in all WWTS. In some cases primary sedimentation is not installed and in other
plants flocculation, by addition of flocculants, is carried out in the primary sedimentation tank
(Hahn et al., 1999).
The objective of secondary treatment is to contact the primary overflow (settled sewage) with
air in the presence of aerobic bacteria and other micro-organisms, which convert the organic
matter to carbon dioxide and water to a variable extent. There are two types of plant
commonly used for this process: bio filters and activated sludge. Most WWTS use primary
and secondary processes. However some plants may have tertiary treatment which, can
involve coagulation, flocculation and rapid gravity filtration.
A novel process for secondary treatment is the lagoon (Salter et al., 1999). This is large unit
several meters deep and can be stirred gently and aerated. Aquatic life including fish can
survive in some lagoons. The residence time in the lagoon is long and they can be used to
treat the more contaminated municipal wastes. In addition secondary pre-treatment can be
carried out using magnetic flocs. In this process the organic contaminants present are
78
3. Organic Pollutants
loaded on to the magnetic flocs at a low pH and washed off in a high pH medium (Booker et
al., 1996).
There is some concern about the use of iron coagulants, which is of direct relevance to this
study. Some iron reagents used in wastewater treatment are made as a by-product of
titanium oxide production. The titanium ore contains traces of vanadium and uranium. Two
other tertiary methods often cited are activated carbon and membrane filtration. Both
however are rather expensive. Activated carbon is a very efficient means of removal of
organic pollutants and the technique is widely used in small domestic plants used to polish
drinking water. Membrane filtration is also very effective in removing particulate material
from water. However, the membranes are expensive and fouling can occur.
It is clear that the regular screening of priority organic pollutants on a day-to-day basis would
be complex and uneconomical. It has been suggested that determination of adsorbable
organic halogens (AOX) be used as an indicator for these priority substances (Hahn et al.,
1999). AOX determination is a relatively easy technique to use (Korner, 2000). These
substances are sorbed from the water on charcoal, which is subsequently pyrolysed. The
hydroxyhalides produced are sorbed and analysed by titration. Another general test
mentioned in the literature (Ono et al., 1996) is the bacterial umu-test, which measures
damage caused by organic pollutants on DNA.
Kow is dimensionless and values vary over the range of at least 10-3 to 107 and are usually
expressed logarithmically. Large Kow values are characteristic of large hydrophobic
molecules which tend to be associated with solid organic matter while smaller hydrophilic
molecules have low Kow values. Octanol-water partition coefficients can be measured directly
by using conventional “shake flask” methods (Leo and Hansch, 1971). This experimental
approach is restricted to compounds of low-to-medium hydrophobicity, since for compounds
with high hydrophobicity, the concentration in the aqueous phase is too low to be measured
accurately.
Kow can also be correlated with various environmental parameters, such as solubility. By
definition, the partition coefficient expresses the concentration ratio at equilibrium of an
organic chemical partitioned between an organic liquid and water. This partitioning is, in
essence, equivalent to partitioning the organic chemical between itself and water. One would
expect that a correlation would exist between the partition coefficient and solubility. Lyman et
al. (1990) presented the following correlation between solubility based on 156 compounds:
1
log = 1.339 log K ow 0.978
Sw
where Sw is the solubility expressed in mol l-1. This correlation was obtained empirically and
the correlation coefficient was found to be 0.874.
79
3. Organic Pollutants
In this study a specific list of organic pollutants has been defined and it can be seen that
their solubilities are very low but the Koc values are very high in the region of 105 indicating
that the sorbtion would be very favourable. From the Koc values and the weight fraction of
organic carbon species present in the feed (f) an estimate of the removal of organic species
can be made. The amount left in the supernatant water as a percentage left (L) is given by:
1
L = 100
K oc f
Thus if f = 10-3 and Koc = 10-5, the percentage left would be 1%. There is limited data
available or actual results but figures for L are generally much higher. (Pham et al., 1997)
report that 30% of PCB and only 25% of the PAHs were removed from a specific treatment
plant.
3.2.4 Modelling
Understanding the processes involved in wastewater treatment is likely to provide a basis for
understanding the pathways and partitioning of pollutants in these processes. The way to do
this is to develop models of the processes and to simulate plants using computers. An
example of such a comprehensive model has been published (Gabaldon et al., 1998). The
model does not specifically include large molecular weight organics.
It is of some of interest to note that there is some work on processes that occur in a sewer.
One study aims to model the emissions of volatile organic compounds in cocurrent air flow in
open and closed sewers (Olsen et al., 1998). Another study measures the removal of COD
and proteins within a sewer (Raunkjaer et al., 1995) and found that there were quite
noticeable losses in a sewer. In another study the sewer pipe was considered to consist of a
sediment above which was a bio-film and above that the water phase (Fronteau et al., 1997).
O’Brien et al. [1995] and Mann et al.[1997] present a first order model for a wastewater
plant. In the secondary section aeration for stripping, biodegradation and sorption on to a
PAC (Powdered Activated Carbon) were considered. PCB, PCDD/F or PAH were not
included but the methodology presented in this paper could be applicable to the study of the
fate of these high molecular weight pollutants in secondary treatment. Work has been done
on modelling trickling filter-beds (Shandalor et al., 1997). This predicts the drop of solids
loading in the water as it trickles down the bed. On the more specific case of organic
80
3. Organic Pollutants
pollutant removal, a detailed paper has been published on the removal of volatile organic
contaminants in a wastewater plant (Melcer et al., 1994). However, again no specific
mention of PAH or similar organics was made.
There have been a number of studies on the degradation rate of PCDD, PCDF and PCBs,
which have been reported in a review article (Sinkkonen et al., 2000). The experiments were
conducted in laboratory rigs and the data reported as half-life analogous to radioactive
decay. The mean half-life quoted is given in Table 3.09.
This study seems to indicate that these organics will not be degraded in a WWTS. These
half-lives are considerably longer than the residence time in a sewage treatment plant or
sewer. As the authors point out the experiments were conducted near ideal conditions and,
in practice, the half lives are believed to be longer than the figures quoted in the table,
especially if the temperature is low.
PAH compounds are believed to be persistent in the environment. There is some work that
presents evidence that some of these compounds can be degraded in periods of 12-80
hours (McNally et al., 1998). Compared with PCDDs this time period is rapid. However,
these experiments on biological degradation of PAH were carried out under ideal conditions.
There was a constant temperature (20oC), specially adapted bacteria were used and
nutrients were added. In a practical case where low temperature and few nutrients are
present, the actual degradation times would be much longer (in the region of 80-600 hours)
so PAH compounds are unlikely to be degraded in a conventional wastewater treatment
plant. Research in Greece by Samara et.al. [1995] and Manoli et al. [1999], shows that the
lower-molecular mass PAHs are removed effectively in Thessaloniki's WWTS, whereas the
higher molecular mass PAHs are resistant to the biological treatment. The heavy molecular
mass PAHs are partially removed by adsorption, whereas the lower molecular mass PAHs
are removed by volatilisation and/or biodegradation.
81
3. Organic Pollutants
The general consensus of the work done to date indicates that the use of coagulants for
removing organics is feasible. However it is impractical as the excessive addition of
coagulants is necessary.
Humic substances account for around 50% of the dissolved organic matter in natural water
(Vik and Eikebrokk, 1989). They are formed easily from waste material and there is evidence
that they will sorb organic matter by binding with them. Activated carbon is widely used as a
means of removing organic compounds from water. The presence of humic acid reduces the
rate of organics uptake (Kilduff et al., 1988). The capacity of activated carbon for
trichloroethylene (Summers et al., 1989, Wilmanki and Breeman, 1990), trichlorophenol
(Najm et al., 1996) and lindane decreased in the presence of humic substances. Other
sorption media such as organoclays (Dentel et al., 1998, Zhoa and Vance, 1998) and an
organic polymer resin (Frimmel et al., 1999) are not so badly affected by the presence of
humic substances. Ying et al., (1988) studied the effects of iron precipitation on the removal
of natural organic compounds like tannic acid and humic acid, and toxic organic compounds
like chlorendic acid (HET), polychlorobiphenyls (PCBs) and organochlorine pesticides.
Freshly formed ferric hydroxide flocs were very effective in removing humic acid and tannic
acid and it was found that the presence of humic acid enhanced significantly the removals of
PCBs and many of the organochlorine pesticides by ferrous and ferric hydroxide
precipitates. Removals were achieved by a combined mechanism of complexation,
adsorption and co-precipitation. This evidence suggests that humic substances are capable
of sorbing organic material.
A process was devised in which organic contaminants were removed by adding humic acid
and a coagulant such as ferric hydroxide (Rebhun et al., 1998). This showed good recovery
for the organics tested. The results of this work suggest that humic acid might be added in a
tertiary cycle. The humic acid could be made by composting grass cuttings, potato peeling
and other waste feeds. Such material could be added to the final effluent of a wastewater
treatment plant followed by contact and flocculation.
82
3. Organic Pollutants
This data in turn relies upon analysis of these organic pollutants. Present methods using
GC/MS are extremely complex and not suitable for routine plant use. Lack of easier methods
for their analysis will hinder the development of simple processes to remove these organic
materials. It could be argued that identification of a specific pollutant is not crucial for plant
development and that a generic test would be suitable. One of the most important aspects of
future work is the development or identification of simple tests for WWTP analysis. The
problem is not confined to treatment plants alone but rapid treatment methods could be used
to detect sources of heavy organic chemicals.
One of the results of the difficulty in doing analyses is that there is little data available on
partitioning process. There is a suggestion that around half the organics fed to a wastewater
treatment plant remain in the supernatant stream. This might well be a surprising result given
the measured property values in the region of 105 (dimensionless) would suggest that there
would be a good binding between organic pollutants and the settled sludge. It is possible
that there is some competition for sorbtion sites in the organic matter from the more
concentrated organic compounds.
With more rapid analysis techniques in place, there would be the opportunity to make
process changes to reduce the amounts of organics present in the final effluents. It is felt
that advanced oxidative techniques such as the use of ozone would not be applicable in the
present context as the organics have a very small concentration in solution and have a low
reactivity. One interesting possibility is in situ treatment in sewers such as adding activated
carbon to contaminated streams. As humic substances are efficient scavengers for organic
pollutants, humic acid derived from composting food waste could be added in a tertiary stage
to strip organics from the final effluent. It is a matter of policy, to see if such ideas should be
promoted further but initial work could start before the rapid analysis methods had been
agreed.
83
3. Organic Pollutants
However, more recent studies (Melcer et al., 1992) suggest that the stripping of volatiles
may not be as significant as was initially thought and biodegradation during secondary
biological wastewater treatment may be the main mechanism of loss of the potentially
volatile compound types (Table 3.10). For example, Melcer et al. (1992) reported that
biodegradation processes removed ≥90 % of the dichoromethane, 1,1,1-trichoromethane,
trichloroethylene, toluene and xylene from a municipal wastewater. Volatilisation was only a
significant mechanism of removal for 1,4-dichlorobenzene (20 %) and tetrachloroethylene
(60 %). The fate and behaviour of volatile organic compounds in wastewater treatment plant
have been modelled numerically by the TOXCHEM computer-based model that incorporates
four removal mechanisms including: volatilisation, stripping, biodegradation and sorption on
to solids (Melcer et al., 1992).
84
3. Organic Pollutants
• Degradable after a lag phase (eg phenol, 2-aminophenol, 3- and 4-cresol, catechol,
sodium benzoate, 3 and 4-aminobenzoic acid, 3-chlorobenzoic acid, phthalic acid,
dimethyl phthalate, di-n-butyl phthalate, pyridine and quinoline);
• No degradation or gas production (3- and 4-aminophenol, 2-chlorophenol, 2-cresol,
2-nitrophenol, 2- and 4-chlorobenzoic acid, bis (2-ethylhexyl)phthalate, hexylene
glycol, neopentyl glycol, n-undecane, n-hexadecane, 2,4-D, dieldrin, cis- and trans-
permethrin, tetrahydrofuran, furan, pyrrole, N-methylpyrrole, thiophene, benzene,
pyrimidine, 1-naphthoic acid);
• Inhibitory in the initial phase of incubation (eg 3- and 4-chlorophenol, 2,4- and 2,6-
dichlorophenol, 2,4,6-trichlorophenol, 3- and 4- nitrophenol, 2-phenylphenol, 2-, 3-
and 4-nitrobenzoic acid, CTAB, MCPA, MCPP, lindane, naphthalene,
anthraquinone);
• Inhibitory throughout incubation (eg 3,5-dichlorophenol, pentachlorophenol, 2,4- and
2,5-dinitrophenol, 4-nonylphenol, sodium dodecylbenzene sulfonate, sodium 4-
octylbenzene sulphonate, 2,4,5-T, butyltin trichloride, dibutyltin dichloride, tributyltin
chloride).
Degradation is generally aided by carboxyl and hydroxyl groups, whereas chloro or nitro
groups tend to inhibit anaerobic biodegradation and gas production.
Figure 3.3 Typical patterns of net gas production (CH4 + CO2) from organic chemicals
incubated anaerobically with diluted primary digested sewage sludge.
1, Easily degradable; 2, Degradable after a lag period; 3, little effect on gas production; 4,
inhibitory in initial phase of incubation; 5, inhibitory throughout incubation
(Battersby and Wilson, 1989).
100 1 2
Net gas production (% theoretical)
}3
Time 4
Inhibition
-100 5
85
3. Organic Pollutants
metabolites are relatively lipophilic and accumulate in the sludge and are also discharged
with the treated sewage effluent. One of the most important consequences of anaerobic
digestion, however, is the production of nonylphenol (NP), which accumulates in digested
sludge. Approximately 50 % of the NPnEO in raw sewage is transformed to NP in digested
sewage sludge. The loadings of LAS and NP to soil in sewage sludge used on farmland are
significantly larger than for most of the other organic contaminants present in sludge and
there is concern about their potential environmental effects. This is particularly the case for
NP in sludge due to its potential oestrogenic activity (UKWIR, 1997). However, in the aerobic
soil environment, these compounds provide substrates for microbial activity and are rapidly
degraded so there is minimal potential risk to the environment or transfer to the human
foodchain. For example, LAS has a short half-life in soil in the range 7 – 22 days in
temperate field conditions (Holt et al., 1989) and the half-life for NP is <10 days (UKWIR,
1997). Current studies at Imperial College, funded by the Food Standards Agency in the UK,
are investigating the potential for plant uptake of NP into staple food crops from sludge-
treated soil.
Another class of organic chemicals, the phthalate acid esters, are also an abundant group of
compounds present in sewage because of their extensive use as plasticising agents. The
phthalates are also suspected as being potential environmental oestrogens (UKWIR, 1997).
Shelton et al. (1984) reported the complete degradation of the lower molecular weight
phthalate esters, and of butyl benzyl phthalate, within 7 days in laboratory scale anaerobic
digesters operated at 35 oC. Therefore, these phthalate compounds should generally be
removed by most municipal anaerobic digesters at the normal mean retention times
operated in practice (>12 days). The extent and rate of biodegradation during anaerobic
digestion is apparently related to the size of the alkyl side chain and compounds with larger
C-8 group are much more resistant to microbial attack. Therefore, di-n-octyl and di-(2-
ethylhexyl)phthalate (DEHP) are considerably more persistent to anaerobic microbial
mineralisation and are generally not removed by conventional anaerobic stabilisation
processes. However, phthalate esters are rapidly destroyed under aerobic conditions,
usually achieving >90% removal in 24 h in activated sludge wastewater treatment systems.
In soil, the reported half-life is <50 d (UKWIR, 1997).
Thermophilic aerobic digestion processes and sludge storage for three months can achieve
similar overall removal rates for organic contaminants as those obtained with mesophilic
anaerobic digestion (WRc, 1994). Thermal hydrolysis conditioning of sludge prior to
conventional anaerobic stabilisation may have a significant influence on the removal of
organic contaminants from sludge, but this is a comparatively new enhanced treatment
process and effects on the destruction of organic contaminants have yet to be investigated.
86
3. Organic Pollutants
For the main list of organic pollutants considered in this report there is little available data of
the concentrations in the influent to the wastewater treatment plant. Paxéus and Schröder
[1996] looked at over 50 organic compounds, in the influents and effluents of the
Gothenburg wastewater treatment plant. The high cost of testing explains the lack of data on
dioxins in urban wastewater.
Most of these compounds were reduced to below the limit of detection during the treatment
process. Some of the organic compounds, such as caffeine were reduced from a level of
37µg.l-1 to 4µg.l-1. Some of the phosphorus containing compounds were not reduced during
the treatment process (although the influents and effluents were quite low at 1µg.l-1). The
overall toxicity of the influent and the effluent were also measured and found to have
decreased by approximately 50% during the treatment process.
450
400
Dioxin concentration (ng TEQ
100
50
0
1944 1949 1953 1956 1958 1960 1998
Year
Figure 3.4 Dioxin content of archived samples of sewage sludge form Mogden WWTS,
UK
It can be seen (Figure 3.4) that there has been a significant reduction in the concentration of
dioxins since the 1950s and 1960s in sludge over recent years.
The concentrations of other organic contaminants in sludge, including, PCBs and PAHs,
have also declined significantly in sludge in the UK. This is due to the control of primary
sources of these substances. In 1984, McIntyre and Lester (1984) measured median and
99th percentile concentrations for PCBs in sludge (444 samples from UK sewage treatment
works) of 0.14 and 2.5 mg kg-1, respectively. Ten years later, Alcock and Jones (1993)
reported the total PCB content of 12 UK sludges from rural, urban and industrial sewage
treatment works ranged between 0.106 to 0.712 mg kg-1, with a mean value of 0.292 mg kg-
1
. These results indicate that overall PCB concentrations in UK sludges have declined
markedly in response to the ban on industrial production, use and discharge of these
substances. Similar trends are apparent in Germany (Table 3.11). In effect, this means that
the chemical composition of sewage sludge is already subject to stringent, albeit indirect,
controls that have been effective in minimising industrial sources and inputs of persistent
organic contaminants.
87
3. Organic Pollutants
Influent Effluent
(µg.l-1) (µg.l-1)
PAHs Austria:
Total PAHs - EPA15 147-625 20-70 Gans et al.,1999
Germany: Hagenmaier et al,
Total PAHs 0.79 1986
Benzo(a)pyrene 0.08
Benzo(k)fluoranthene 0.05
Greece: Manoli et al, 1999
Benzo(a)pyrene 0.022 0.005
Fluoroanthene 0.24 0.029
Indeno (1,2,3-cd) pyrene 0.015 0.005
France 0.05-0.44 0.02-0.09 ADEME, 1995
Germany 33 Koch et al, 1989 &
Balzer et al 1991
UK 51.8 (5.6 to 30.8 (2.4- Morris et al, 1994
349) 147)
DEHP Austria 4.4 0.3 Hohenblum et al.,
2000
Germany 122 (7-232) 15 (5.6-184) Faltin, 1985
Anionic Italy 290-4800 - Braguglia et al,
Surfactants 2000
Detergents France 1-26 0.1-2.7 ADEME, 1995
LAS Austria 400-3500 11-55 Scharf et al., 1995
Germany 5400 67 Feijtel et al 1995
Greece 129 (35- Kilikidis et al. 1994
325)
Italy 4600 43 Feijtel et al 1995
Netherlands 4000 9 Feijtel et al 1995
Spain 9600 140 Feijtel et al 1995
UK 15100 10 Feijtel et al 1995
NPE Austria: Hohenblum et al.,
Nonylphenol- 2,096,000 363,000 2000
monoethoxylate
Nonylphenol- 13,093,000 639,000
diethoxylate
Italy: Di Corcia et al.
NP 4 1994
NPEO 27
NPEC 145
Sweden 0.5-6.0 Paxéus 1996a
Germany 0.02 0.002 Koppe et al, 1993
88
3. Organic Pollutants
Other organic
pollutants: France 0.1-0.4 <0.1-0.5 ADEME, 1995
Chlorophenols 300
Chlorinated 1.15
organics 10
Pesticides
VOCs
Germany Ternes et al, 2000
Iodinated X-Ray 4.3
contrast 3.3
substances: 0.18
iopamidol 0.17
diatrizoate 1.6
iothalamic acid 7.5
iomeprol
iopromide
Total Phenols Italy 2.5-300 Italian Regional
Environmental
Protection Agency
Dioxins Italy: 0.024-16.9 Italian Regional
Environmental
Protection Agency
PAHs: wastewater from 8 different sewage treatment influents was investigated in 1996 by
the UBA [Gans, et.al., 1999]. Similar PAHs content were determined, except for the influent
from a chemical plant, which had an approximately 1,000 times larger concentration. PAHs
especially, with a low molecular weight were found in high concentrations. Apart from the
higher PAH content of the wastewater from the chemical plant, no significant differences
could be detected between municipal and industrial influents. The PAHs content of the
effluent was about 10 times smaller than the influents [Gans et.al.1999].
The Danish regulation of the application of waste products [Ministry of the Environment and
Energy 1996] sets certain cut off values for the maximum concentrations of organic
contaminants in sludge to be distributed on agricultural land as shown in Table 3.13.
Concentrations of PAHs in Danish sewage sludge are also shown in Table 3.14 The PAH
concentration of the nine selected compounds were all found to have mean concentrations
above the concentrations permissible for use on agricultural land in Denmark.
Danish Standards 1997 - cut off values 2000 - cut off values
mg.kg-1 DS mg.kg-1 DS
LAS 2,600 1,300
nonylphenol (including nonylphenol 50 10
ethoxylates)
PAHs* 6 3
DEHP 100 50
*(total concentration of nine selected PAHs) Acenaphthylene, Fluorene, Phenanthrene, Fluoranthene,
Pyrene, Benzo(b,j,k)fluoranthene, Benzo(a)pyrene, Benzo(g,h,i)perylene and Indeno(1,2,3,-cd)pyrene
The values in bold are difficult to achieve, as they are far below current sludge
concentrations. If 50% of pyrene and phenathrene is from food sources and gives sludge
concentrations of > 300mg.kg -1 ds, then this emphasises how difficult these standards are to
achieve.
The mean concentrations of LAS, NPE and DEHP were found to be within the Danish limits
for use on agricultural land but the range of concentrations in all cases went over the cut off
limits; therefore many of the sludges would not be allowed to be used on agricultural land.
89
3. Organic Pollutants
The concentrations of some of the organic contaminants in the sludge were found to depend
strongly on the wastewater treatment process [Danish EPA]. The concentrations of LAS, NP
and NPE were significantly lower (P<0.005) following activated sludge treatment than in
mixed activated and digested sludge treatment, presumably due to extended aeration.
It can be seen that government and other institutions are trying to introduce limits for certain
pollutants and that concern for wastewater pollution reduction is increasing. Nevertheless, it
is noted that important discrepancies exist in analysis techniques, even within a country,
hence slowing the determination of limits, particularly for PAHs and PCBs. Due to the
expected increase in sludge production and the reinforcing of the legislation in relation to the
concentration limits for potentially toxic elements and organic pollutants, it seems necessary
throughout Europe to harmonise analysis techniques and the pollutants targeted in the
control of wastewater and sludge quality. Discharge standards to UWW collecting systems
for industries and possibly reformulation of certain domestic products should be determined
in order to reduce pollution entry into the systems.
90
3. Organic Pollutants
91
3. Organic Pollutants
92
3. Organic Pollutants
References
1. Berna JL et al, 1989 11. Hohenblum, P, et al 22. Rapaport RA, et al
2. Bodzek, B. et al, 2000. 1990.
1999. 12. Holt MS et al 1992. 23. Rappe et al 1989
3. Bridle, T.R. et al 1983 13. Leschber, R. 1997 24. Scharf, S, et al. 1997
4. Cavelli L, et al 1993 14. Litz. N, et al, 1998. 25. Smith, S.R. 2000
5. Chang, A.G. et al 15. Manoli, E. et al 1999. 26. Statistika
1995. 16. McAvoy DC, et al meddelanden 1998
6. Conseil supérieur 1994. 27. Sweetman 1994
d'hygiène publique de 17. McEvoy & Giger 1986 28. Tørsløv J, et al 1997.
France, 1998 18. McIntyre. A,E, et al 29. UKWIR 1995
7. Drescher-Kaden et al 1984 30. USEPA 1992
1992, 19. Moreda, JM, et al 31. USEPA 1999
8. Eljarrat. E, et al 1999. (1998a) 32. Wahlberg,.C, et al
9. European Union, 2000 20. Moreda, JM, et al 1990
10. Hessische (1998b) 33. Wild. S,R, et al 1989.
Landesanstalt fur 21. Prats D, et al 1993. 34. Braguglia et al 2000
Umwelt (1991-96).
Table 3.15 shows the occurrence of certain organic pollutants in sewage sludge in Germany.
Compound Occurrence
in sludge
Benzo(a)anthracene +++
Benzo(a)pyrene +++
Benzo(k)fluoranthene +++
Dibenzo(a,h)anthracene +++
Indeno(1,2,3-cd)pyrene +++
PCB-1242 ++
PCB-1254 +++
PCB-1221 ++
PCB-1232 ++
PCB-1248 ++
PCB-1260 +++
PCB-1016 +
2,3,7,8-Tetrachlordibenzo-p-dioxin ++
Frequency of occurrence: +++ frequent (90-100%), ++ less frequent, + low frequency
93
4 Health and Environmental Effects of Pollutants in UWW and SS
Copper, Cr, Zn, Se, are essential trace elements, however, they are potentially toxic
elements, and above certain concentrations, may interfere with or inhibit the actions of
cellular enzymes. Effects are summarised in Table 4.1, together with the Maximum
Concentration Limits (MCL) in drinking water (Source: EPA and WHO).
Potentially toxic elements at high concentrations, are acutely toxic to humans. High
concentrations are rare in urban waste water, but could possibly result from accidental spills,
although there is limited exposure from this route. The major concern is exposure to low
concentrations over longer time periods. This is chronic exposure and may have more subtle
effects.
The chemical form and corresponding bioavailability of potentially toxic elements to plants,
fungi, micro-organisms and animals are also important, affecting regulation regarding the
compound. Complex dietary interactions are inherently protective limiting the accumulation
of metals in animal body tissues (see Case Study a). The phytotoxic concentrations of Zn
and Cu in plant leaves less than the zootoxic concentration of these elements in plant
produce consumed by animals and humans. Technically based, precautionary soil limit
values for these metals protect crop yields and the human diet from the potentially toxic
effects of metals in sewage sludge, see Case Study (a).
94
4 Health and Environmental Effects of Pollutants in UWW and SS
Table 4.1: Summary of the acute and chronic effects of the pollutants
PTE Drinking Water Acute Health Effects Chronic Health Effects Carcinogenicity Notes
Standards
EU WHO US
EPA
Cu 0.1-3 2 1 Irritation of mouth and throat, Liver and kidney damage, "pink disease", No evidence
mg.l-1 mg.l-1 mg.l-1 headaches, dizziness, nausea, cirrhosis
diarrhoea, gastric ulcers,
jaundice, renal damage, death
Zn 0.1-5 5 Stomach and digestion Immune system damage, and interferes No evidence Taken up by plants,
mg.l-1 mg.l-1 problems, dehydration, impaired with the body's ability to take in and use phytotoxic
muscular coordination other essential elements such as copper
and iron
Cd 0.005 0.003 0.005 Digestive tract irritation, colitis, Half-life = 10-40 years. Lung, kidney, and Strong evidence in Taken up by plants,
mg.l-1 mg.l-1 mg.l-1 vomiting, diarrhoea, death. hematopoietic system damage due to build animals, weak phytotoxic
up, fragile bones, anaemia, nerve or brain evidence in
damage in animals humans
Cr 0.05 0.05 0.1 Allergic responses in skin, Damage nose and lungs, increases risks of Evidence in High potential for
VI mg.l-1 mg.l-1 mg.l-1 chromium VI irritates nose, non-cancer lung diseases, ulcers, kidney, humans and bioaccumulation in
lungs, stomach, and intestines, and liver damage. Birth defects and animals aquatic organisms
convulsion, death reproductive problems in mice
Hg 0.001 0.001 0.002 Nausea, vomiting, diarrhoea, Brain, lung, kidney, and damage to Evidence in mice Binds to dissolved
mg.l-1 mg.l-1 mg.l-1 increase in blood pressure, skin developing foetus, neurological disorders, matter not
rashes, eye irritation, renal depression, vertigo, and tremors phytotoxic, High
failure potential for
bioaccumulation in
aquatic organisms
Ni 0.05 0.02 0.04 Allergic reactions, lung damage Chronic bronchitis and reduced lung Evidence of lung Phytotoxic, very
-1 -1 -1
mg.l mg.l mg.l function, lung disease. Affects blood, liver, and nasal sinus mobile in water
kidney, immune system, reproduction and cancers in
development in mice and rats humans
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4 Health and Environmental Effects of Pollutants in UWW and SS
Pb 0.05 0.01 0.015 Anaemia, constipation, colic, Non-specific: damage to nervous system, Evidence in Not usually
mg.l-1 mg.l-1 mg.l-1 wrist and foot drop, renal kidneys, and immune system. In children, animals phytotoxic,
damage. In children, symptoms can cause decrease mental ability and bioconcentration in
are irritability, loss of appetite, reduced growth. In adults, can cause a shellfish
vomiting, and constipation. decrease in reaction time and affect
memory, miscarriage, premature births, and
damage to male reproductive system
As 0.05 0.01 0.05 Nausea, vomiting, diarrhoea, Skin keratosis, decrease in the production Evidence in Taken up by plants,
mg.l-1 mg.l-1 mg.l-1 damage to tissues including of blood cells, bone marrow suppression, humans, of which are sensitive
nerves, stomach, intestines and abnormal heart function, liver/kidney increased risk of to lower
skin, damage, impaired nerve function, damage liver, bladder, concentrations than
to foetus in animals kidney, and lung animals,
cancer, may inhibit bioaccumulation in
some DNA repair fish and shellfish,
mechanisms persistent in the
environment
Ag 0.01 - 0.05 Breathing problems, lung and Argyria and may affect brain and kidneys No evidence
mg.l-1 mg.l-1 throat irritations, and stomach
pains, allergic reactions,
necrosis, haemorrhage, and
pulmonary oedema
Se 0.01 0.01 - Dizziness, fatigue, irritation, Brittle hair, deformed nails, and loss of Suspected human
mg.l-1 mg.l-1 collection of fluid in lungs, feeling and control in arms and legs, carcinogen: liver
bronchitis, rashes, swelling, reproductive effects in rats and monkeys, and lung tumours
and birth defects in birds observed in rats
and mice
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4 Health and Environmental Effects of Pollutants in UWW and SS
Over 6,000 organic compounds have been detected in raw water sources many of which are
due to commercial activities. These compounds are present in many industries, processes
and by-products, and are wide spread in a number of domestic products. They may also
enter wastewater from surface run off. LAS and NPE are widely used in detergents and are
ubiquitous in the environment.
Examinations of the surfactant toxicity revealed that anionic and non-ionic surfactants are
non-toxic to man upon oral intake, but can be very toxic for marine life. Table 4.2 shows the
toxicity of anionic and non-ionic surfactants [Berth and Jeschke, 1987]
Table 4.2 Toxicity of anionic and non-ionic surfactants [Berth and Jeschke, 1987]
Surfactant Toxicity
LD50 fish (mg/l) LD50 Daphnia (mg/l)
LAS 3 - 10 8.9 - 14
NPE 1.5 - 11 4 - 50
Sewage sludge is treated to reduce its fermentability, nuisance (particularly odour) and
vector attraction potential as well as to reduce bulk and improve its physical characteristics
to aid handling, dewatering and acceptability for use on agricultural land. These techniques
include physical, chemical and microbiological manipulation of the sludge and may involve
mechanical dewatering, heating, chemical reactions and microbiological transformation
processes that may influence the loss, or potential formation, of organic contaminants. Loss
mechanisms include (Wild and Jones, 1989; Rogers, 1996):
• Volatilisation;
• Biological degradation;
• Abiotic/chemical degradation eg hydrolysis;
• Extraction with excess liquors;
• Sorption onto solid surfaces and association with fats and oils.
Some chemicals are more susceptible to these transformation/loss mechanisms than others
and certain treatment processes can increase the concentration of conservative compounds
that are retained as volatile solids are removed during stabilisation action are due to the
formation of stable reaction intermediate compounds.
Sewage sludge potentially contains thousands of organic compounds derived from industrial,
domestic, atmospheric and natural dietary sources. The total organic matter content of
sludge is typically in the range 60-80%, depending on the extent of stabilisation treatment
and volatile solids destruction. The vast majority of the organic content is environmentally
benign material that confers part of the agronomic benefit associated with sewage sludge
use on farmland by improving the physical and structural characteristics of treated soil.
However, certain anthropogenic compounds are potentially toxic and would be detrimental to
human health if they were to transfer from sludge-treated soil to the foodchain in
toxicologically significant amounts. The range of organic compounds known to exist in
sludge is extensive and diverse. For example, Drescher-Kaden et al. (1992) reported that
332 organic substances, with the potential to exert a health or environmental hazard, had
been identified in German sludges and 42 of these were regularly detected in sludge.
The main route of entry of environmental contaminants into the human foodchain is by
uptake into the edible parts of crop plants. However, despite the increasing intensity and
extent of scientific investigation into the potential environmental consequences of organic
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Chlorinated paraffins – There are >200 commercial chlorinated paraffin formulations in use
as plasticisers in PVC and other plastics, extreme pressure additives, flame retardants,
sealants and paints. Total production of short chain paraffins in the EU is approximately
15000 t y-1. Illicit disposal of oils containing paraffins into the wastewater system may be a
significant route of entry into the environment. Approximately 50 % of the lubricating oils
used by industry in Sweden may be released into the air or WWTS.
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4 Health and Environmental Effects of Pollutants in UWW and SS
concentrations of the TeBDE and PeBDE congeners were present in sludge (15 and 19 µg
kg-1, respectively).
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4 Health and Environmental Effects of Pollutants in UWW and SS
Synthetic fats – In addition to Alcock’s list there have been recent concerns in the US about
synthetic fat substitutes that are used in food products. These compounds are not toxic to
humans, but are persistent and are not biodegraded in sewage and sludge treatment or in
soil (pers. com. T.J. Logan, N-Viro, USA).
Pharmaceuticals are covered in more detail in Case Study (d). Some of the bodycare
products are covered in more detail in Case Study (e).
Polyelectrolytes
Polyelectrolytes based on polyacrylamide and cationic copolymers are used extensively in
sludge treatment to aid dewatering. The polyelectrolyte concentration in mechanically
dewatered cakes is relatively high and typically in the range 2500 – 5000 mg kg-1 ds.
Furthermore, they only degrade relatively slowly by abiotic processes in cultivated soil at a
rate of 10 % per year (Azzam et al., 1983). Acrylamide is a common monomer associated
with polyelectrolytes and is potentially toxic to humans and is a reported carcinogen (IARC,
1994). Concern about the implications for human health from the residual monomers in
polyelectrolytes used in drinking water treatment has resulted in them being withdrawn from
this application in Japan and Sweden, and stringent controls on their use are in place in
Germany and France (Letterman and Pero, 1990). These factors give rise to potential
environmental concerns about the long-term accumulation of polyelectrolytes in sewage
sludge and sludge-treated soil.
The limited available evidence suggests that no environmental problems have been
identified from the application of polyelectrolytes to soil. Acrylamide monomer residuals are
rapidly biodegraded in the environment and are unlikely to represent a risk to human health
in sludge (Gustavsen, 1998). Furthermore, polyelectrolytes are frequently applied directly to
soil as soil conditioning agents to maintain soil structural conditions and as a carrier gel for
fluid drilling pre-germinated seeds in agricultural and horticultural practice (Fordham and
Biggs, 1985). In the fluid drilling technique seedlings of sensitive pregerminated crops
emerge directly from the injected polyacrylamide gel. This practical example illustrates that
polyelectrolytes do not have a phytotoxic action in soil. An investigation of the potential
impacts of polyelectrolytes on nitrification processes in soil (Cartmell et al., 1998) showed no
effect on nitrate accumulation at ten times the normal rate of addition of polyelectrolyte to
soil in sludge, but nitrification was partially inhibited when the dose was increased to 100x
the normal input. Polyelectrolyte was added directly to soil in this study to assess the worse-
cased effects on nitrification processes in a controlled laboratory incubation. In practice,
however, polyelectrolyte compounds are strongly sorbed to the sludge solids and this is
likely to significantly reduce their availability and potential toxicity to soil microorganisms.
Compared to metals, organic pollutants have only recently been identified as having
potential adverse human health effects. Most organic pollutants are present in the
environment at very low concnetrations. Exposure to these compounds, for example through
drinking water, is very low. However, as some of these compounds may bioaccumulate or
have effects at low concentrations chronic health effects are starting to be investigated for
some of these compounds. Table 4.3 presents acute and chronic health effects of the major
organic pollutants covered in this report, and the limits set for these compounds in drinking
water.
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4 Health and Environmental Effects of Pollutants in UWW and SS
Table 4.3 Summary of health effects for organic pollutants
Compound MCL in Drinking water Acute Health effects Chronic Health effects Carcinogenicity Notes
EU WHO USEPA
DEHP 10 µg.l-1 8 µg.l-1 6 µg.l-1 Usually low acute Damage to liver and Some evidence in Synthetic substance,
Emulsified toxicity: mild testes, reproductive rats and mice, adsorbs to soil and
Hydro- gastrointestinal effects, birth defects mutagenic at high sediments,
carbons disturbances, doses bioconcentrates due to
nausea, vertigo lipophilicity
PCBs 1.0 µg.l-1 0.5 µg.l-1 Acne-like eruptions Similar to acute Some evidence in Adsorbs to soil and
Organo- and pigmentation of poisoning: irritation of rats sediments, persistent,
chlorine the skin, hearing and nose, throat, and GI bioconcentrate, and
vision problems, tract, changes in liver accumulate in fat
spasms function and
reproductive systems
PAHs 0.2 µg.l-1 0.7µg.l-1 0.2 µg.l-1 Red blood cell Developmental and Some evidence from Adsorbs to soil and
Benzo(a Benzo(a) damage, anaemia, reproductive effects, humans and animals sediments, weak
)- - suppressed immune birth defects degradation, lipophilic,
pyrene Pyrene system bioaccumulate
LAS 200 µg.l-1 Gastrointestinal Kidney and liver toxicant Synthetic compound, toxic
Surfactants problems to marine life: LC50= 3-10
mg/l, biodegrades easily in
aerobic conditions, no
accumulation in sediments
and biological tissues
NPE 200 µg.l-1 1-5 µg.l-1 Allergies, endocrine Has an oestrogenic Lipophilic, mainly affects
Surfactants disrupting chemical effect on fish aquatic organisms,
partially biodegraded in
the environment
metabolites are very toxic
and persistent
PCDD/PCDF 0.00003 Chloracne, rashes, Thymic atrophy, damage Lymphoma, Highly volatile, binds to
µg.l-1 discoloration, to the hormonal and melanoma in soil and particles,
USEPA excessive body hair, immune systems, humans, can accumulates in fat,
website large species spontaneous abortions, increase risk of persistent, birth defects in
differences in toxicity, alteration in glucose several types of animals
very specific metabolism cancer in man.
EU: Water treatment directive
WHO:Guidelines for drinking water quality Vol.2 (1996).
USEPA:Standards for maximum permissible values in sewage sludge/soils. Estimating concern levels for concentration of chemical substances in the enviroment. Washington
DC (1984). USEPA website: http://www.epa.gov/safewater/mcl.html
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and organic pollutants content in wastewater and sewage sludge
Because of this, a variety of instruments have been attempted at national level, with varying
success, on different levels to reduce UWW pollution closer to at source. These instruments
are consistent with an overall strategy of waste minimisation, polluter pays, and reduction at
source and include individual regulatory, economic and voluntary and educational
instruments.
Table 5.1 Summary of Available Instruments
Instruments Regulation Economic Voluntary Educational
The following selected examples demonstrate strategies for the minimisation of waste at
source through these instruments:
• Regulatory Instruments:
• The Prohibition of Mercury Clinical Thermometers in France
• Economic Instruments:
• Wastewater Tax in Germany
• Charges on Cadmium in Fertilisers in Sweden
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5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge
The use of traditional command and control instruments involves licensing of the use and
discharge of material to UWW. This approach is notoriously difficult to monitor and control
effectively. In the case of particularly difficult pollutants, targeted product bans can be a more
cost effective solution where clear alternatives are available and the production of the
material in question is relatively easy to regulate.
Mercury is used in a broad area of applications. Industrial uses of mercury may be found in
the electro-technical industry to produce batteries or fluorescent tubes or in dental practices
for fillings. Other industries require mercury for the production of instruments such as
manometers, barometers and thermometers. It is estimated that the total production of
mercury in France for industrial productions amount to an average of 60 tonnes per year.
Impact: Mercury is of particular health concern for not only are humans exposed to mercury
directly when the product breaks, but they also may be exposed after it is disposed and
accumulates in UWW and sludge. It can also leach from landfills through the water waste
pathway or be directly released in the wastewater system after disposal in sinks and toilets –
raising concern for the risk of human exposure and environmental contamination. It is also
estimated that before the introduction of the ban on the marketing of clinical mercury
thermometers, an average of 15 – 20 million mercury-thermometers were in circulation in
France. These are equivalent to 12 tonnes of mercury – about 20% of the yearly amount
produced. It is also estimated that an average 1.5 – 5 million of these thermometers were
broken every year, releasing between 3 and 10 tonnes of mercury in the environment yearly
and causing significant health and environmental concern. (Romp, 1993 in Öko Institut,
Berlin).
Measure: Under the new French regulation [Arreter of 24 December 1999, Journal Officiel,
31 Decembre], the marketing of clinical mercury thermometers is prohibited both nationally
and at EU level, as from March 1, 1999. However, the enactment does not prohibit export to
non-EU nations. The main objectives of the ban being that of minimising mercury waste and
prevent its release into the environment, hence reducing risk to humans.
Costs: Although difficult to evaluate precisely, the implementation of the regulation resulted
in two types of costs: 1) Reprocessing Costs associated to the reprocessing mercury
thermometers and 2) Replacement Costs for the purchase of new (electronic or eardrum)
devices. The average cost of an electronic thermometer ranges between 11 and 30 EURO
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and organic pollutants content in wastewater and sewage sludge
per unit, whilst a professional device costs around 305 EURO. The cost of an eardrum
thermometer (an infra-red device) ranges around 69 EURO. The professional timpanic
device costs between 305 and 610 EURO. Assuming that at least 15% of mercury
thermometers are collected in the first year, the total cost of the scheme amounts to about
3.81 million EURO.
Effectiveness: Although still at its early stage, the ban has been very successful and other
nations such as Germany and Sweden are already following similar policy measures. It is
estimated that the ban will reduce mercury waste by 12 tonnes a year – a reduction of 20%
of the total annual mercury production in France. However, such action should also be taken
for other industrial sectors using mercury - and French policy is seemingly moving towards
this direction – so as to further minimise the quantity of mercury present in the environment
and reduce the risk to human health and the environment.
Economic Instruments
Economic instruments may be used to provide a continuing incentive for reduced use of a
material and even product substitution. Nevertheless; evidence suggests that taxes and
charges need to be carefully designed and targeted so as to promote continuing waste
reduction. The social and economic implications of taxes and charges may make their
introduction controversial, and the costs of their administration can make them as complex to
administer as command and control regulation.
This measure is a “downstream” charge on discharges, and demonstrates how the creation
of economic incentives alone may not be more effective in promoting reductions than
command and control measures.
Measure: The Federal Wastewater Tax was adopted in September 1976, comprising a tax
on sewage discharges; the amount payable was established on the basis of the amount and
harmfulness of the waste. The objective of the tax was better regulation of discharges and to
promote a reduction in wastewater pollution over all
Measure: An important reason for the introduction of the cadmium charge was that it creates
an ongoing incentive to reduce the concentrations (Swedish EPA, 1991) in fertilizers. Since
November 1994, the charge rate is SEK 30 (EURO 3.3) per gramme of cadmium if the
cadmium content exceeds 5 mg per kg phosphorus (about 2.2 mg Cd per kg P2O5) (Swedish
EPA, 1997).
Impact: According to the Swedish Board of Agriculture, the content of cadmium in fertiliser
has gradually fallen from 35-40 mg Cd per kg phosphorus (before the introduction of the
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5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge
charge) to about 23 mg in 1994/95 and 16 mg in 1995/96. The Board conclude that the Cd
charge in combination with the demand (for a low content of Cd in fertiliser) by the
agricultural sector has kept Cd levels on a low level (Jörnstedt, 1998). Drake and Hell-Strand
(1998) concluded that the combination of governmental policy (including the charge and a
standard) and voluntary efforts has been successful in reducing the content of cadmium in
phosphorus fertilisers. However, it was not possible to estimate the relative importance of
the different measures.
Costs: State tax gross revenues in 1996 were around 10 million SEK (1 million EURO), and
the administrative costs are estimated to be around 1% of the gross revenues (Drake and
Hellstrand, 1998). The tax is administrated by the National Tax Board, together with the tax
on nitrogen. Importers and producers report quantities and contents every month. The only
control made seems to be ‘tax audits’ (concerning the accounting of the firms involved). In
1999, 25 such audits were performed (corresponding to about one ‘man-year’). The
authorities do not measure the actual cadmium content of fertilisers. Some problems with
illegal imports by small firms of fertilisers from Poland and the Baltic states (probably of
Russian origin) are reported (Jörnstedt, 2000).
For the businesses using chlorinated solvents, currently only two main options are available
to deal with the waste: regeneration of the solvent (10%) and incineration (90%). The
problem with regeneration is that the process may affect the added stabilisers, which are
required for the stability of the solvent at high temperature and humidity. Hence, it is
necessary to treat the regenerated solvent with new stabilisers. Nevertheless, it is usually
cheaper than destruction of the waste, which in France costs around 4100 FF per tonne.
However, generally only larger firms employ this solution.
Measure: Associations have been created in the dry cleaning sector in order to organise
widespread regeneration of solvents, and these are starting to cover other solvent using
sectors. These organisations co-ordinate the collection and treatment of wastes. The
Agences de l'Eau subsidise dry cleaners who adhere to these associations in order to help
finance the cost of the collection of their wastes.
Costs: A typical dry cleaning facility produces 400 kg of chlorinated waste per year and the
cost of collection and treatment is around 3500 FF per year, which represents about 1% of
their revenue [ADEME, 1995].
Some instruments amount to an indirect subsidy to industry, others enforce the polluter pays
principle by creating an incentive to manage waste through the adoption of producer
responsibility, as in the packaging waste directive. The following examples include a range
of instruments adopted by government and industry in cooperation, including targeted
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and organic pollutants content in wastewater and sewage sludge
This measure constitutes a specific drive and effort by authorities to collect dangerous and
harmful waste from homes. While effective in its own terms it is not a long-term solution to
the problem of discharges to UWW. It may be effective to deal with continuing risks of
contamination from smaller and diffuse sources, and be used in connection with the adoption
of a longer-term waste minimisation and collection strategy and public education campaign.
Measure: One of the first targeted waste collection initiatives carried out in France was in
1989, where 11,500 kg of waste products were collected over 16 days (see Table 5.2).
Costs: A more recent example is given by the 2 day collection in 1994 in the area of
Boisset-Gaujac (Gard) where 114 kg of chemical products, 169 kg of paint, 12 kg of
aerosols, 27 kg of solvents, and 29 kg of pesticide products were collected and dispatched
separately for treatment at a cost of about 12,000 French francs [ADEME, 1997]1.
Effectiveness: Experience has shown that is it more efficient to appropriately equip waste
reception centres for handling special wastes rather than organising random collection days.
In contrast to targeted waste collection, the adoption of a comprehensive waste minimisation
strategy directed at particular sectors has demonstrated longer term and verifiable results.
This is another example of targeted intervention by public authorities, this time engaging a
particular sector in the long-term management of industry specific problems.
Italy is the principal European location for the leather and tannery sector in terms of
establishments, employment and production. Tanneries are mostly small and medium sized
enterprises, with only 10% of them employing more than 20 people. The industrial area
covered by the plan is located in the Valle del Chiampo, in the province of Vicenza. The area
embraces 10 municipalities, of which Arzignano is the most important with more than half of
the tanneries. The tannery area is the largest in Europe and supplies 50% of the Italian
production. Manufacturing includes shoes, furniture and other leather goods (Vicenza Dept.
of Environment, 1997)
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5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge
being chromium III, sulphur, chlorides, solvents and organic wastes. (Vicenza Dept. of
Environment, 1997). The tanning process comprises two phases - covering and fixing, where
the pelts are sprayed with paints and chemicals for treatment. It is estimated that around
80% of the solvents used become hazardous waste and 1997data from the Dept. of
Environment of Vicenza indicate that the solvents used for the finishing process amount to
20.000 tonnes per year, 85% for the covering phase, 15% for the finishing phase. Metoxy
propanol is the solvent most used in tanneries and is classified as Class III hazard
substance under Italian law, which has 5 classes of hazardous substances for which
maximum allowed emissions are set.
Measure: In 1997, the Dept. of Environment of Vicenza introduced new measures to tackle
the environmental problems of the spray finishing process. The intervention focused on two
main aspects: 1) the introduction of innovative machinery, such as the more efficient low
pressure airbrushes or high pressure airless brushes instead of high pressure devices; plus
2) the use of chemicals dissolved in solution. ‘Gruppo Conciario Veneto’ a tannery
association comprising 4 companies (La Veneta, Conciaria Adriatica, Sacpa and Veneta
Conciaria Valle Agno), with a total of 340 employees, 26.500 m2 of indoor plant and a 1997
turnover of 103 million. EURO, adopted a scheme reducing use of, and ultimately replacing,
the solvent metoxy propanol with alternative substances. Other substitutes are currently
being tested.
Effectiveness: As a result of the waste minimisation scheme, the use of Metoxy was
significantly reduced from 7,300 kg in August 1998 to 1,300 kg in December 1998 (- 82%),
but has been replaced by the less hazardous isopropyl alcohol (Class IV), which has in turn
increased in consumption. However, the total quantity of solvent used decreased from
10,650 kg to 5,007 kg per month (- 53%) and therefore less toxic waste has been generated
and released by the tannery (no quantitative data available).
Costs: The reduction in utilised solvents also brought significant economic benefits, with a
reduction in monthly consumption equivalent to 64%, from 10,590 EURO in August 1998 to
3,794 EURO in December 1998. These economic savings appear to be the main incentive
and persuasive tool to company innovation.
These cases are further examples of targeted intervention at the local level, representing a
programme of sources and discharge identification, and the first example of a truly
“voluntary” initiative through the adoption of negotiated approaches to the reduction of
problematic discharges.
Measure: Anjou Recherché has studied five regions of France which have full statistical data
and 34 UWW collecting systems. This research programme allows many SME polluters to
be identified. Following the identification of industries that are potential polluters, a contract
is drawn up between local industry and the mayor of the area. The contracts are called
special conventions for discharge, and about 2000 have now been set up, mainly in the
South West region of France around Toulouse. The contract determines pollution reductions
and modifies discharge conditions into the UWW collecting system.
In Tours the "eaux industrielles" initiative was established in 1988. This initiative aimed to
control the quantity of discharges into the UWW collecting system based on monthly
analyses on the sludge quality are carried out to control for pollution. In 1996 it was found
that copper and mercury concentrations were very close to the recommended limit and much
higher than the averages for France (Table 5.3).
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and organic pollutants content in wastewater and sewage sludge
Table 5.3 Average concentrations (g t-1) in potentially toxic elements in the Tour
sludges [from ADEME, 1997] *French Standard NF U 44 041
Visits to the businesses potentially capable of releasing copper were undertaken and it was
found that the problem initiated from a mirror manufacturing company. Effluents were
composed of degreasing waters, discharges from the silver and copper adding steps.
Certain observations were made: the neutralising pH in the treatment of the degreasing
waters was not alkaline enough to precipitate the metals and the pH was not checked
regularly enough. Thirty days after this intervention, the copper concentration showed
significant reduction. For mercury, medical activities were investigated, as seen with the
Anjou Recherché Case Study and it was discovered that the pollution was mainly due to
discharges from two hospitals and one analytical laboratory.
Effectiveness: As the WWTP receives less contaminated wastewater, the manufacturer pays
less for the treatment of wastewater. Furthermore, it avoids the cost of landfilling the sludge,
as it can then be used in agriculture, decreasing overall costs.
In Denmark, about 45 industries perform wet treatment of textiles, i.e. pre-treatment, dying,
printing and/or after treatment. The majority of these companies are located in the County of
Ringkjøbing. This type of business consumes large amounts of water, energy and
chemicals.
Measure: The County of Ringkjøbing, in close collaboration local authorities and the
Federation of Danish Textile and Clothing Industries set up a working party to launch and co-
ordinate evaluation of chemicals used in the textile dye process. This working party
established a score system to govern chemicals. The score system is based on four
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and organic pollutants content in wastewater and sewage sludge
parameters. Parameter A represents the estimated amount of the chemicals discharged into
the environment as wastewater. Parameter B is a score on biodegradability, C is a score on
bioaccumulation, and D is a score on toxicity. Importantly, a lack of information about a
certain product will automatically result in a high score. The score system was implemented
in 1992-1993 and the dye works in the County of Ringkjøbing undertook to inform the
supervisory authorities about their consumption of chemicals according to the score system.
The reporting system allows both administrators and company managers to select priority
chemicals and subject them to close examination, on the basis of information filled in the
chemical supplier’s specification sheets. For example, in "Egetæpper a/s" a company which
dyes and manufactures tufted carpets produces an annual score report. This report is used
by the company and the local environmental authorities scope environmental problems,
analyze the consumption patterns, and to find opportunities for product substitution and
cleaner production technologies. In particular, the company's purchasing policy requires an
environmental impact assessment , including the score allotted, before products are bought..
Impacts: The number of products with a high score used in the production at Egetæpper
a/s has been reduced considerably between 1992 and 1997. This is partly because some of
the products are no longer used by the company and partly because huge efforts have been
made in order to procure missing data on the effects these products have on the
environment. Egetæpper a/s' environmental report from 1995, the consumption of dye stuffs
and excipients has been listed and in this report it is stated that:
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and organic pollutants content in wastewater and sewage sludge
Measure: Centre d’Information sur l’Eau based in Paris launched a campaign to alert people
to the problems caused by disposing of compounds down the sink or the toilet. In order to do
so, they distribute a leaflet where they note that the following substances should not be
disposed of into UWW which include;
The leaflet also stresses that collection systems are in place in many areas and that
information about these is available, and that using a waste disposal unit when connected to
the UWW collecting system is prohibited, as is discharging rainwater from gutters into the
UWW collecting systems when a separate system is in place in the area. The centre had
over 7000 enquiries in 1998.
Measure: Eco-labeling. Initiatives such the ‘Nordic Swan’ and ‘Good Environmental Choice’-
were developed by the Swedish Society for Nature Conservation (SSNC) and the Danish
Society for the Conservation of Nature (DSCN) respectively. These were aimed at phasing
out undesirable chemicals in washing powders and have significantly reduced the use of p
LAS (Linear Alkyl Benzene Sulphonate), and Nonylphenol. Eco-labelling campaigns were
launched by both the SSNC and DSCN, against washing powders containing LAS, whilst at
the same time promoting the use of ‘Swan’ or ‘Good Environmental Choice’ labelled washing
powders. In the past decade, the eco-label ‘Good Environmental Choice’ has become one of
SSNC most important tools for dealing with environmental problems. The initial campaign
was launched in 1988 with the publication of one of many green consumer guides, which
included information about household chemicals - some of which were found to be
replaceable with more suitable alternatives.
Use: LAS is the most important surfactant used in Europe and is found in considerable
quantities in washing powders (up to 50%). Some 300000 tonnes of LAS were sold in
Europe in 1999, but concerns for its environmental threat have risen since LAS is toxic to
aquatic animals and plants. LAS is only degradable in the presence of oxygen, which is not
always present in wastewater treatment plants. In addition, it is estimated that about 15-20%
of the amount of LAS entering a water treatment plant ends up in sludge with no further
degradation (S. Hagenfors, 2000).
Effectiveness: Products which do not contain LAS or Nonylphenol and have gained
considerable market share since the launch of the campaign. “In Sweden, products with this
label accounted for 95% of sales by 1997 and consumer choice lead to a decline in use of
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5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge
LAS from 6,300 tonnes per year to 260 tonnes per year” (Danish Environmental Agency
2000). The published guide was a success and prompted consumers to demand for more
detailed information about domestic products and their potential environmental impact.
Coincidentally one the main environmental issues in the region at the time was that of
widespread eutrophication of Scandinavian water bodies which subsequently induced a
demand by consumers for environmentally friendly products. In brief, public awareness
made the market for eco-labelled products grow in Sweden, so that after the first
manufacturer (Unilever) launched its eco-labelled detergent, other multi-nationals had to
follow.
In Sweden, eco-labelling has however been limited in terms of product range and multi-
national manufacturers have not introduced other eco-labelled products, with the exception
of a few minor producers that specialise in ‘green’ products. In other Scandinavian countries,
the market share of ‘Swan’ products is significantly smaller, with 15% in Finland and less in
Norway and Denmark; the difference in share thought to be due to less public awareness
campaigning. Yet, in the last ten years, the Swedish market for eco-labelled products has
undergone important modifications. It is estimated that presently 60% of the chemical
ingredients in soap, shampoo, detergents have been substituted or removed, the remaining
40% of chemicals falling within the list of substances approved by the ‘Swan’ and ‘Good
Environmental Choice’ guidelines. The 38000 tons of chemicals subject to substitution have
been replaced by 29000 tons of approved substances, the difference (9000 tons) having
been removed. The substitute chemicals are all approved by eco-labels and are more
biodegradable in sewage treatment plants and sludge, meaning less environmental risk and
less treatment costs. As a result, it is estimated that the use of LAS in Sweden has been
reduced by 95% (S. Hagenfors, 2000).
In addition, the development of the eco-label ‘Swan’ has prompted Stockholm Water Co. to
initiate a plan for the identification of measures to reduce hazardous household wastes being
flushed down the drain and into WWTP. This lead to the establishment of ‘environmental
stations’ or collection points and to the launch of a thorough public awareness and
information campaign about the impacts of household products on the aquatic environment
In 1996, the trophy ADEME "Economic and clean technologies" went to the STEN society,
which is a metal finishing company which managed zero cadmium discharges by
concentrating the cadmium-containing effluents through evaporation and recovered the
metal through electrolysis [ADEME, 1997].
5.6 Conclusion
The review of National Practices with respect to UWW demonstrated a range of problems,
and identified some strategies for dealing with diffuse and small-scale sources of water
pollution.
Without upstream control, UWW treatment cannot treat all wastewater pollutants, resulting in
effluent and sludge quality problems. A range of measures are likely to be most effective in
mitigating problems, and the appropriate policy mix will vary according to the pollutant,
industry structure, local conditions and social factors, and there should be room for local
discretion.
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5. Review of EU and national measures to reduce the potentially toxic elements
and organic pollutants content in wastewater and sewage sludge
alternatives will be pursued through the use of subsidies to waste reduction or collection.
Targeted Voluntary and Educational Initiatives may assist but the full costs and benefits of
specific instruments are difficult to assess.
Full Cost Recovery for Waste and Water Services (under the Water Framework Directive)
will assist in making the costs of dealing with particular pollutants more transparent.
Nevertheless, the use of economic and alternative instruments and strategies should be
recognized as the legally appropriate implementation measures in both EU and National
Legislation, and the competent authorities should be legally empowered to establish and
participate in alternative measures, including substitution and recovery schemes.
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6 CASE STUDIES
(e) Personal Care Products, Fragrances in Urban Waste Water and Sewage
Sludge
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Section 6. Case Studies
Introduction
The platinum group of metals (PGMs), sometimes referred to as the platinum group
elements (PGEs), comprise the rare metals platinum (Pt), palladium (Pd), rhodium (Rh),
ruthenium (Ru), iridium (Ir) and osmium (Os) and are naturally present in a few parts per
billion (µg/kg) in the earth’s crust. The elements are noble chemically unreactive metals, and
are found in nature as native alloys, consisting mainly of platinum.
Recently these metals have gained importance as industrial catalysts including vehicle
exhaust catalysts (VECs). This use and possible implications for human health were the
subject of an earlier review undertaken by Imperial College, London for the UK Department
of the Environment (Farago et al, 1995; 1996).
Increasing understanding of the environmental damage of vehicle emissions has led to the
introduction of stringent emission control standards throughout the western world. Since
1974 all new cars imported or produced in the United States have had catalytic convertors
fitted, cutting down hydrocarbon and carbon monoxide emissions. In 1977 they were fitted to
a substantial proportion of all cars sold in America, where at the time, this application
accounted for 32% of the total Pt usage (Herbert, et al., 1980).
Vehicle exhaust catalysts have also been used in Japan since 1974. Vehicle exhaust
catalysts were also introduced in Germany in 1985, in Australia in 1986, and into the UK at
the beginning of 1993 in response to the emission standards equivalent to the US standards
which were introduced in the EC at that time. Other uses of PGMs are noted in later
sections.
Sources
The PGMs are found in nickel, copper and iron sulphide seams (Bradford, 1988). They are
currently mined in South Africa, Siberia and Sudbury, Ontario. World mine production of the
PGMs, of which 40-50% is platinum, has steadily increased since 1970. This reflects the
increasing world-wide use of PGM vehicle catalysts (IPCS, 1991). From 1988-1992 world
mine production was essentially constant at around 255 tonnes per year (WMS, 1994). The
amount of PGMs present in the earth’s crust down to a depth of 5km, and hence
technologically attainable, are still enormous when compared with present requirements, but
only a fraction of the pertinent ores is sufficiently rich for commercial exploitation. Of the total
of 3x1011 tonnes of PGMs in the earth’s crust, 3x103 tonnes have been mined, and 7x1010
tonnes are minable (Renner and Schmuckler, 1991).
The total worldwide supply of Pt for 1999 and 2000 was 138 tonnes and 153 tonnes
respectively for Pd 230 tonnes and 224 tonnes respectively, and for Rh 14.2 tonnes and
20.9 tonnes respectively (Johnson Matthey, 2000)
By far the greatest use of PGMs both in Europe and worldwide is in vehicle catalysts, with
additional major uses in the chemical industry, electrical and electronics industries,
petroleum industry, the manufacture of jewellery, as a cancer treating drug in medicine, as
alloys in dentistry and in the glass industry.
Demands by application for 1999 and 2000 for PGMs are shown in Table a.1. (Johnson
Matthey, 2000)
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115
Section 6. Case Studies
Trends over time in platinum and palladium uses by application for Europe are shown in
Table a.2 and a.3.
Of particular interest is the increased demand for palladium in Europe, largely in response to
the introduction of Euro Stage III legislation from January 2000; palladium – rich catalysts
will meet stricter emission limits for petrol models, resulting in a further move away from
platinum technology (Johnson Matthey 2000).
Catalytic convertors
A catalytic converter is a unit about the size of a small silencer that fits into the exhaust
system of a car. The metal catalyst is supported on a ceramic honeycomb monolith and
housed in a stainless steel box similar in shape to that of a conventional silencer. About 1-3g
of PGM is contained in some vehicle exhaust catalysts, approximately 50g of PGM per cubic
foot of catalyst (Steger, 1994). Due to the commercial sensitivity of these products it is
difficult to obtain data on the exact amounts in each of the many different formulations of
catalyst. The honeycomb made of cordierite contains 300 to 400 square channels per
square inch (6.45cm2), and is coated with an activated high surface area alumina layer
called the washcoat (Farruato, 1992) containing small amounts of the precious metals,
platinum, palladium and rhodium in varying proportions. The conventional three-way
catalysts typically contain 0.08% platinum, 0.04% palladium and 0.005-007% rhodium
(Hoffman, 1989).
These metals convert over 90 percent of carbon monoxide (CO), hydrocarbons (HC) and
nitrous oxides (NOx) into carbon dioxide (CO2), water (H 2 O) and nitrogen (N2). Platinum is
an effective oxidation catalyst for carbon monoxide and hydrocarbons, but it is more
sensitive to poisoning than palladium and so can only be used in cars which use unleaded
petrol. Palladium is becoming increasingly used instead of platinum due to the higher costs
of the latter. The rhodium oxidises the hydrocarbons and reduces the NOx emissions. Base
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Section 6. Case Studies
metals are also incorporated, cerium being the most frequently used; others include calcium,
strontium, barium and iron.
Recycling
Of the total platinum consumption in the United States, approximately thirty per cent is
accounted for by vehicle catalysts (IPCS, 1991). The recovery of spent autocatalysts from
vehicles at the end of their lives is regarded as important and substantial secondary sources
of platinum as well as palladium and rhodium (Torma and Gundiler, 1989). The quantity of
spent autocatalysts greatly increased in the United States from 1984 to 1988. These
scrapped autocatalysts present an important secondary source of the platinum group
metals.
On current projections it is expected that 3.5 million catalysts will be available for recycling in
the UK by 2000.
Although a rapid increase in Pd in sediments from the Palace Moat, Tokyo, Japan was
reported by Lee (1983) between 1948 and 1973, it seems unlikely that this was connected
with car catalytic convertors since there were few in use in Tokyo by 1973.
Emissions of PGMs arise as a result of deterioration of the catalytic convertors, mainly due
to thermal or mechanical strain and acid fume components, and are intensified by
unfavourable operational conditions (misfiring, excessive heating) which may even destroy
the converter (Schäfer and Puchelt, 1998).
Emission rates range between several ng and µg of Pt per km driven depending on whether
they were measured in motor experiments or calculated on the basis of environmental
concentrations (König et al., 1992). Platinum is mainly emitted as a metal or an oxide with
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Section 6. Case Studies
particle sizes in the nm range, bound to small articles of washcoat material (Schlögl et al.,
1987).
Several workers have reported accumulation of Pt, Rh and Pd in road dusts and soils
(Zereini et al, 1993; Schäfer et al 1995; Farago et al 1996; Heinrich et al, 1996; Schäfer et
al, 1996).
Mostly inert under atmospheric conditions, the reactivity of Pt increases significantly if these
nanoparticles are brought into contact with soil components. Lustig et al., (1996)
demonstrated that humic substances considerably enhance the reactivity of Pt clusters in
the nm-range under atmospheric conditions. Using road-dust from a tunnel, it was
demonstrated that within hours Pt can be fixed to several humic acids with different
molecular weights. The low solubility of Pt in deionized water increases significantly even
under reducing conditions when certain anions or complexing agents are used (Nachtigall et
al., 1996).
A detailed study has been undertaken in several sites in southwest Germany, selected on
the basis of traffic density and morphology, including roads in Stuttgart with 120,000 vehicles
per day and near Heidelberg with 100,000 vehicles per day (Schäfer and Puchelt, 1998). At
these two locations, Pt concentrations in the 0-2 cm surface soil adjacent to the road ranged
from several hundred µg/kg to local background values (≤ 1 µg.kg-1) at less than 20 m from
the road. Maximum Pd and Rh values were 10 and 35µg.kg-1 respectively. The PGM
concentration decreased significantly with depth.
However the maximum PGM concentrations in soils at Heidelberg were only 25 percent
those at Stuttgart, even though the traffic density was only 20% lower. The authors
suggested that this could be due to frequent traffic jams at the Stuttgart site “leading to
excessive emissions due to unfavourable working conditions of the engines”.
Urban road dusts collected in Stuttgart at the same time showed concentrations of Pt
ranging up to 1000 µg.kg-1, 110 µg.kg-1 Rh and 100 µg.kg-1 Pd; these reflect short-term
inputs of PGMs. A ratio of around 6 Pt: 1 Rh in traffic influenced soils and dusts has been
reported by Schäfer et al (1996).
A recent estimate of total Pt emission in the vicinity of roads in Germany over the period
1985-2018 was 2,100 kg (using emission factors of 0.65 µg.kg-1 for highways, 0.18 µg.kg-1
for federal and national streets and 0.065 µg.kg-1 for district and city streets) (Helmers and
Kummerer, 1999). These different emission rates reflect the increase in Pt load of exhausts
with increasing speed of the car.
Accumulation of Pt was clearly shown in road dusts and surface soils adjacent to roads in
the UK in 1994 (Farago et al, 1996, 1998). In the heavily trafficking London Borough of
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Section 6. Case Studies
More recently a study in the city of Nottingham, UK, compared Pt and Pd concentrations in
garden soils and road dusts taken in 1996 and 1998 and archived samples taken in 1982
(which represented levels before the introduction of catalytic convertors) (Hutchinson, 2001).
Significant increases for both Pt and Pd were found in road dusts (see Tables a.4 and a.5
and Figure a.1) with values ranging up to 298 ng.g -1 and 556ng.g-1 respectively for Pt and Pd
in 1998 .
Table a.4 Summary results for Pt in garden soils (0-5cm) and road dusts from
Nottingham (ng.g-1) aResidential streets with low traffic densities; b Includes major roads
with high traffic densities (from Hutchinson, 2001)
Table a.5 Summary data for Pd in garden soils (0-5 cm) and road dusts in Nottingham
(ng.g-1) a Residential streets with low traffic densities; b Includes major roads with high traffic
densities (from Hutchinson, 2001)
An EU-funded study under the Environment and Climate Programme, CEPLACA, involved
laboratories in Madrid, Gothenburg, Sheffield, Rome and Neuherberg. Changes in catalyst
morphology over time were studied using SEM/EDX and laser induced breakdown
spectrometry (LIBS) (Palacious et al, 2000). Catalysts were used up to 30,000 km in a roller
dynamoneter following a driving cycle representing urban and non-urban driving conditions.
Releases of PGMs were found to decrease with time. For new petrol catalysts mean
releases were 100, 250 and 50 ng.km-1 for Pt, Pd and Rh respectively. In diesel catalysts Pt
release ranged from 400-800 ng.km-1.
The effect of catalyst ageing was large. At 30,000 km releases were reduced to around 6-8
ng/km Pt, 12-16 ng/km Pd and 3-12 ng/km Rh for petrol catalysts. In diesel catalysts, the Pt
release ranged from 108-150 ng/km.
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Section 6. Case Studies
The difference between diesel and petrol was ascribed to the different composition of the
washcoat and the different running conditions of diesel engines.
Soluble forms of PGMs emitted (in dilute HNO3) were significant for the fresh catalyst but
less than 5% of the total amount. A previous study had reported 10% of the total Pt emission
to be water soluble for fresh petrol catalysts (König et al, 1992).
At 30,000 km the amount of soluble PGMs released was similar or slightly higher than at 0
km. One possible explanation suggested for the relatively high amount of soluble PGMs
related to the relatively high chloride concentration in fresh washcoat (i.e. one example
quoted of 3.4 wt %). The authors suggested that the formation of soluble PtCl6, PdCl2 , PdCl4
or RhCl 3 could be favoured at the high temperature and humidity that can be reached in the
catalyst. The chloride concentrations in aged catalysts are normally very much lower.
However, further laboratory tests using spiked solutions showed the instability of these
chloro-complexes in the final exhaust fumes solution. It was thus thought possibly that the
soluble or labile PGM fraction of the exhaust could be higher than those measured
(Palacious et al, 2000).
An important conclusion from this study was that “no clear relation could be observed
between the labelled amount of PGMs in the different catalysts studied and the measured
amount released through car exhaust fumes. Different catalytic converter manufacturers,
different car engines, even if running under the same conditions during the sampling period,
and the well-characterized non-uniform behaviour of the catalyst could account for the lack
of an observed correlation”.
Effluents from hospitals contain platinum from excreted anti-neoplastic drugs, cisplatin and
carboplatin, though workers in Germany have concluded that these are only of minor
importance to environmental inputs from other sources and in particular from the use of
catalytic convertors (Kümmerer and Helmers, 1997). These drugs were introduced 25 years
ago to treat various tumours and are usually administered in the hospital environment. The
platinum passes into hospital sewage which is then treated with household sewage in
WWTS.
The authors monitored effluent samples from the University Hospital of Freiberg and two
communal hospitals and found total inputs of platinum of around 330g/year from the
University Hospital and 12 g/year from the Community Hospital. These equated to a
consumption per bed per day of 600 µg Pt for the University Hospital and 85 µg Pt the
community hospital. Extrapolation on a national basis, this amounted to an upper limit for the
input in Germany of 141 kg Pt per year (c. 645,000 hospital beds (German Statistical
Federal Agency, 1994) and a lower limit of 20 kg/year, with an average calculated value of
28.6 kg/year. Comparisons with other sources are shown in Table a.6.
Table a.6 Sources and sinks of platinum in Germany (from Kümmerer and Helmers,
1997)
Source Amount Pt (kg/year) Reference
Catalytic converters 15 König et al., 1992
emissions Zereini, F., personal
communication 1996
Hospital effluents 28.6 Kümmerer and Helmers, 1997
Sewage sludge 100.4 - 400.8 Laschka and Nachtwey German
Statistical Federal Agency, 1995
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Section 6. Case Studies
A broader study based on hospitals in Belgium, Italy, Austria, the Netherlands and Germany
aimed to provide reliable data with which to quantify sources of platinum in the environment
from hospitals with other sources (Kümmerer et al, 1999). This study was supported by the
LIFE95/D/A41/EU/24 Project of the European Community.
It was shown that 70% of the Pt administered in carboplatin and cisplatin is excreted and will
therefore end up in hospital effluents. Pt concentrations measured in the total effluent of the
different hospitals ranged widely from less than 10 ng.l-1 (the detection limit) in the Belgian
and Italian hospitals to cca. 3,500 ng.l-1 for the Austrian and German hospitals. In all cases
the influent of the WWTS was below 10 ng.l-1 as a result of dilution within the waste water
system.
Annual emissions by hospitals and cars in Germany, Austria and the Netherlands are listed
in Tables a.7 and a.8 and compared in Table a.9.
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Section 6. Case Studies
In this study the highest concentrations of Pt in WWTP influents were found at the beginning
of rain periods and at the end of cold periods when snow was melting. It was then concluded
that the main inputs of Pt into municipal sewage were from urban and road run-off from
traffic and other Pt emitting sources and not from hospital emitted sewage (Kümmerer et al,
1999).
Knowledge on these sources, the species involved and their environmental properties is
sparse if not non-existent.
A study of PGMs in sewage sludge incineration ashes from the municipal WWTS at
Karlsruhe, Germany, showed Pd concentrations to have increased from 64 to 138 µg.kg-1
from 1993 to 1997, with Rh increasing from 4.8 to 6.3 µg.kg-1; Pd varied from 300 to 450
µg.kg-1 with no significant trend although these concentrations were 10-fold higher than in
1972 (Schäfer et al, 1999). The authors drew attention to the Pt/Rh ratio in the sludge of c.
20:1 which differs greatly from that of 6:1 typically found in environmental samples
influenced by traffic emissions. They then estimated that, as more than 90% Rh is used for
the production of catalytic convertors, and as Pt and Rh are emitted in a ratio of 6:1, that the
contribution of traffic to the Pt concentration in sludge is only c. 30%, a result similar to that
found in Munich by Laschka et al (1996). They thus suggested that the greater part of Pt in
sewage sludge must come from sources other than catalytic convertors, such as hospital
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Section 6. Case Studies
and medical effluents or industrial emissions. They drew attention to the fact that “in cities
with a jewellery industry, noble metal concentrations in sewage sludge far exceeded normal
values even before the introduction of catalytic convertors” (Lottermoser, 1994).
Laschka and Nachtwey (1997) analysed Pt on primary and secondary effluents and in
primary and digested sludge from two sewage treatment plants in Munich, where platinum
pollution from industry, hospitals and traffic is considerable. Samples were taken before and
after rainfall in October 1994 and July 1995. In general Pt concentrations in effluents were
higher during rainy weather compared to dry weather. The Pt loading in secondary effluents
was lowest for the period Monday/Tuesday (i.e. after the weekend), which was considered
typical for industrial loads; the authors concluded that during dry weather, the platinum load
originated mainly from industry. Comparison of the average Pt load in primary and
secondary effluents in Munich, indicated a removal rate of 74% and 70% in the treatment
plants. These elimination rates were lower than those typical for other metals such as Pb
and Cd, which was attributed by the authors to the stabilizing effect of chloride (>100mg.l-1 in
domestic sewage, or to the low Pt content of untreated sewage (<0.1 µg.l-1).
This study confirmed the enrichment of Pt in sewage sludge, which was present in materials
from the 2 Munich treatment plants in concentrations ranging from 86 to 266 µg.kg-1.
Sludges from other large towns and centres of industry had previously been found to contain
10 to 130 µg.kg-1 Pt and from smaller rural plants <10 to 50 µg.kg-1 Pt (Lottermoser, 1994).
In this earlier study, an exceptionally high value of 1070 µg.kg-1 had been found in sludge at
Pforzheim, a town with a jewellery industry.
The study of Laschka and Nachtwey (1997) concluded that “in a large industrial centre such
as Munich, automobile traffic is not the dominant source of Pt in municipal sewage”.
A recent review article by Helmers and Kümmerer (1999) has attempted to quantify the
sources, pathways and sinks of Pt in the environment. The authors noted that there was as
yet not enough data to reliably investigate Pd and Rh fluxes, noting the lack of good quality
assurance for Pd analysis and the paucicity of environmental data on Rh. An examination of
archived sewage sludge ash from Stuttgart, Germany showed a continuous increase in Pt
concentrations since 1984. With an estimated 5 x 1010 kg of sewage sludges for Germany in
the early 1990’s and c. 250 mg.kg-1 Pt in sewage sludge, this amounts to some 12,500 kg of
Pt, some 2 orders of magnitude higher than the Pt flux emitted by traffic. Much smaller Pt
concentrations (mean 35 mg kg-1) have been found in smaller German purification plants.
Assuming that 50% Pt emitted by cars is received by sewage systems and taking into
account the amounts of Pt in effluents from hospitals being completely received by sewage
systems, the authors calculate that for Germany Pt received in the influents of WWTS from
both these major sources amounted to 42.9 kg in 1994 and 56.4 kg in 1996. They thus
considered an additional input of around 10 kg Pt per year from industrial sources.
If around 70% of the Pt influent is removed within the WWTS into sludge, the remaining 30%
is emitted into freshwater (see Table 10). In Germany 30% of the sewage sludge is used on
agricultural land and 70% disposed of as sludge or incinerated sludge ash. Losses to the
atmosphere from incineration are not yet known.
Table 10. Partition of anthropogenic Pt fluxes (in kg) within German WWTS
Year Received by Remaining in Disposal with Deposited Released into
the WWTS the sewage sludges or agriculturally freshwater
sludges ashes with sludges
1994 42.9 30.9 21.6 9.3 12
1996 56.4 40.6 28.4 12.2 15.8
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Section 6. Case Studies
Helmers and Kümmerer (1999) consider the possibility of extrapolating these results to other
European countries, taking into account traffic densities, catalytic convertor policies etc., with
the qualification that “since there is no highway speed limit in Germany, highway Pt
emissions of other countries may be halved in comparison with the German situation”
(Helmers, 1997).
Current scientific opinion would seem to agree that PGMs emitted as autocatalyst particles
remain bound to these and have limited mobility in the road and soil environment (Rauch et
al, 2000). Experimental studies under laboratory conditions, in which ground catalysts have
been added to soils under varying conditions of pH, chloride and sulphur concentrations
have indicated that post-deposition processes in soils and waters are of minor importance
and that “the risk of a health endangering contamination of the environment, and especially
groundwater, at present seems negligible, as the PGM species behave relatively inertly”
(Zereini et al, 1997). However transformation of PGMs into more mobile forms has not been
ruled out and indeed Rauch et al (2000) suggest that this may occur “in the roadside
environment, during transport through the stormwater system or in the urban river”.
In the absence of detailed study, it would seem impossible at this stage to apportion soluble
PGM species in the influents and effluents of WWTS’s to specific PGM sources from traffic,
hospital or industry, or to transformation/mobilisation of Pt and other PGMs in the
environment and/or waste water system, or indeed in the processing plant.
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Section 6. Case Studies
Conclusions
• exhaust emissions from motor vehicles using catalytic convertors (both petrol and
diesel) and subsequent runoff from road surfaces and roadside soils;
• emissions in effluents from hospitals using the anti-cancer drugs cirplatin and
carboplatin,
• industrial uses including jewellery manufacture, electronics and glass manufacture.
Several studies over the past decade have shown a steady increase in the use of PGMs.
Reliable quantitative information has shown that in general by far the greatest input of Pt and
Pd into the environment and into WWTS is from vehicle exhaust catalysts, with hospital
effluents accounting for some 6 to 12 per cent Pt. In large industrial centres, such as
Munich, inputs from other sources (presumed industrial) may exceed those from catalytic
convertors and hospitals. Quantitative knowledge of these sources is not currently available.
The solubility of PGMs entering the environment and the influents of WWTS is thought to be
low, though reactions within the soil/dust and wastewater environments need further study.
Interactions with chloride ions and humic substances may well increase solubility and thus
bioavailability.
Around 70 per cent of Pt in the influents to WWTS is removed with treatment into sludge,
which may then be applied to agricultural land or incinerated. Where land application is
practical, studies into uptake into pasture and foodcrops are recommended. The 30 per cent
of Pt emitted into freshwater systems will potentially increase Pt levels in drinking water
supplies.
At present there is no evidence of health risks arising from increasing levels of PGMs in the
roadside environment, in sewage sludge or in drinking water. However, as levels of use
continue to rise, it would seem prudent to focus research into factors influencing their
solubility and bioavailability, their uptake and input into food crops and drinking water and
into multiple exposure routes into the population.
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Section 6. Case Studies
Summary
Urban runoff source control practices have been the centre of an ongoing discussion
involving maintenance and quality issues. This review will provide a brief overview of
available techniques and structures and summarise their design characteristics. A
discussion on performance will focus on water quality but comments on maintenance will
also be included to allow the reader to form an overall opinion. A number of source control
application case studies in Europe will be discussed from the point of view of performance.
Introduction
Urban Runoff has traditionally been treated as a water quantity problem and the usual
approach to solving it has been a system of buried pipes designed to convey water
downstream as soon as possible (CIRIA, 1999). Several problems in this traditional
approach have been identified including possible flooding in downstream areas due to
alteration of natural flow patterns, water quality issues that are not dealt with within the pipe
system and largely ignored amenity aspects (such as water resources, landscaping potential
and provision of varied wild habitat). These considerations have led to an effort of rethinking
surface water drainage methods within the following framework:
This framework and the practices and drainage systems that were developed from it, are
collectively referred to in the UK as “sustainable urban drainage systems” (SUDS) (CIRIA,
1999) or more generally “source control” (Urbonas and Stahre, 1993) or “best management
practices” (BMPs) 1 (Jefferies et al., 1999). They essentially confirm with the emergence of
Agenda 21 as a local action-planning basis for strategic and integrated approaches “to halt
and reverse the effects of environmental degradation and to promote sound environmental
development” (United Nations, 1992). Source Control includes structures such as:
1
The fact that this Report adopts the widely used terms SUDS and BMPs to refer to source
control and distributed storage practices does not imply that it necessarily considers them either
“sustainable” or “best”. The positive and negative aspects of these practices will be discussed in the
following paragraphs.
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Section 6. Case Studies
Basic design characteristics and principles of use of the most widely used of these systems
will be presented in the following paragraph and are summarised in Table 1.
The techniques presented will be grouped in four categories according to the CIRIA
recommendations: (a) filters and swales, (b) permeable surfaces (c) infiltration devices and
(d) ponds (CIRIA, 1996; CIRIA, 1999). The overall structure of an urban catchment with
source control can be seen in the schematic in Figure b.1.
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Section 6. Case Studies
Permeable surfaces:
These include porous pavements, gravelled
areas, grass areas and other types of
continuous surfaces with an inherent system of
voids. The water passes through the surface to
the permeable fill, allowing for storage,
transport and infiltration of water. The actual
amount of water stored is dependent on the
voids ratio, the plan area and the structure’s
depth. It acts as a trap for sediment thus
removing a large number of pollutants from the
runoff, but keeps them within the particular site.
The principal mechanism for pollutant retention
is thought to be adsorption onto materials
within the pavement construction (Pratt, 1989).
Maintenance should ensure that the voids are
not filled by sand and silt and such an
operation may prove costly, as the surface
structure can deteriorate under external
pressure. The US, France, Holland, Austria
and Sweden have used porous surfaces for Figure b.3. Porous Pavement (after CIRIA
both traffic and pavement areas (Diniz, 1976; 1994)
Hogland, 1990). A typical structure can be
seen in Figure b.3.
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Section 6. Case Studies
Infiltration devices:
Soakways and infiltration trenches are below
ground and are filled with a coarse material.
They drain water coming in the infiltration
device from a pipe or a swale directly to the
surrounding soil. Their operation is based on
increasing the natural capacity of the soil for
infiltration but effectiveness is ultimately limited
by soil permeability. The volume of storage
therefore is dependent on soil infiltration
potential. Physical filtration can remove solids,
while biochemical reactions caused by
microorganisms growing on the fill or the soil
can degrade hydrocarbons. The level of
treatment depends on the size of the media
and the length of the flow path (CIRIA, 1999).
Extensive use of soakways in Sweden and the
US as well as in the UK generally provide
positive feedback on maintenance and
operation (Pratt, 1989; CIRIA, 1996). Areas
that are drained through infiltration structures of Figure b.4. Soakway (after CIRIA, 1996)
different types include car parks, roads, roofs
pavements and pedestrian sidewalks. Pollution
levels in these types of urban runoff can be
however significant and there is therefore
serious risk of introducing the pollutants to the
groundwater. Additionally the introduction of
water to the soil may cause geotechnical
problems. Figure b.4 describes a typical
soakway.
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Section 6. Case Studies
Figure b.6. Typical arrangement of a reed bed treatment pond (after CIRIA, 1994)
Performance
130
Section 6. Case Studies
Table b.1. Functions and water quality attributes of different source control structures
(after CIRIA, 1994)
France has also had experience in particular aspects of SUDS (for detention basins and
ponds). Nascimento et al. (1999) provide an overview of the French experience in detention
basins use and performance. In France, detention basin use dates back to the 1960s,
together with the construction of the “Villes Nouvelles”. Their use was limited, but these
facilities are increasingly popular as indicated in Deutsch et al. (1990) (Reported in
Nascimento et al., 1999). Recent research has focused in the quality side of performance of
the ponds with the QASTOR database created by CEREVE as a centre point (Saget et al.,
1998). The database aims to collect and analyse all French national data related to urban
wet weather discharge that have been collected in 19 catchments since 1970. The efficiency
of detention basins in reducing pollutants is the result of a large number of variables
including physical, chemical and biological characteristics of pollutants, precipitation regime,
detention time and quality of maintenance services (Nascimento et al., 1999). Table b.2
identifies the potential annual and short-term efficiency of detention basis recorded by Adler
(1993) as reported in Nascimento et al, (1999). The Table draws from studies conducted by
the French institution CEMAG-REF. The presented data were for basins installed in
separate drainage systems and the results indicate that such storage facilities can have a
reasonable performance even over quite short time scales.
However, despite such evidence, when the issue of integrating detention basins into the
urban context is concerned, the outcome may be very different according to the specific
case. For the UK the high pollutant loading to urban detention basins, which has been
reported, has led to concerns about long-term siltation (and loss of effective storage volume)
and water quality (especially in terms of health risks). Sansalone (1999) describes the
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Section 6. Case Studies
results of measurements taken in a field scale infiltration trench. Figure b.7, summarises
some of the findings, indicating significant potentially toxic element removal efficiency
exceeding 80% after 1 year of runoff loadings.
The Technical University of Denmark (Mikkelsen, et al. 1996a and 1996b) has been involved
in a series of tests to examine the effects of stormwater infiltration on soil and groundwater
quality. They found that potentially toxic elements and PAHs present little groundwater
contamination threat, if surface infiltration systems are used. However, they express concern
about pesticides, which are much more mobile.
Recent and ongoing studies in the US have tried to identify the potential hazards from the
use of infiltration systems.
In particular, a multi-year research project sponsored by the US EPA addresses the potential
problem of groundwater contamination due to stormwater infiltration (Pitt, Clark and Palmer,
1994; Pitt et al., 1997; Pitt, Clark and Field, 1999). In the case of pesticides the research
found that heavy repetitive use of mobile pesticides, such as EDB, on site with infiltration
devices likely contaminates groundwater. Fungicides and nematocides must be mobile in
order to reach the target pest and hence, they generally have the highest contamination
potential. Pesticide leaching depends on patterns of use, soil texture, total organic carbon
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Section 6. Case Studies
content of the soil, pesticide persistence, and depth to the water table (Shirmohammadi and
Knisel 1989). A pesticide leaches to groundwater when its residence time in the soil is less
than the time required to remove it, or transform it to an innocuous form by chemical or
biological processes. The residence time is controlled by two factors: water applied and
chemical adsorption to stationary solid surfaces. Volatilization losses of soil-applied
pesticides can be a significant removal mechanism for compounds having large Henry’s
constants (K h), such as DBCP or EPTC (Jury, et al. 1983). However, for mobile compounds
having low Kh values, such as atrazine, metolachlor, or alachlor, it is a negligible loss
pathway compared to the leaching mechanism (Alhajjar, et al. 1990).
Restricted pesticide usage in areas with high infiltration potential has been recommended by
some U.S. regulatory agencies. The slower moving pesticides were recommended provided
they were used in accordance with the approved manufacture’s label instructions. These
included the fungicides Iprodione and Triadimefon, the insecticides Isofenphos and
Chlorpyrifos and the herbicide Glyphosate. Others were recommended against, even when
used in accordance with the label’s instructions. These included the fungicides Anilazine,
Benomyl, Chlorothalonil and Maneb and the herbicides Dicamba and Dacthal. No
insecticides were on the “banned list” (Horsley et al, 1990).
In the case of potentially toxic elements, problems may appear when infiltrating
stormwater using a rapid infiltration system (Crites 1985), such as a dry well. Most metals
have very low solubilities at the pHs found in most natural waters and they are readily
removed by either sedimentation or sorption removal processes (Hampson 1986). Many are
also filtered, or otherwise sorbed, in the surface layers of soils in infiltrating devices when
using surface infiltration. Table 3 discusses the pollutants found in stormwater that may
cause groundwater contamination problems when allowed to infiltrate through infiltration
devices.
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Section 6. Case Studies
Table b.3. Groundwater Contamination Potential for Stormwater Pollutants (after Pitt et al., 1994)
134
Section 6. Case Studies
Conclusions
The control of diverse pollutants requires a varied approach, including source area controls,
end-of-pipe controls, and pollution prevention. All dry-weather flows should be diverted from
infiltration devices because of their potentially high concentrations of soluble potentially toxic
elements, pesticides, and pathogens (Pitt et al., 1999) Similarly, all runoff from
manufacturing industrial areas should also be diverted from infiltration devices because of
their relatively high concentrations of soluble pollutants. In areas of extensive snow and ice,
winter snowmelt and early spring runoff should also be diverted from infiltration devices.
All other runoff should include pre-treatment using sedimentation processes before
infiltration, to both minimize groundwater contamination and to prolong the life of the
infiltration device (if needed). This pre-treatment can take the form of grass filters, sediment
sumps, wet detention ponds, etc., depending on the runoff volume to be treated and other
site-specific factors. Pollution prevention can also play an important role in minimizing
groundwater contamination problems, including reducing the use of galvanized metals,
pesticides, and fertilizers in critical areas. The use of specialized treatment devices can also
play an important role in treating runoff from critical source areas before these more
contaminated flows commingle with cleaner runoff from other areas (Pitt et al., 1999).
Sophisticated treatment schemes, especially the use of chemical processes or disinfection,
may not be utilised, provided there is no danger of forming harmful treatment by-products
(such as THMs and soluble aluminium).
The use of grass swales and percolation ponds that have a substantial depth of underlying
soils above the groundwater is preferable to using dry wells, trenches and especially
injection wells, unless the runoff water is known to be relatively free of pollutants. Surface
devices are able to take greater advantage of natural soil pollutant removal processes.
However, unless all percolation devices are carefully designed and maintained, they may not
function properly and may lead to premature hydraulic failure or contamination of the
groundwater (Pitt et al., 1999).
It should be clear that although SUDS have great potential in both quantity and quality
control in urban runoff, each case should be assessed individually, and an incremental
approach containing both high tech and low-tech solutions is the most likely development
scenario (Butler and Parkinson, 1997). Direct application of such methods across different
regions and countries is not always appropriate and must also include consideration of the
local socio-economic and administrative circumstances associated with the operational
design, which can be primary inhibitors to the implementation of innovative technology.
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Section 6. Case Studies
Introduction
In Northern and Central Italy there is a high density of small-scale, artisanal enterprises and
activities. For example, in the region of Veneto (North-Eastern Italy), artisanal activities
account for 20% of the regions exports. The area of Vicenza, a provincial town in the Veneto
region, represents one of the largest agglomerations of artisanal activities in Italy. With a
population of 109,000 inhabitants, the municipality of Vicenza has a total of about 1600
small to medium-scale enterprises (SMEs).
The environmental impact of artisanal activities is less clearly understood than the impact
from industrial activities. While there are a large number of point sources, each source
contributes a very low wastewater flow rate, closer to the wastewater discharge from
residential units than from industrial sites. Nevertheless wastewater from artisanal activities
may be dramatically different to that from residential units, both in terms of pollutant
concentration and the presence of specific pollutants.
Due to the presence of specific pollutants, wastewater discharge is regulated in the same
way as industrial wastewater (i.e. in terms of pollutant concentration limits), even though
artisanal wastewater flow rates may be orders of magnitude lower than industrial ones
[Italian law by decree n. 152, 1999]
EBAV (Ente Bilaterale Artigianato Veneto, a non-profit bilateral organisation representing the
interests of both artisanal workers and enterprises) sponsored a study on the origin and
contribution of pollutants to urban wastewater. The aim of the study was to assess the load
of pollutants from different artisanal activities, in comparison to the total load originating from
the urban wastewater system. In addition, the pollutant load from artisanal activities was
subdivided into load from discharged wastewater and load from concentrated liquid wastes
(which are separated and collected by external firms), to assess if wastewater segregation
could significantly affect pollutant load from artisanal activities.
Wastewater for the whole Vicenza area is treated by four WWTS (Table c.1). The total
capacity is about 137,900 p.e. (population equivalent) with a total flow rate of about 23.2
million m3 year-1.
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Section 6. Case Studies
Table c.1 capacity of the four municipal wastewater treatment plant of Vicenza
municipality p.e.=population equivalent
Total load
Along with artisanal wastewater samples, influent and effluent samples from the four
municipal WWTS were analysed for a large number of pollutants including: B, Cd, Cr(III),
Cr(VI), Mn, Ni, Pb, Cu, Zn, and anionic surfactants. From each of the four WWTS a large
number of influent and effluent samples were taken and analysed. Using the specific
wastewater flow rate and the influent concentration, the pollutant load was calculated for
each plant. Table c.3 reports the total load as sum of the pollutant loads of the WWTS,
assuming that urban wastewater is treated by only one hypothetical centralized plant.
Total pollutant load in Table c.3 is reported as average value, based on the average
concentration from 20-50 samples. In addition, the maximum load and the upper 95%
confidence interval are given. The last column reports the average removal efficiency based
on the comparison of influent and effluent pollutant concentrations.
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Section 6. Case Studies
Table c.3 Pollutant load to the hypothetical centralized WWTS of Vicenza municipality
A typical example of the analytical work performed for each category of artisanal activity is
reported in Tables c.4 and c.5 for car repair shops. A rough statistical analysis of the results
has been performed to obtain the average concentration and the upper limit of the 95%
confidence interval (Max 95%). In addition the maximum value (Max) is also reported.
Table c.5 Pollutant concentrations (mg l-1) in the segregated wastewater of 6 car-
repair shops
Pollutant load was calculated for the selected enterprises and extrapolated to the total
number of enterprises for each category. Even though each enterprise was equipped with its
own treatment plant, pollutant loads were calculated on the basis of concentrations in the
untreated wastewater, hypothesizing a scenario where no pre-treatment is performed and
138
Section 6. Case Studies
the wastewater is discharged directly into the UWW collecting system. Similar calculations
were performed using concentrations and volumes of segregated wastewater (spent baths).
So, for the enterprises that separate wastewater for treatment by external firms (for recovery
and detoxification), two potential pollutant loads were given with reference to the two
hypothesized scenarios:
• all the wastes (concentrated and diluted wastewater) are discharged into the urban
wastewater system without pre-treatment (Table c.6 D and S);
• the spent baths are treated externally, whereas wastewater is directly discharged into
the urban wastewater system (Table c.6 D only).
The most significant pollutants are: suspended material, COD, oils, surfactants, organic
solvents, copper, and zinc.
Considering both discharged and segregated wastewater the total pollutant load for Zn, Cd,
Cu and, above all, Pb is very high. However upon careful segregation of concentrated
wastewater (D only), the pollutant load is significantly reduced. The careful segregation of
spent baths induces a decrease of about one order of magnitude in the percentage of lead
originating from car repair shops.
The principal pollutants from these artisanal activities are: suspended solids, lead, ammonia,
nitric nitrogen, and surfactants. As can be seen in Table c.6 the pollutant load from the
ceramic and photoceramic shops is minimal due to the low wastewater flow rate. Only lead
seems to represent a significant load. In the case of ceramic shops, segregation of
concentrated wastewater is not very significant in terms of reducing pollutant load.
The principal pollutants from these enterprises are: suspended solids, chromium (VI),
nickel, lead, copper, and cyanide. Segregation and external treatment of concentrated
wastes does not appear to significantly reduce the lead load because this load originates
mainly from the discharged diluted wastewater.
The most significant pollutants originating from this activity are: suspended solids, COD,
lead, copper, zinc, total phenols, organic solvents, and surfactants. Table c.6 shows that by
simply segregating concentrated wastes the pollutant load to the WWTS from wood
processing and furniture manufacturing shops is dramatically reduced. Other specific wood
processing pollutants such as arsenic were not analysed.
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Section 6. Case Studies
Several pollutants originate from metallurgists and mechanic shops: suspended solids,
COD, cadmium, chromium, nickel, lead, zinc, copper, sulphates, chlorides, phosphorus, oils,
solvents, and surfactants. Pollutant concentrations in wastewater are typically much lower
than in segregated wastewaters (see Table c.7) which have high average concentrations of
pollutants such as; nickel, lead, copper and zinc. Separation of concentrated wastes
reduces the load to the WWTS significantly.
The area of Vicenza represents one of the most important districts for gold manufacturing in
Italy, with up to 258 artisanal goldsmith shops. The main pollutants originating from gold
manufacture are: COD, boron, cadmium, copper, zinc, and surfactants. However goldsmiths
shops are characterized by very low wastewater flow rates, with an average of about 1 cubic
meter per day per unit.
In terms of contribution to the pollutant load, the 258 goldsmiths shops represent a high
contribution of Cd, Cu, and Zn. This is mainly due to the fact that goldsmith shops used to
add spent concentrated baths to the diluted wastewater in order to recover precious metals
during the wastewater treatment before discharging it into the sewer.
The most significant pollutants originating from this activity are: COD, fat, oils, and
surfactants. Cu and Zn are the only metals to be above the limits of detection in wastewater.
Principal pollutants originating from this activity are: suspended solids, COD, and
surfactants. The contribution of the 88 shops to the total metals pollutant load is generally
low, due to the low contribution in terms of flow rate, that is an average of about 0.07% of
the total UWW flow rate. Mercury is an important pollutant in wastewater linked to dental
practices, which is not considered in this particular study but is referred to in section 2.1.2 of
this report.
This is the category with the largest number of shops in the Vicenza’s municipality. The main
pollutants originating from hairdressers are: suspended solids, COD, and surfactants.
The main pollutants originating from laundrettes and dry-cleaners are: suspended solids,
COD, surfactants, chlorides, and solvents.
The most significant load of pollutant from the 88 laundrettes and dry-cleaners is for Cd
although overall the levels for this pollutant were very low .
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Section 6. Case Studies
Table c.5 Pollutant load from specific artisanal activities. D=discharged wastewater,
S=segregated wastewater, (- = not reported).
Pollutant loads from all artisanal activities of Vicenza municipality were calculated, summing
the loads of each specific activity as reported in Tables c.7 and c.8.
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Section 6. Case Studies
Table c.7 Total pollutant loads from artisanal activities in the Vicenza municipality,
considering both discharged and segregated wastewater
Table c.8 Total pollutant loads from artisanal activities in the Vicenza municipality,
considering discharged wastewater only
POLLUTANT TOTAL POLLUTANT LOAD FROM PERCENTAGE
ARTISANAL ACTIVITIES (g/day) OF TOTAL LOAD
TO WWTS
average max(95%) max
B 2909 4774 38832
Cd 24 51 498 36.9
Cr(III) 11 27 100 1.8
Cr(VI) <LOD. <LOD. <LOD.
Mn 0.6 1.7 13 0.01
Ni 33 92 206 0.5
Pb 50 127 491 7.9
Cu 338 621 3873 9.5
Zn 987 1827 6963 8.8
chlorinated solvents 6400 17739 140800
MBAS 50911 87609 342922 24.3
flow rate m3/day 1633 2526 5559 2.6
p.e. 5867 10508 42102 4.3
<LOD = below limit of detection
In terms of flow rate the contribution of all artisanal activities is typically low (2.6%). It
remains relatively low (4%) in the worst scenario case, where the artisanal activities
discharge at the upper limit of the confidence interval of their cumulative wastewater flow
rate, while the total UWW flow rate remains at the average value. In contrast, the percentage
contribution of artisanal activities to the total load is very high for pollutants such as: Pb, Cd,
Cu, Zn, Cr III, and surfactants.
Figures c.1 and c.2 compare the load of each specific activity to the total load of a
hypothetical centralized WWTS, for potentially toxic elements and surfactants, respectively.
Figure c.1 clearly shows that only car-repairers, goldsmiths shops, metallurgists and
mechanics contribute significant amounts of potentially toxic elements to UWW, with respect
142
Section 6. Case Studies
to the total metal load of the all activities. The main activities responsible for the surfactant
load in UWW are; hairdressers, goldsmiths, and food workshops (Figure c.2).
9000
8000
7000
average load (g/day)
6000
5000
4000
3000
2000
1000
0
AL AU CE GA GR LG MA ME OD OR PR PU TS VE tot
60000
50000
average load (g/day)
40000
30000
20000
10000
0
AL AU CE GA GR LG MA ME OD OR PR PU TS VE tot
143
Section 6. Case Studies
With the exception of surfactants and cadmium, the high pollutant loads from artisanal
activities are notably reduced when the concentrated wastes are not considered (Table
c.23). The poor effect of waste segregation on surfactant load is explained by the fact that
the major surfactant contribution derive from activities that do not practice waste
segregation: hairdressers, goldsmiths shops, and food workshops (Figure c.2).
Assuming that the fate of sewage sludge produced from the hypothetical centralized WWTS
is used in agriculture, the maximum admissible pollutant concentration in sludge must be
considered. From this value a maximum admissible pollutant concentration in the UWW may
be calculated according to the following equation:
Ci Qf 100 %H 2O
C
R% Q
where C is the maximum influent concentration permitted for sludge disposal
Ci is the maximum pollutant concentration allowed in sludge to land
R% is the removal efficiency (%) in the treatment plant
Qf is sludge flow rate in m3 day-1 calculated on the basis of the production of 1.87 l/inhabitant
with 95.5% of humidity
Q is the influent wastewater flow rate
% H2O is the water content of the sludge (95.5%)
Table c.9 Pollutant contribution of artisanal activities to the admissible load for sludge
disposal in agriculture, considering both discharged and segregated wastewater
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Section 6. Case Studies
Table c.10 Pollutant contribution of artisanal activities to the admissible load for
sludge disposal in agriculture considering only discharged wastewater
In Tables c.9 and c.10 the concentration limits imposed by law for sludge used in agriculture
are reported. From these limits the concentration limit in the influent and the consequent
admissible load were calculated. In the last column the impact of artisanal activities on the
sludge characteristics are reported in terms of percentage load from artisanal activities with
respect to the total admissible load for sludge disposal (calculated using average values).
Table c.10 considers the highest possible pollutant loads in the hypothesis that waste
segregation does not take place. Even in this pessimistic hypothesis, the impact of artisanal
activities is typically low. The highest metal contribution is for Ni, representing 11% of the
admissible load. In the worst case scenario, considering all the maximum loads, artisanal
activities by themselves almost reach the admissible Cd and Ni loads.
The average impact on sewage sludges, without considering the concentrated spent baths
(Table c.9) is less than 5% for all the metals.
Validation of the Case Study with results from a recent study on hairdressers’ shops
in a different area of Veneto region
To validate the results obtained in the study described above, EBAV undertook an additional
study specifically addressed to activities of hairdressers and beauticians. This study,
performed during 1999-2000, considered a group of shops representing all the hairdressers
and beauticians located in the district of Valdagno (Vicenza), which discharge their
wastewater into the UWW collecting system of the municipality of Trissino (Vicenza). In this
validation study the number of shops examined was about 22% of those present in the area,
compared to only 6% of hairdressers in the Vicenza Case Study. Typically one wastewater
sample was drawn from each shop. A rough statistical analysis of the results has been
performed to obtain the average concentration; then the average values have been
increased by 10% to take into account the effects of highly polluted wastewater (due to
typical products such as shampoos or dyes).
In Table c.11 the average pollutant concentrations are reported, as well as the average
wastewater flow rate per unit. In this case wastewater production was even lower than in the
case of Vicenza (600 l.day-1 vs 900 l.day-1). The contribution of hairdressers’ shops to the
total wastewater flow rate entering the Trissino WWTS was 0.33%, whereas in Vicenza area
this was about 0.45%. From the average concentrations (with a safety increase of 10%) and
from wastewater flow rates the pollutant load from the total 135 shops to the Trissino WWTS
was calculated. Where data was available (chromium and surfactants), this load was
compared with the total pollutant load to the WWTS. Data from Valdagno area confirm the
negligible contribution of chromium load, and other potentially toxic elements as well, to the
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Section 6. Case Studies
The data presented above, while confirming the negligible contribution of this artisanal
activity to the total load of metallic pollutants, suggest that the extrapolation of the results
from Vicenza Case Study may result in an overestimation of the contribution of artisanal
activity to the pollutant loads in the WWTS systems.
Table c.27 Pollutant concentrations and pollutant loads from hairdressers and
beauticians in the district of Valdagno (Vicenza)
POLLUTANT AVERAGE POLLUTANT LOAD* PERCENTAGE OF LOAD
CONCENTRATION (g/day) TO WWTS
(mg/l) (%)
Cr(III) <0.1 <5 <0.1
Anionic surfactants 44 3915 8.2
Non ionic surfactants 51 4590 6.2
Total surfactants 99 8775 7.2
Flow rate 0.6 (m3/day x shop) 81 (m3/day) 0.33
*based on average + 10%
Conclusions
Cases like the Vicenza district, with artisanal activities deeply rooted in residential areas are
common in Italy and in other EU regions. As shown in the validation case of Valdagno, in
other districts the contribution of artisanal activities to the pollutant load of the UWW system
may be lower.
The principal pollutants originating from these artisanal shops are potentially toxic elements
such as Cd, Ni, Pb, Cu, and Zn, and surfactants.
The main conclusion of this study was that, by segregating concentrated liquid wastes, the
contribution of artisanal activities to the pollutant load was dramatically reduced, at least for
potentially toxic elements. However, only some of the artisanal activities in this Case Study
practised wastewater segregation. One issue raised by artisanal representatives was the
economic cost of segregation of wastewater. It is felt that the stringent environmental
requirements concerning wastewater from Italian artisanal shops, considered industrial
wastewater, do not compensate efforts for waste segregation.
Artisanal activities that did not practice segregation of concentrated liquid wastes include
goldsmiths, hairdressers and food manufacturing shops, which are also the main enterprises
responsible for the surfactant load in wastewater. As a consequence, neglecting the
contribution of segregated liquid wastes did not significantly affect the total load of
surfactants from artisanal shops. This load typically represents one fourth of the total
surfactant load to the WWTS. It may be anticipated that, if careful segregation of the
concentrated liquid wastes were extended to all the artisanal activities, a dramatic decrease
of potentially toxic element and surfactant load from the artisanal activities would be
obtained. Even though the wastewater flow rate from artisanal shops would not decrease
significantly, the pollutant load could be reduced to negligible values with respect to the total
pollutant load.
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Section 6. Case Studies
Introduction
In Italy there are about 6,000 small to medium gold and jewellery manufacturing shops, most
of which are concentrated in three main production districts: Arezzo (Tuscany), Vicenza
(Veneto) and Valenza Po (Piemonte). In the period 1995-1999 the Italian Government and
the Association of Artisanal Activities sponsored a large research programme, carried out by
the National Research Council, in support of Craft Goldsmiths Production and Trade. The
programme tackled problems relating to:
The Italian Water Research Institute (IRSA) carried out a survey on management practices
for wastewater, produced in small to medium gold manufacturing shops in Arezzo (Marani,
1997). According to the Association of Goldsmiths, the results obtained in the survey of
Arezzo district may confidently be extended to draw conclusions about national practices in
goldsmiths’ shops. There is no information on the losses of Au, Ag, PGMs from the gold and
jewellery shops to the wastewaters in this research programme. More data on PGM is
presented in Case Study (a).
The most prevalent processes are those starting from wire or plate to produce rings, chains
and medals. Hollow bars may be used to produce lighter objects. Gold or silver goods may
also be produced using micro-casting or electrolytic processes (electro-forming). All
production cycles have common final steps: object assembly, polishing, finishing and
cleaning.
Different production cycles and processes generate wastewater in the gold manufacturing
shops. Casting operations to prepare wire or plate do not typically require aqueous
solutions, with exception of small volumes for washing crucibles. In contrast, the preparation
of hollow bars requires nitric acid, hydrochloric acid, caustic soda, and ammonia solutions.
The wastewater resulting from micro-casting comes from water used to break the gypsum
mould and rinse waters. The “gypsum” waters are segregated from the other wastewater
produced in the workshops and recycled after a settling step.
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Section 6. Case Studies
re-circulated after elution through an ion exchange column (anionite). The concentrated
cyanide solutions produced by column regeneration are sent to external firms.
In the final steps of assembly and finishing, the operations producing liquid wastewater are:
• acid pickling,
• galvanic treatments,
• surface shining,
• washing steps.
Usually spent pickling baths are treated by external firms. The waters derived from surface
shining generally contain metal powder. In addition, the final step generates large amounts
of wastewater as well as surfactants present in the spent baths.
Finally hand and floor washing waters, do not typically require pre-treatment and could be
sent to the sewer. However as they may contain gold and silver powder they are not directly
discharged into the sewer. Instead they are sent to the internal wastewater treatment plant.
Here the insoluble precious metals are concentrated in the sludge which, is dried and sent to
specialised firms for recovery of precious metals.
Soapy waters contain high concentrations of detergents, along with fatty substances and
metal powder. Other pollutants such as phosphates and ammonia typically originate from
the detergents used in these workshops.
The acids contained in the acid wastewater are: sulphuric acid, nitric acid, hydrochloric acid,
hydrofluoric and fluoboric acid. This wastewater may also contain high concentrations of
potentially toxic elements such as copper, zinc, iron and nickel.
“Gypsum” waters containing suspended gypsum particles, are recycled several times after
sedimentation of the suspended material. Then they are committed, together with the
sedimented gypsum, to external firms for final disposal.
The cyanide waters contain free cyanide and soluble cyano-complexes of gold and silver.
For safety reasons these waters are treated separately to oxidize the cyanide before
sending them to the wastewater treatment plant.
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Section 6. Case Studies
Conclusions
In examining the pollutant concentrations in these wastewaters (considering the results
obtained for the 12 shops sampled), the pollutants most often detected with concentrations
higher than admissible limits for discharge are: surfactants, copper, zinc, cadmium and
boron. Surfactants, copper and zinc are detected in all samples whereas boron and
cadmium are present in 75 % and 60% of samples respectively. Surfactants, derived
generally from washing processes, are present in wastewater with an average concentration
of 34 mg.l-1 MBAS and a maximum value of 118.5 mg.l-1 MBAS. The average boron
concentration found in the wastewater of small jewellery shops examined is 13.5 mg.l-1, with
a maximum value of 100 mg.l-1. The presence of boron in these wastewaters may be due to
processes such as soldering (where boron is used as borace), voiding and washing, or
through the use of other materials e.g. hydrofluoboric acid, detergents.
For potentially toxic elements, the average concentrations of copper and cadmium detected
in wastewater are 14.2 mg.l-1 Cu and 0.4 mg.l-1 Cd, with maximum values of 61 mg.l-1 Cu
and 1 mg.l-1 Cd. Zinc concentration is highly variable, which is probably due to the different
manufacturing steps of the shops, with an average value of 22 mg.l-1 but a maximum value
of 270 mg.l-1.
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Introduction
Pharmaceutical substances are a group of compounds, which until recently, have not been
of major concern with regards to their environmental effects. These compounds are
developed for their biological effect (primarily in humans), to cure disease, fight infection or
reduce symptoms. If these substances enter the environment they may have an effect on
aquatic and terrestrial animals, due to these biological properties and the fact that some of
them may bioaccumulate. Unlike other organic compounds, such as PCBs whose use has
been discontinued over the last 20 years, pharmaceuticals are used widely and they and
their metabolites may easily enter the UWW system. Pharmaceuticals use is also expected
to increase in Europe with the increasing avearge age of the population.
Current research demonstrates that drugs and their metabolites entering water supplies and
the food chain may pose a real threat, both to the ecosystem and to human health, and risk
assessments are slowly being carried out. However, many problems must be overcome,
such as the fact that these compounds are very changeable and are usually present in
mixtures and at low concentrations. Furthermore, pharmaceuticals have a wide variety of
structures and activities and that they may act synergistically (Alcock, 1999). There are
many different pharmaceuticals substances and approximately 3000 pharmaceutical
compounds are discharged into UWW collecting systems (ENDS, 2000). Sewage sludge is
predominantly disposed of on agricultural land, as is manure from farms and both of these
products will contain large amounts of pharmaceutical substances. Unfortunately, very little
is known about the fate of these compounds in the environment and the potential long-term
impacts. Many pharmaceutical substances though, have the same characteristics as organic
compounds; i.e. they are lipophilic, which tends to be a requirement to be able to pass
membranes, and some are designed to be persistent so that they are not inactivated before
achieving their healing effect (Halling-Sørensen, 1998).
A large amount of pharmaceutical products from both categories are prescribed each year.
For example in Germany, 100 tonnes of human drugs were prescribed in 1995 (Ternes,
1998c). This probably reflects the amounts prescribed in other countries of Western Europe,
relative to population size. Over the counter pharmaceutical sales will also increase this
figure. It is likely that a high concentration of drugs may find their way into wastewater,
making wastewater and sewage sludge major vectors for the entry of these compounds into
the environment. However, this will depend on the chemico-physical behaviour of the
pharmaceuticals in question.
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Section 6. Case Studies
Figure d.1: Scheme for the main fates of drugs in the environment after application
[after Ternes, 1998c.]
The main entry routes of pharmaceutical substances into the environment are through;
disposal of wastewater treatment end products: effluent and sewage sludge; and manure
spreading onto agricultural land or even from the excreta of grazing animals (Figure d.2).
Fish farms also use medical substances as feed additives, but most of the food is not eaten
and is deposited straight onto the sea-bed (Halling-Sørensen, 1998).
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Section 6. Case Studies
The compounds
For the purpose of risk assessments, pharmaceutical compounds have been divided into
four activity groups: antibiotics, antineoplastic drugs, antiparacetic drugs, and hormone
disrupters. However, there are many other groups of pharmaceutical compounds, such as
lipid regulators, which have been found ubiquitously in the environment and are highly
persistent compounds (Daughton, 1999).
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Section 6. Case Studies
Antibiotics:
Antibiotics are widely used as medicines for human and animals treatment, also used widely
as growth promoters in veterinary use. According to the Swiss environmental research
institute, in the EC 54000 tonnes of antibiotics were used in human medicine in 1997.
Veterinary use amounted to 3500 tonnes of medicines and 1600 tonnes of growth promoters
(ENDS, 2000). Due to the effect of bans the use of growth promoters is expected to decline.
According to a study carried out by Halling-Sorensen (1998), most antibiotics are not very
persistent in the environment, particularly in soils, and the most widely used growth
promoters have been shown to have no effect on invertebrates, even at relatively high
concentrations. However soil bacteria may be more sensitive (ENDS, 2000).
Veterinary drugs tend to end up in manure and so have the potential to contaminate soils
where manure or slurry is spread. Levels of antibiotics in soil around a pig farm studied
reached up to 1400µg.kg-1, due to presence of antibiotics in the animals’ feed (ENDS, 2000).
The increased use of antibiotics has led to an increase in drug resistant micro flora. This
resistance is actually favoured by low concentrations of antibiotics (Jorgensen, 2000), thus,
the presence of antibiotics in the environment may be an important problem.
Anti-neoplastic drugs
These anti-cancer drugs are mainly used in hospitals rather than in households. They are
primarily used for chemotherapy and are found sporadically, in a range of concentrations in
the environment (Daughton, 1999). Anti-cancer drugs act as non-specific alkylating agents,
which means that no receptors are required, hence, they have the potential to act as
mutagens, carcinogens, teratogens, and embryotoxins (Daughton, 1999). The most widely
used substance is cyclophocamide (CP). In Denmark, approximately 13 to 14 kg of CP is
used in hospitals each year, and approximately 6 kg are prescribed by pharmacies
(Christensen, 1998). Thus, it is assumed that a total of 20 kg are used per year
(Christensen, 1998). Anti-cancer drugs are also referred to in the Case Study on Platinum
Group Metals.
Analgesic drugs
Analgesic drugs are used for pain relief and are probably the most commonly used
medicines.
Endocrine-disrupting substances
There is increasing concern about compounds that interfere with the hormonal system.
Endocrine disrupting substances block or trigger oestrogenic effects by binding to receptors.
Receptor-specific responses are particularly problematic as they can affect people for which
they are not intended (Christensen, 1998). An endocrine-disruptor may have an ‘agonistic
effect’ where it binds to the receptor instead of the natural hormone and causes a response,
or it may have an ‘antagonistic effect’ where the binding of the compound prevents the
natural one from binding and producing the required response (Environment Agency of
England and Wales, 1998). Other effects may also occur, showing that the process is very
complex and affects many systems in the body.
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Section 6. Case Studies
Of these, oestrogens are of a major concern, as they are excreted in an inactive form but
are found to be reactivated in sewage effluent. Oestrogens are organic molecules derived
from cholesterol, which can bind to receptors and cause a physiological response
(Montagnani et al., 1996). The purpose of the endocrine system is to regulate metabolic
activity, which requires a degree of interaction with the nervous system (Montagnani et al.,
1996). Because oestrogen receptors are located in the cell nucleus, oestrogen-like
molecules can thus enter the cell and could potentially interact with DNA, causing damage
which may lead to tumour formation (Montagnani et al., 1996). Prolonged exposure to these
compounds may induce female characteristics in males. There is increasing speculation that
these compounds may be linked to reduction in male fertility and reproductive complications
(Montagnani et al., 1996).
In the UK, research has shown that male fish exposed to the natural hormone: 17β-
oestradiol, oestrone, and the synthetic hormone: ethinyloestradiol, from domestic sewage
effluent, developed hermaphrodite characteristics (Alcock et al., 1999). It was also found that
these hormones were present in the biologically active form, having been transformed and
reactivated after excretion and not degraded during wastewater treatment (Alcock et al.,
1999). However, research carried out by the Ministry of Agriculture, Food and Fisheries
(MAFF) along the river Lea, UK determined that although estrogenic substances are likely to
be present in wastewater effluents, the development of female characteristics in male fish
present in WWTS lagoons is unlikely to be due to these substances, as the transformation is
only possible at a very early stage in their development (Montagnani et al., 1996). Due to the
widespread use of estrogenic substances and their entry into the environment via sludge
and effluent from WWTS, aquatic environments may be acting as a sink for these
substances. Natural and synthetic estrogens are extremely widely present/used. Although
the contribution these compounds make to oestrogenic effects is thought to be small, they
are are of concern because of their highly persistent and potent nature (ENDS, 2000).
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Section 6. Case Studies
Table d.2: Major drugs and drug groups and their consumption in Denmark, in 1997
[ENDS, 2000, Christensen, 1998, and Halling-Sørensen, 1998].
It was also found that a total of 110 tonnes of antibiotics were used as growth promoters,
feed additives or as medicines, on livestock and fish farms (Halling-Sørensen, 1998). In
1994, the overall production of antibiotics in Germany was 1831 tonnes, of which Penicillin
contributed 624 tonnes (Hirsch, 1999). It should be noted that the amount of antibiotics used
for human and veterinary purposes, 37.7 tonnes and 110 tonnes respectively, is in the same
range as the amounts of certain pesticides used (Hirsch, 1999). A paper published by Goll
van (1993) estimates that if the total amount of growth promoters used in the Netherlands
was spread on their 2 million hectares of agricultural land, this would give a yearly average
of 130mg of antibiotics and metabolites/m2 (Halling-Sørensen, 1998).
The pharmaceutical substances predominantly used in hospitals must also take into account
compounds such as X-ray contrast media. Iodinated X-ray contrast media are very stable
biochemically, so they tend to be excreted unmetabolised. In Germany, 500 tonnes per year
of X-ray contrast media are used and iopromide (CAS 73334-07-3) alone accounts for 130
tonnes per year (Ternes, 2000). Other X-ray contrast substances used in the EU are:
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Section 6. Case Studies
diatrizoate (CAS 131-49-7) an ionic X-ray diagnostic drug, iopamidol (CAS 60166-93-0) and
iopromide (CAS 73334-07-3) both non-ionic X-ray diagnostic substances, iothalamic acid
(CAS 2276-90-6) and ioxithalamic acid (CAS 28179-44-4) both ionic X-ray diagnostic
substances.
Other biologically active compounds are common in wastewater, and there is increasing
evidence that such substances are widely present in the environment. Danish research has
found that up to 68 different drug residues can be detected in the environment. Compounds
such as caffeine, nicotine, aspirin, and paracetamol are all frequently detected (ENDS,
2000). More studies are now looking at the prevalence of these drugs and their metabolites
in wastewater and sewage sludge. For example, clofibric acid (2-(4-chlorophenoxy)-2-
methylpropionic acid), which is a breakdown product of lipid-regulating drugs, is highly
persistent and resistant to wastewater treatment, as usually only 15-51% is removed (ENDS,
2000). Lipid regulating drugs are commonly prescribed and it is thought that the daily load of
clofibric acid to UWW collecting systems in Denmark, is around a few kilograms (ENDS,
2000). Concentrations of clofibric acid have also been detected in sewage effluent in
micrograms per litres, and in nanograms per litres in water bodies such as rivers and lakes
(ENDS, 2000). In the UK, clofibric acid has been detected in the 1 µg.l-1 range in the aquatic
environment, and in Germany, it has been detected at concentrations up to 165 ng.l-1
(Ternes, 2000).
Antibiotics have been also widely detected. In Germany, concentrations up to 5 µg.l-1 were
found in WWTS effluents, which is comparable to the data collected by Richardson and
Bowron in 1985 (Hirsch, 1999). Five of the 18 compounds investigated were frequently
detected in German WWTS effluent and rivers: erythromycin, roxithromycin, clarithromycin,
sulfamethoxazole, and trimethoprim. The highest concentration was detected for
erythromycin degradation products, at a median value of 2.5 µg.l-1 in WWTS effluent and a
maximum value of 6 µg.l-1 (Hirsch, 1999). The other four antibiotics were only detected at
levels below 1 µg.l-1 (Hirsch, 1999). Median values for the concentrations detected in surface
waters are one order of magnitude lower than those detected in WWTS effluent (Hirsch,
1999), (see Figure d.3).
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Section 6. Case Studies
Analyses for tetracycline and penicillins found no detectable amounts in five WWTS effluents
or surface waters (Hirsch, 1999). Tetracyclines tend to form stable complexes with calcium
and other ions, thus contaminating the sediment rather than the water (Hirsch, 1999).
Penicillins tend to be easily eliminated, as they are very susceptible to hydrolysis of the β-
lactam ring (Hirsch, 1999). Ground water samples were also slightly contaminated by
sulphamethoxazole and sulphamethazine (not used in human medicine), due to infiltration
from application of contaminated sewage sludge or manure to agricultural land. The samples
collected contained concentrations of sulphonamide residues up to 0.48 µg.l-1 (Hirsch,
1999).
X-ray contrast media are also widespread in German wastewater influent and effluent.
Loads of the most frequently used compounds, such as iopromide were found to exceed
1µg.l-1 during the working week but decreased at weekends as X-rays did not tend to be
performed (Ternes, 2000). Maximum concentrations detected were greater than 3 µg.l-1 (up
to 15 µg.l-1 for iopamidol). Median values were around 0.25-0.75 µg.l-1, which indicates their
ubiquity in German wastewater treatment effluents (Ternes, 2000). The compounds detected
depended on the region and on the practices of particular hospitals in that area.
Antiseptics are another major group of pharmaceutical compounds commonly used both in
households and in medical practices. It has been found that major antiseptics, such as
chlorophene and biphenol, are present at concentrations up to 0.05 µg.l-1 in wastewater
(Ternes, 1998b). However, biphenol tends to be eliminated at rates of 98% during treatment
and chlorophene at 63% (Ternes, 1998b). These compounds, particularly clorophene, are
detected in rivers at similar concentrations. This is probably due to the fact that they are also
used in many household detergents and disinfectants, as well as in veterinary medicine on
farms, so leading to widespread contamination of the aquatic environment.
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Section 6. Case Studies
In the UK, analysis of sampled effluents found that natural hormones (17β-oestradiol and
oestrone) are present in the range 1.4 to 76 ng.l-1, whereas the synthetic hormone
(ethinyloestradiol) was only found in 3 out of the 7 effluents analysed and at comparatively
low levels: 0.2 to 7 ng.l-1 (Alcock et al., 1999). The source of these is thought to be mainly
from human excretion products. It was also found that the hormones were present in the
biologically active form, suggesting that they had been transformed and reactivated after
excretion (Alcock et al., 1999).
In Germany, raw sewage was found to contain 0.015 µg.l-1 of 17β-estradiol and 0.027 µg.l-1
of oestrone and it was also found that oestrone and 17α-ethinyloestradiol were not efficiently
removed during wastewater treatment (Ternes, 1999a). In contrast, 17β-oestradiol and 16α-
hydroxy-oestrone were eliminated with a higher efficiency: around 64-68% (Ternes, 1999a)
(See Figure d.4).
Figure d.4: Elimination percentages and loads of estrogens during passage through a
municipal sewage treatment plant located near Frankfurt/Maine over 6 days [Ternes,
1999a].
In discharges from the treatment plants, all compounds could be detected in the ngl-1 range
(Ternes, 1999a), however oestrone was predominant with concentrations up to 0.07 µgl-1
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Section 6. Case Studies
and a median value of 0.009 µgl-1. The compounds 17α-ethinyloestradiol and 16α-hydroxy-
estrone were found at the detection limit of 0.001 µg l -1 (Ternes, 1999a). Oestrone was the
only compound detected in 3 of the 15 rivers sampled at concentrations between 0.7 and 1.6
ng l-1 (Ternes, 1999a). Therefore, it seems that these compounds, particularly natural
oestrogens, are not degraded in the treatment system and tend to accumulate in sludge and
effluent. However, the loads entering receiving waters are quite low. DEHP is also an
endocrine-disrupting compound. In Sweden, it has been found in all sewage sludge samples
analysed, with concentrations between 25-660 mg kg-1 dry weight (Alcock et al., 1999).
In Italy, drinking water, rivers, and sediments have been analysed to determine the extent of
environmental contamination by pharmaceuticals (see Table d.4), (Zuccato, 2000).
Table d.4: Concentrations of medicinal drugs in drinking water, river water, and
sediments [Zuccato, 2000].
DRUG DRINKING WATER (ngl-1) RIVER WATER (ngl-1) RIVER SEDIMENTS (ng kg-1)
Po (Piacenze Po
Lambro Adda Lambro Adda
Milan Lodi* Varese and, (Piacenze,
(Milan)* (Sondrio) (Milan) (Sondrio)
Cremona)* Cremona)*
Atenolol <LOD <LOD <LOD 169·9-241·9 49·5-84·3 <LOD <LOD <LOD <LOD
Bezafibrate <LOD <LOD <LOD 134·3-202·7 15·1-22·4 1·6 130 <LOD <LOD
Ceftriaxone <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Clofibric acid <LOD 3·2-5·3 <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Cyclophospha
<LOD <LOD <LOD 2·2-10·1 <LOD <LOD <LOD <LOD <LOD
mide
19·6-
Diazepam <LOD
23·5
0·2 0·7-1·2 0·5-0·7 <LOD <LOD <LOD <LOD
Erythromycin <LOD <LOD <LOD <LOD-17·4 0·7-0·9 <LOD 630 400-600 10
Furosemide <LOD <LOD <LOD 85·1-88 <LOD <LOD <LOD <LOD <LOD
Ibuprofen <LOD <LOD <LOD 90·6-92·4 <LOD-4·0 1·0 220 <LOD <LOD
Lincomycin <LOD <LOD <LOD 6·8-13·8 1·2-4·6 <LOD 130 <LOD <LOD
Oleandomycin <LOD <LOD <LOD <LOD-0·8 0·4-4·8 2·7 <LOD <LOD <LOD
Ranitidine <LOD <LOD <LOD <LOD-9·4 <LOD <LOD 150 <LOD-410 <LOD
Salbutamol <LOD <LOD <LOD <LOD-3·1 <LOD-4·6 <LOD <LOD <LOD <LOD
Spiramycin <LOD <LOD <LOD 8·4-68·3 <LOD <LOD 2900 <LOD-380 380
Tilmicosin <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD
Tylosin <LOD 0·6-1·7 <LOD <LOD-2·2 <LOD <LOD 2640 <LOD-130 <LOD
(<LOD = below the limit of detection)
It can be seen that most drugs were measurable in these media, showing widespread
contamination. The concentrations measured could potentially give rise to human exposure
in the ng day-1 range, which is 3-4 orders of magnitude lower than the concentrations
capable of producing pharmacological effects (Zuccato, 2000). Hence, acute exposure is
assumed to be unlikely, but long-term effects must still be studied.
In Germany, occurrence of drugs in WWTS and rivers has been studied (Ternes, 1998c).
Results showed maximum values in average loads of up to 3kg.day-1 for salicylic acid in the
influent and up to 114g.day-1 for carbamazepine in the effluent (Ternes, 1998c).
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Section 6. Case Studies
Figure d.5: Elimination of different drugs during passage through a municipal sewage
treatment plant near Frankfurt/Maine over 6 days [Ternes, 1998c].
From Figure d.5, it appears that more than 60% of the compounds in the influent were
usually removed during treatment of wastewater: ranging between 7-99% removal (Ternes,
1998c). Only carbamazepine, clofibric acid, and phenanzone were less efficiently eliminated
(Figure d.6). However, complete elimination was not usually achieved; thus receiving waters
may potentially be contaminated. Subsequently, a screening programme of 49 different
German WWTS effluents was carried out, in addition to river sampling. Lipid regulating
agents were found in the majority of the WWTS effluents, and in many river samples but in a
much lower concentration (Ternes, 1998c). Polar metabolites of the compounds were
usually detected. For example, clofibric acid was detected at levels up to 1.6 µg.l-1 in WWTS
effluent and in the ng.l-1 range in rivers, which illustrates the importance of metabolites
(Ternes, 1998c). Anti-inflammatories , such as, ibuprofen and naproxen, were also detected.
Diclofenac was present in the highest concentration at median levels of 0.81 µg.l-1 in treated
effluent effluent and 0.15 µg.l-1 in rivers (Ternes, 1998c). In the case of betablockers, the
highest median concentration was found for metoprolol at 0.73 µg.l-1 in WWTS effluent and
0.45 µg.l-1 in rivers (Ternes, 1998c). β2-sympathomimetics were also present but in very low
concentrations. Anti-cancer agents such as cyclophosphamide and ifosamide were detected
at levels of 0.02 µg.l-1 and 0.08 µg.l-1 respectively in WWTS effluent; however, they are
associated with presence of hospital effluents, and are not widespread (Ternes, 1998c).
Carbamazepine, an anti-epileptic drug was widespread in the aquatic environment, with a
high median value of 2.1 µg.l-1 in effluent and 0.25 µg.l-1 in rivers (Ternes, 1998c). Annual
prescriptions of carbamazepine amount to approximately 80 tonnes per year in Germany, it
then becomes metabolised and glucuronides are excreted. However treatment of
wastewater cleaves these metabolites back to the parent compound, increasing the
environmental concentrations (Ternes, 1998c).
Table d.6 shows specific studies on pharmaceuticals in the environment and the
concentrations found for the different substances (Halling-Sørensen, 1998).
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Section 6. Case Studies
Ground water pollution has been detected in some instances, mainly due to leaching from
landfill sites containing pharmaceutical wastes (Halling-Sørensen, 1998). In Berlin, clofibric
acid has been detected in drinking water at concentrations between 10 ng.l-1 and 165 ng.l-1
and in all surface water samples around Berlin, suggesting extensive contamination (Halling-
Sørensen, 1998).
River water is often polluted with pharmaceutical compounds. Most groups of compounds,
i.e. antibiotics, antineoplastic agents, and ethinyloestradiol, have been detected between 5-
10 ng.l-1. A study conducted by Richardson and Bowron (1985), investigated the exposure of
human pharmaceuticals in the river Lea in England and found that over 170 substances are
used in excess of 1 tonne per year in the river’s catchment. This allowed them to predict a
concentration of at least 0.1µg.l-1 in the river water (Halling-Sørensen, 1998).
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Section 6. Case Studies
162
Section 6. Case Studies
163
Section 6. Case Studies
Table d.6 summarises the occurrence of certain pharmaceuticals in the environment. It can
be seen that some pharmaceuticals, such as lipid regulators, X-ray contrast media,
antibiotics etc., are ubiquitous and extremely persistent in the environment, some are even
present in drinking water: clofibric acid for example has been found at concentrations up to
0.27 µg.l-1 in some German waters. This would breach EC regulations if the compounds
were classed as pesticides (ENDS, 2000). However only a fraction of the drugs on the
market, have been investigated regarding their occurrence in the environment.
Pharmaceutical compounds enter the body and are then often metabolised in the liver
through oxidation, reduction, or hydrolysis to “phase I” metabolites, which tend to be more
toxic than the parent compound. Other reactions, such as conjugation, metabolise the
compounds into “phase II” metabolites, which tend to be inactive and more polar and water-
soluble. It has also been observed that phase II metabolites are often reactivated into the
parent compounds, either during treatment of wastewater and sewage sludge or in the
environment. For example, chloramphenicol glucoronide and N-4-acetylated sulphadimidine
(phase II metabolites of the antibiotics chloramphenicol and sulphadimidine, respectively),
are reactivated in liquid manure (Halling-Sorensen, 1998). This shows the importance of the
investigation of metabolites as well as parent compounds.
For example, 17β-oestradiol, is administered orally and mainly undergoes first-pass hepatic
metabolism, being transformed to oestrone and oestriol, which are less potent (Christensen,
1998). Other metabolites are also formed but to a lesser extent. Experiments using the
diluted slurry of activated sludge from a WWTS, were undertaken to investigate the
persistence of natural oestrogens and contraceptives under aerobic conditions (Ternes,
1999b). The natural oestrogen 17β-oestradiol, was oxidised to oestrone, which is then
linearly removed with time. Rapid elimination also occurred for16α-hydroxy-oestrone.
However, the contraceptive 17α-ethinyloestradiol was persistent and highly stable under
environmental conditions (Ternes, 1999b). Two glucuronides of 17β-oestradiol were cleaved
to their parent compounds and 17β-oestradiol was re-released in an activated form (Ternes,
1999b). This indicates that the microorganisms present have the ability to deconjugate
oestrogen glucuronides. It is interesting to note that glucuronide conjugates are the main
oestrogen metabolites excreted by humans, so during wastewater treatment, the
concentration of free oestrogen increases due to the cleavage of the glucuronide moieties
from the compounds. As a result, the predominant presence of oestrone in WWTS effluents
and rivers is due to; its high stability during treatment; the cleavage of glucuronide
conjugates from oestrone and 17β-oestradiol; and the oxidation of the latter to oestrone
(Ternes, 1999b).
Penicillin antibiotics are eliminated rapidly and have short half-lives in the body, usually 30-
60 minutes, and very high concentrations are excreted in urine: it has been determined that
up to 40% of penicillin V is excreted unchanged (Christensen, 1998).
Antibiotics are generally believed to leave humans unchanged by the body metabolism (see
Table d.7) (Hirsch, 1999) and it has been determined that up to 90% of the parent
compounds are excreted unchanged (ENDS, 2000). These active products can be excreted
either as unchanged compounds or as conjugates; 30-90% of administered antibiotics are
excreted via urine as active substances (Alcock et al., 1999). This introduces the problem at
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Section 6. Case Studies
Table d.7: Human prescription amounts and excretion rates of antibiotics [Hirsch,
1999].
A study looking at the amounts of antibiotics in human faeces found trimethoprim and
doxycycline at concentrations between 3-40 mg.kg-1, and erythromycin at concentrations
around 200-300 mg.kg-1 (Hirsch, 1999). Elimination at treatment plants is usually incomplete,
ranging between 60-90% (Ternes, 1998b). Polar antibiotics are probably not removed
efficiently because elimination is mainly due to adsorption on activated sludge, which is
mediated through hydrophobic interactions (Hirsch, 1999). As a consequence, receiving
waters and other environmental media may become contaminated. Furthermore,
erythromycin and other drugs such as naproxen and sulphasalazine, have survived in the
environment for over a year (Zuccato, 2000). Clofibric acid was also found to survive for 21
years and although its use has been stopped, it is still detected in rivers and lakes in Italy
(Zuccato, 2000).
In work by Kummerer (2000), two clinically important groups of antibiotics have been studied
with regards to their biodegradability. Chinolones and nitromidazoles possess different
chemical structures, actvity spectra and modes of action. The study found low rates of
biodegradation for ciprofloxacin, ofloxacin, and metronidazole; it also found that the
genotoxicity of these compounds remained unaffected during treatment (Kummerer, 2000).
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Section 6. Case Studies
The different groups of antibiotics were active against bacteria present in wastewater
(Kummerer, 2000).
Only a few compounds have been studied regarding their behaviour in wastewater treatment
and the results are varied. Compounds such as the analgesics, ibuprofen and naxoproxen,
have been found to have removal efficiencies between 22-90% and 15-78% respectively
(ENDS, 2000). It has also been determined that 70-80% of the drugs administered in fish
farms, are transferred into the environment (Halling-Sorensen, 1998).
Table d.6 gives an overview of the present knowledge on the environmental fate of specific
pharmaceuticals. It can be seen that most hormones, such as oestrogen, are persistent in all
areas and that most of the antibiotics used for human treatment are not biodegradable. The
majority of other compounds used for human treatment are also non-biodegradable, with the
exception of the following: paracetamol, nicotinamide, ibuprofen, caffeine, and aspirin. The
compounds used in veterinary treatment tend to be more biodegradable than human
pharmaceuticals, although the speed of degradation will depend on environmental
conditions, such as pH, and temperature.
It has also been determined that iodinated X-ray contrast media are not degraded during
wastewater treatment, due to their high polarity (log K ow of iopromide = -2.33) (Ternes, 2000).
These compounds are designed to be highly stable to give optimum results during X-ray, so
are not readily biodegradable. Ninety percent of X-ray contrast media are excreted
unmetabolised (Ternes, 2000); hence, receiving waters will also tend to be contaminated.
Concentrations up to 0.49 µg.l-1 for iopamidol were detected in receiving rivers (Ternes,
2000). It appears that groundwater may also become contaminated, as concentrations of up
to 2.4 µg.l-1 were identified for iopamidol as a result of infiltration by polluted surface water
(Ternes, 2000). The concentration of X-ray contrast media in receiving water bodies is lower
than that detected in wastewater effluent; however, due to the high persistence of such
media in the environment, this reduction seems to be less important than for other
pharmaceutical compounds (Ternes, 2000). This shows that pharmaceutical compounds
have the ability to infiltrate aquifers and survive for many years. Pentobarbital, clofibric acid,
benzafibrate, diclofenac, and carbamezepine, have all been found in aquatic environments,
persisting there for up to 20 years (Ternes, 2000).
With the exception of Denmark, there is very little data available on the use and quantities of
pharmaceuticals, which renders the task of studying the fate of these compounds in
wastewater very difficult. The list of pharmaceutical substances could be exhaustive and
prioritisation is necessary.
Certain physical processes occur that may be used to degrade these contaminants: sorption
to solids, volatilisation, chemical degradation, and biodegradation. The effectiveness of
sorption and volatilisation can be determined using the octanol water partition coefficient
(Kow) and Henry's law constant (Hc) [Rogers, 1996]:
• if log Kow is less than 2.5, the compound has a low sorption potential (i.e. it will not
adsorb onto soil particles and will not be very lipophilic),
• if log Kow is between 2.5 and 4, the compound has a medium sorption potential,
• if log Kow is greater than 4, the compound has a high sorption potential and is very
lipophilic.
• if Hc is greater than 1x10-4 and Hc/Kow is greater than 1x10-9, the compound is thought
to have a high volatilisation potential,
• if Hc is less than1x10-4 and Hc/Kow is less than 1x10-9 the compound is thought to
have a low volatilisation potential.
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Several models, using Kow, Koc, and Hc, have been developed in order to take all these
characteristics into account in order to prioritise pollutants. This has enabled an assessment
to be made of the exposure risk to such pollutants, through consuming food derived from
sludge-amended soil. Two parameters are important when trying to determine movement of
contaminants through the food chain: persistence, and non-polarity. Easily metabolised or
polar compounds do not move through the food chain. As bioconcentration increases with
lipophilicity, compounds with high log Kow values will tend to accumulate in the food chain
(Duarte-Davidson, 1996).
The low concentration of individual pharmaceutical compounds, coupled with their metabolic
characteristics leads to incomplete removal in WWTS (Daughton, 1999). They tend to be
non-volatile, so transport and movement through the environment will occur via aquatic
media. In fact, their polarity and non-volatile characteristics will often prevent them from
leaving the aquatic environment (Daughton, 1999). As it has been seen earlier, metabolites
also tend to be cleaved to the parent compound during wastewater treatment and then
released afterwards.
Nutraceuticals/Herbal Remedies
During the last several years, the popularity of nutritional supplements was codified by the
creation of a new term for the subclass of highly bioactive food supplements called
nutraceuticals (Daughton and Ternes, 1999) also referred to as nutriceuticals.
Nutraceuticals are a rapidly growing commercial class of bioactive compounds, usually
botanicals, intended as supplements to the diet. Nutraceuticals and many herbal remedies
can have potent physiologic effects. These are a mainstay of alternative medicine and have
enjoyed explosive growth in use in the United States and Europe during the last decade.
Many are used as food supplements that have either proven or hypothesized biologic activity
but are not classified as drugs by the FDA, primarily because a given botanical usually has
not one but an array of distinct compounds whose assemblage elicits the putative effect and
because these arrays cannot be easily standardized. As such, they are not regulated and
are available over the counter (heavily promoted via the Internet). Even in those cases in
which the natural product is identical to a prescription pharmaceutical (e.g., the Chinese red-
yeast product Cholestin newly introduced to the United States contains lovastatin, an active
ingredient in the approved prescription drug Mevacor used to lower cholesterol levels), a
recent ruling (Borman , 1998; Zeissel, 1999). prevented the FDA from regulation.
The significance of dietary supplements in the United States led to the creation of the Office
of Dietary Supplements (ODS) via the DSHEA in 1995 under the National Institutes of
Health (NIH) (DSHEA, 1994). The ODS maintains a searchable database (International
Bibliographic Information on Dietary Supplements [IBIDS]) of published scientific literature
on dietary supplements (NIH Office of Dietary Supplements, 1999).
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Although these substances are readily available off the counter, not always in a
characterized/standardized forms, an effort is underway to patent various nutraceuticals by
standardizing the extracts and thereby making them available only by prescription. The
patenting of hundreds of multiple-molecule nutraceuticals for therapeutic purposes could
lead to more widespread use of these substances.
Another example is Kava, which is prepared from the root of Piper methysticum, used of its
mild narcotic effect among other effects. The active ingredients in Kava are believed to be a
suite of lipophilic lactones comprising substituted -pyrones (methysticin, kavain, yangonin,
and others) (Shao, et.al.,1998). These compounds display a host of effects in humans, but
nothing is known about their effects on other organisms or fate in WWTS.
There are many nutraceuticals, both new and ‘traditional’, experiencing increased
consumption. These few examples illustrate the unknowns regarding whether these
compounds are being excreted, surviving WWT, and then having possible effects on aquatic
organisms. Nutraceuticals and herbal remedies would have the same potential fate in the
environment as pharmaceuticals, with the added dimension that their usage rates could be
much higher, as they are readily available and taken without the controls of prescription
medication. However, because these compounds are natural products, they would be
expected to biodegrade more easily .
At the beginning of the 1980s, environmental risk assessment was introduced for new
chemicals but it took a decade later for drugs to be included in the discussion. In Europe,
since the 1990's, there has been a distinction made between compounds for human use and
those used in veterinary practice. For several years legislation has been implemented for
veterinary medicines. The EU Directive 81/852/EEC, (Amended 1993), introduced the
requirement for a tiered environmental risk assessment of new veterinary products, and
attempts are being made to implement this for a review of existing substances (ENDS,
2000). Currently, environmental risk assessment consists of examining the likely
environmental sectors and if levels of pharmaceutical compounds exceed the trigger values
set, such as 100 µg.l-1 in manure, further data is required (ENDS, 2000). The technical
directive [Directive 81/852/EEC, amended 1993] concerning veterinary medical products
outlines the basic requirements for conducting an environmental risk assessment (Halling-
Sorensen, 1998). The technical directive [Directive 75/318/EEC, amended 1993] concerning
human medical products does not refer to any ecotoxicology or ecotoxicity tests and no
guidance is given on how to carry out an environmental risk assessment for drugs used by
humans. However, a draft directive for human pharmaceuticals is currently being devised,
proposing that risk assessment should be part of the approved procedure of new medical
substances (Halling-Sorensen, 1998). The EC is proposing a similar programme for human
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medicines: if drug concentrations in surface waters are predicted to exceed 0.01 µg.l-1,
toxicity testing is required to find the no effect level (NOEC) (ENDS, 2000). Although
environmental assessment of the potential impacts of newly developed drugs has been
expected in the EU since the 1st of January 1995 (Christensen, 1998), it is should be noted
that the end point of human exposure is not usually investigated. Also, assessment of
individual compounds is usually based on a limited number of tests but pharmaceuticals in
the environment may affect a large number of different organisms and species, so this ability
should be reflected in the tests carried out (Stuer-Laurisden, 2000). Pharmaceuticals may
not affect the standard test species and give rise to false negative results (Stuer-Laurisden,
2000).
A risk assessment study was carried out in Germany looking at salicylic acid, paracetamol,
clofibrinic acid, and methotrexate (Henschel, 1997). As seen previously in this Case Study,
these compounds were present in the environment and had toxic effects in at least one
standard ecotoxicological test. The most sensitive reaction however, was to a non-standard
test incorporating relevant end points for the pharmaceuticals (Henschel, 1977), so proving
the limitations of standard tests.
Risk assessment for pharmaceuticals in the environment has not usually been carried out
due to the lack of data and the need for more precise and sensitive measures in the
environmental sectors. Some high consumption compounds, such as antibiotics and clofibric
acid, are being released into the environment and have been found to be widely present in
aquatic environments, sediments and soils. Although the liver often metabolises
pharmaceutical compounds to more easily hydrolysed compounds, the metabolites can be
cleaved back to the more hydrophobic, active parent compounds by bacteria, which can
then persist and bioaccumulate.
There is a strong opinion that there are more pressing environmental problems than
pharmaceuticals and that these compounds do not pose a large risk because they are
present in such low concentrations (ng.l-1), with most effects only seen in the mg.l-1 range
(ENDS, 2000). As already stated though, disease resistance to pharmaceuticals is favoured
by low concentration exposure and compounds such as antineoplastic agents and hormones
have effects at very low levels. The effects of active compounds in the low, ng.l-1 range,
cannot be excluded, as experience with pesticides shows, impacts can be significant at low
levels (Stuer-Laurisden, 2000).
At the moment, most toxicity tests performed investigate acute impacts on specific species.
However, as most compounds in question are persistent and are discharged continuously
into the environment at low levels, it would appear to be more relevant to look at the chronic,
long-term impacts of exposure to low concentrations over all trophic levels. Some of the
long-term, chronic impacts that may be of concern are genotoxicity and reproduction
impairment. It has been found that Daphnia are tolerant to most antibiotics within the mg.l-1
range but that exposure to these levels over several weeks causes death, probably because
of toxic effects in the food organisms (ENDS, 2000). The effects of continuous exposure to
even low levels of pharmaceuticals in the environment are very complex and affect many
different organisms. More studies are necessary with regards to the long-term impacts and
the potential synergistic effects of exposure to a mixture of drugs.
Exposure route is very important in determining environmental loading, as the dose and
duration of exposure are important parameters in risk assessment. Drugs tend to be
released in low concentrations, although local discharges, such as those coming from
hospitals, may have higher concentrations (Jorgensen, 2000).
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Section 6. Case Studies
A study carried out in Italy (Zuccato, 2000), found that most drugs were present in drinking
water, river water and sediments, but that human exposure would only be in the ng day-1
range, which is much lower that the concentration where effects are expected to be
observed. The study concluded that risk seems negligible but possible long-term exposures
and impacts still need investigation. The same was found with X-ray contrast media, which
were ubiquitous in the aquatic environment and highly persistent. No acute toxic effects
were observed, in Daphnia magna or in bacteria, algae, fish, and crustaceans (Ternes,
2000). Long-term exposure was not investigated.
Risk assessments were carried out on three pharmaceuticals, using the computer program
EUSES, which was developed as a support to the technical guidance document for risk
assessment on new and existing substances (Christensen, 1998). The three compounds
assessed were; the synthetic estrogen, 17α-ethinylestradiol; the antibiotic, penicillin V; and
the antineoplastic agent, cyclophosphamide. This program estimated environmental fate and
human exposure based on worst-case scenarios, using data on the physico-chemical
properties of the compounds and amounts consumed. The results indicated that for all three
there was negligible human risk. However, the author stressed the point that many
uncertainties are associated with this method and that the drugs, although seemingly
insignificant, still contribute to the total toxic load in the environment, and that interactions
may have ecotoxicological impacts.
Research in Denmark attempted to carry out a risk assessment for the 25 most highly used
drugs in the primary health sector in Denmark, including furosemide, paracetamol,
ibuprofen, and estradiol (Stuer-Laurisden et al., 2000). Different parameters are used to
calculate environmental exposure: biodegradation, bioaccumulation, and bioavailability are
three of the most important. Nevertheless, it has been seen that biodegradation of
pharmaceuticals does not happen very often. Bioaccumulation in the human body does not
happen for drugs, as they are metabolised to more polar compounds that can then easily be
excreted. The bioavailability of drugs is different if it is bound to solids, adsorbed, or
dissolved. However, as seen above, the octanol-water partition coefficient can be used to
determine bioaccumulation, and other parameters can be used to determine bioavailability.
However, this information on the properties of the compounds is not readily available. They
found that ecotoxicology data was available only for 6 of the 25 compounds, and
biodegradation data only for 5 (Tables d.9 and d.10) (Stuer-Laurisden et al., 2000).
Predicted environmental concentrations (PEC) should be determined for the system where it
is anticipated that the highest values would be found, i.e. aquatic ecosystems and sewage
sludge (Jorgensen, 2000). In order to do so, modelling could be a useful tool; however, not
many models have yet been developed and validated due to the lack of data in this area
(Jorgensen, 2000 and Halling-Sorensøn,1998). The predicted environmental concentrations
for the 6 compounds were calculated and all exceeded 0.001µg.l-1, which is the cut off value
in EU legislation for carrying out more investigations. The majority of the PECs are between
1-100ng.l-1, it is only for the top 5 compounds that these reach the µg.l-1 range (Stuer-
Laurisden, 2000). The predicted no effect concentration (PNEC) is based on
ecotoxicological data and the PEC/PNEC ratio was found to exceed one only for ibuprofen,
paracetamol, and acetylsalicylic acid and below one for estrogen, diazepam, and digoxin
(Stuer-Laurisden, 2000). This showed that data is only partially available, preventing
complete risk assessments. Nevertheless, it was concluded, with this data, that ibuprofen,
aspirin, and paracetamol may pose a risk; hence, contradicting other studied that had
concluded these were efficiently removed by treatment and did nor reach hazardous levels
in the environment (ENDS, 2000). The efforts are hampered by the fact that concentrations
measured in sludge and effluent vary extensively, and furthermore comparisons of predicted
concentrations in sludge based on Kow, sludge-water partition coefficients (Kd), or acid-base
constants (pKa) also reveal large variations (Stuer-Laurisden, 2000).
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The cost/benefit stage of risk assessment is extremely important: the indirect and direct
effects of the drug on the environment and the human body must be known in order to make
an informed decision (Jorgensen, 2000 and Halling-Sørenson,1998). This can allow
selection of a substitute drug that has the same benefits but fewer environmental impacts.
Hence, lack of data for toxicity but also environmental concentrations prevent calculation of
risks.
In France, and the UK, there are procedures for returning prescribed but unused
pharmaceuticals. In France, these plans are encouraged by the ADEME "RETOUR" initiative
(ADEME, 1997a), which also encourages the distributor to include the costs of collection and
treatment into the product's selling price. This strategy is useful for reducing the amount of
polluted domestic and artisanal (laboratories, photographic shops etc) wastewater through
special collections for specific pollutants such as thermometers, medicines, and paint
leftovers. Most areas in France have implemented such programmes and they are
successful.
If the assessment of a drug gives a high risk, the response may not have to be the phasing
out of the drug, but maybe just the collection and specific treatment of the faeces and urine
containing this compounds (Jorgensen, 2000). Environmental risk assessment should be
part of the development of all new drugs and could be used as a marketing tool, as public
concern for the environment is increasing (Jorgensen, 2000).
Analysis tools and their sensitivity must be improved for the determination of the very low
concentrations of drugs. A method obtaining detection limits within the ngl-1 range for
various pharmaceutical compounds, particularly neutral basic drugs such as betablockers,
has been developed, using advanced solid phase extraction, modified derivatisation
procedures and LC-electrospray-MS/MS detection (Ternes, 1998a). This allows detection
down to 10ng.l-1, in different aqueous matrices. In another study, determination limits down
to 5ng.l-1 were achieved for phenolic compounds and other acidic drugs, such as lipid
regulators and acetylsalicylic acid metabolites, using solid phase extraction and methylation
or acetylation of the carboxylic and phenolic hydroxyl groups, followed by detection by
GC/MS (Ternes, 1998b).
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multi-stage biofilm process removing all organic matter and the toxicity is no longer
measurable (Rosen, et.al. 1998).
Pharmaceutical compounds must become priority substances in the same way as persistent
organic pollutants are. Judgements on the relative priorities are based on the knowledge at
the time and the priority list will obviously change over time as more studies are carried out
and more data is gathered. Pharmaceuticals are widely used and mainly disposed of
through the sewerage system, allowing their entry into the environment continually, as
removal rates can be compensated by replacement rates (Daughton and Ternes, 1999).
They are concerning because they are biologically active and are usually lipophilic and
potentially bioaccumulating. Many resist biodegradation, within the WWTS and in the
environment, and can end up in surface and ground waters, as well as sediment and soils
and are found to be highly stable under environmental conditions. Furthermore, metabolites
tend to be cleaved and transformed back to the parent compounds once in the environment,
increasing the concentrations and justifying the importance of metabolites. Many can have
unpredicted and unknown side effects particularly after long-term exposure to low
concentrations. Aquatic ecosystems are the most vulnerable, as this is the main
environmental compartment where pharmaceuticals are found ubiquitously.
Analytical methods must be improved to detect pharmaceuticals at very low levels and
sampling procedures must be of very high quality so as not to cause contamination. More
information on the physicochemical, ecotoxicity, and ecotoxicological characteristics, using
appropriate tests that better accommodate subtle end points, of drugs and their metabolites
should be obtained in order to allow environmental risk assessments to be carried out.
Furthermore, this may lead to the validation of modelling techniques that could speed up the
whole process. Furthermore, use patterns of drugs in all countries is still very limited and
should be determined, as it is essential for the elaboration of amounts released into the
environment.
Screening of high use drugs should be carried out and samples with high potential should
then be subject to more analyses (Daughton and Ternes, 1999). Furthermore, a more
precautionary view on the potential impacts of the drugs should be adopted and more
studies are required to elucidate these effects at the concentrations observed and also
investigating additive and synergistic effects of mixtures (Daughton and Ternes, 1999).
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(e) Personal Care Products, Fragrances in Urban Waste Water and Sewage Sludge
Personal care products are defined as chemicals marketed for direct use by the consumer
(excluding off the counter medication with documented physiologic effects) and having
intended end uses, primarily on the human body (products not intended for ingestion) or in
the household. In general, these chemicals alter odour, appearance, touch, or taste without
displaying significant biochemical activity (Daughton and Ternes, 1999). Most of these
chemicals are used as the active ingredients or preservatives in cosmetics, toiletries and
fragrances. They are not used for treatment of disease, but some may be intended to
prevent diseases (e.g., sunscreen agents). In contrast to drugs, almost no attention has
been given to the environmental fate or effects of personal care products, the focus has
traditionally been on the effects from intended use on human health.
Personal care products differ from pharmaceuticals in that large amounts can be directly
introduced to the environment and unlike medicinal compounds, there are rarely
recommended doses. These products can be released directly into recreational waters or
volatilised into the air. Because of this direct release they can bypass possible degradation
in UWWT. Also, in contrast to pharmaceuticals, less is known about the effects of this broad
and diverse class of chemicals on non-target organisms, such as aquatic organisms. Data
are also limited on the potential adverse effects on humans. For example, common
sunscreen ingredients, 2-phenylbenzimidazole-5-sulfonic acid and 2-phenylbenzimidazole,
can cause DNA breakage when exposed to UV-B (Stevenson and Davies, 1999).
The quantities of personal care products produced commercially can be very large. For
example, in Germany alone the annual output was estimated to be 559,000 tonnes for 1993
(Statistisches Bundesamt, 1993). A few examples are given below of common personal care
products that are ubiquitous pollutants, which may possess varying degrees of bioactivity.
Table e.1 Personal care and fragrances produced in Germany (1993)
• Preservatives
Parabens (alkyl-p-hydroxybenzoates) are one of the most widely and heavily used types of
antimicrobial preservatives in cosmetics (skin creams, tanning lotions, etc.), toiletries,
pharmaceuticals, and even foodstuffs (up to 0.1% wt/wt). Although the acute toxicity of these
compounds is very low, Routledge et al.[1998] report that these compounds (methyl through
butyl homologs), display weak oestrogenic activity. Although the risk from dermal application
in humans is unknown, the probable continual introduction of these benzoates into
wastewater treatment systems and directly to recreational waters from the skin, leads to the
question of risk to aquatic organisms. Butylparaben showed the most competitive binding to
the rat oestrogen receptor at concentrations one to two orders of magnitude higher than that
of nonylphenol and showed oestrogenic activity in a yeast oestrogen screen at 10-6 M .
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• Disinfectants/Antiseptics
A wide range of disinfectants are used in large amounts, not just by hospitals but also by
households and livestock breeders. These compounds are often substituted phenolics as
well as other substances, such as triclosan. Biphenylol, 4-chlorocresol, chlorophene,
bromophene, 4-chloroxylenol, and tetrabromo-o-cresol [Ternes et al 1998] are some of the
active ingredients, at percentage volumes of < 1-20%. A survey of 49 WWTPs in Germany
[Ternes et al 1998] routinely found biphenylol and chlorophene in both influents, up to 2.6
µg/L for biphenylol and up to 0.71 µg.l-1 for chlorophene, and effluents. The removal of
chlorophene from the effluent was less extensive than for biphenylol, with surface waters
having concentrations similar to that of the effluents.
• Sunscreen Agents
The occurrence of sunscreen agents (UV filters) in the German lake Meerfelder Maar was
investigated by Nagtegaal et al. [1997]. The combined concentrations of six sunscreen
agents (SSAs) identified in perch (Perca fluviatilis) in the summer of 1991 were as high as
2.0 mg.kg-1 lipid and in roach (Rutilus rutilus L) in the summer of 1993, as high as 0.5 mg.kg-
1
lipid. Methylbenzylidene camphor (MBC) was detected in roach from three other German
lakes. These lipophilic SSAs seem to occur widely in fish from small lakes used for
recreational swimming. Both fish species had body burdens of SSA on par with PCBs and
DDT. The bioaccumulation factor, calculated as quotient of the MBC concentration in the
whole fish (21 µg.kg-1) versus that in the water (0.004 µg l-1), exceeded 5,200, indicating high
lipophilicity. The fact that SSAs (e.g., 2-hydroxy-4-methoxybenzophenone [oxybenzone] and
2-ethylhexyl-4-methoxycinnamate) can be detected in human breast milk (16 and 417 ng.g-1
lipid, respectively) [Hany et al 1995] shows the potential for dermal absorption and
bioconcentration in aquatic species. No data have been published on newer SSAs such as
avobenzene (1-[4-(1,1-dimethylethyl)phenyl]-3(4-methoxyphenyl)-1,3-propanedione).
• Perfume Ingredients
The raw ingredients in perfumes include essential oils, plant extracts and animal secretions,
and synthetic or semi synthetic (natural material that has undergone some chemical
modification) compounds. Thousands of these substances can be blended to create
perfumes. These can be used directly as perfumes or as scents in other products, for
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Section 6. Case Studies
example in cosmetics, cleaning agents and air fresheners. Perfume ingredients may enter
the urban wastewater system directly from domestic sources, such as in the washing agents
or from being washed off skin in the case of perfumes and cosmetics.
The organic compounds found in perfumes that may be of environmental or health concern
include
- nitro-musk compound,
- polycyclic musk compound,
- solvents and fixatives
- other fragrances.
Details of the physical properties of these compounds are included in Appendix B. Health
and environmental effects of the compounds discussed are also briefly introduced within this
case study.
This case study will focus on musk compounds. Fragrances (musks) are ubiquitous,
persistent, bioaccumulative pollutants that are sometimes highly toxic; amino musk
transformation products are toxicologically significant.
Synthetic musks comprise a series of structurally similar chemicals (which emulate the odour
of the more expensive, natural product, from the Asian musk deer), used in a broad
spectrum of fragranced consumer items, both as fragrance and as fixative. Included are the
older, synthetic nitro musks (e.g., ambrette, musk ketone, musk xylene, and the lesser
known musks moskene and tibetene) and a variety of newer, synthetic polycyclic musks that
are best known by their individual trade names or acronyms.
The major musks used today are, the polycyclic musks (substituted indanes and tetralins),
which account for nearly two-thirds of worldwide production and the inexpensive nitro musks
(nitrated aromatics), accounting for about one-third of worldwide production. These
substances are used in nearly every commercial fragrance formulation (cosmetics,
detergents, toiletries) and most other personal care products with fragrance; they are also
used as food additives and in cigarettes and fish baits (Gatermann, et.al. 1998)
The nitro-musks are under scrutiny in a number of countries because of their persistence
and possible adverse environmental impacts and therefore are beginning to be phased out
in some countries. Musk xylene has proved carcinogenic in a rodent bioassay and is
significantly absorbed through human skin; from exposure to combined sources, a person
could absorb 240 µg/day [Bronaugh et al 1998]. The human lipid concentration of various
musks parallels that of other bioaccumulative pollutants, such as PCBs [Schmid 1996].
Worldwide production of synthetic musks in 1988 was 7000 tonnes [Gattermann et al 1998]
and worldwide production for nitro musks in 1993 was 1,000 tonnes, two-thirds of which
were musk xylene [Kfferlein 1998]
Synthetic musks first began to be identified in environmental samples almost 20 years ago
[Yamagishi 1981 and 1983]. By 1981, Yamagishi et al. had identified musk xylene and musk
ketone in gold fish (Carassius auratus langsdorfii) present in Japanese rivers and soon after
[Yamagishi et al 1983] in river water, wastewater, marine mussels (Mytilus edulis), and
oysters (Crassosterea gigas). This was followed by a number of studies in Europe, some of
which are summarised in table e.2.
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Section 6. Case Studies
Musks are refractory to biodegradation (other than reduction of nitro musks to amino
derivatives), which explains why they have been detected in water bodies throughout the
world [Gattermann et al 1998]. They also are very lipophilic [octanol-water partition
coefficients are similar to those for DDT and hexachlorocyclohexane , Winkler et al, 1998]
and therefore can bioaccumulate, leading to very high concentrations being measured in
some studies.
The values for the three most prevalent musks in the Elbe river study (table e.2) were within
the same order of magnitude as those for 15 polycyclic aromatic hydrocarbons (PAHs) and
exceeded those for 14 common polychlorinated organic pollutants (only hexachlorobiphenyl
[HCB] and p,p´-DDT were of similar concentration). Also, all the 31 water samples contained
musk ketone (2-10 ng.l -1), Galaxolide (36-152 ng.l -1), and Tonalide (24-88 ng.l-1); Celestolide
was found only at 2-8 ng.l-1. These higher values exceeded those for all the polychlorinated
organics and the PAHs. The occurrences of individual musks are sometimes correlated as a
result of their use as mixtures in commercial products. In Germany, the nitro musks are
being replaced by the polycyclic musks, therefore resulting in lower concentrations for musk
ketone [Winkler et al, 1998].
Although the significance of the aquatic toxicity of the nitro and polycyclic musks is
debatable (genotoxicity from the polycyclics seems not to be a concern) [Kevekordes 1998],
the aminobenzene (reduced) versions of the nitro musks can be highly toxic. These reduced
derivatives are undoubtedly created under the anaerobic conditions of sewage sludge
digestion. Behecti et al. [1998] tested the acute toxicity of four reduced analogs of musk
xylene on Daphnia magna. The p-aminodinitro compound exhibited the greatest toxicity of
the four, with extremely low median effective concentration (EC50) values averaging 0.25
µg.l-1 (0.25 ppb).
Recently, the amino transformation products of nitro musks were identified in wastewater
treatment effluent and in the Elbe River, Germany. Gatermann et al. [1998] identified musk
xylene and musk ketone together with their amino derivatives 4- and 2-amino musk xylenes
and 2-amino musk ketone. In wastewater entering treatment plants, the concentrations of
musk xylene and musk ketone were 150 and 550 ng.l-1, respectively. In the effluent, their
concentrations dropped to 10 and 6 ng.l-1, respectively. In contrast, although the amino
derivatives could not be detected in the influent, their concentrations in the effluents
dramatically increased, showing extensive transformation of the parent nitro musks: 2-amino
musk xylene (10 ng.l-1), 4-amino musk xylene (34 ng.l-1), and 2-amino musk ketone (250
ng.l-1). It was concluded that the amino derivatives could be expected in wastewater effluent
at concentrations more than an order of magnitude higher than the parent nitro musks. In the
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Section 6. Case Studies
Elbe, 4-amino musk xylene was found at higher concentrations (1-9 ng.l-1) than the parent
compound.
Because synthetic musks are ubiquitous; used in large quantities; introduced into the
environment almost exclusively via treated wastewater; and are persistent and
bioconcentratable, they are prime candidates for monitoring in both water and biota as
indicators for the presence of other personal care chemicals. Their analysis, especially in
biota, has been thoroughly discussed by Gatermann et al. [1998] and by Rimkus et al.
[1997].
It is thought that musk compounds can bioaccumulate in human tissue [spinnrad website
2000] and act as hormones, because they bind to the hormone receptors of the cells
[Gerhard, I umweltmedizin website 2000]. However, there is insufficient data for an adequate
toxicologically assessment for both the nitro- and the polycyclic musk scents [Antusch,
1999].
Emission Data
At the present time the quota of the polycyclic musk scents amounts to approximately 85 %
of total musk production worldwide, and the quota of nitro-musk scents is approximately 12
% [Rebmann et al., 1998].
o for musk-xylene: 0.12 µg.l-1 (concentration range: 0.03 – 0.31 µg.l-1) and
o for musk-ketone: 0.63 µg.l-1 (concentration range: 0.22 – 1.3 µg.l-1).
The mean emission levels in Germany were quantified as 20 µg/inhabitant/day for musk-
xylene and 90 µg/inhabitant/day for musk-ketone [Eschke et al., 1994].
In Vienna, Austria, extensive testing of wastewater was carried out at the pilot plant of the
city’s main WWTP, during 1999. Concentrations of musk compounds in WWTP influent and
effluent are shown in Table e.3.
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Section 6. Case Studies
Table e.3: Musk compound concentrations in influent and effluent of the pilot WWTP
Simmering, Austria in 1999 [Hohenblum et al., 2000].n: number of samples analysed.
LOD: limit of detection
Compound Type of Sample Range Mean
(µg.l-1) sample number > (µg.l-1) Value
LOD (µg.l-1)
Musk-xylene Influent 4 0.023 - 0.037 0.031
(n=4) Effluent 0 - -
Musk-ambrette Influent 0 - -
(n=4) Effluent 0 - -
Musk-moskene Influent 0 - -
(n=4) Effluent 0 - -
Musk-tibetene Influent 0 - -
(n=4) Effluent 0 - -
Musk-ketone Influent 4 0.049 - 0.069 0.056
(n=4) Effluent 4 0.038 -0.053 0.049
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Section 6. Case Studies
The pollution of the river Ruhr (Germany) with musk compounds was found to be relatively
low, with maximum concentrations of 0.08 µg.l-1 and 0.03 µg.l-1 for musk-ketone and musk-
xylene, respectively. Fish from the Ruhr contained residues of musk compounds in their
muscle flesh, at concentrations below 10 µg.kg-1 wet weight [Eschke et al., 1994].
The polycyclic musks, HHCB (galaxolide, abbalide) and AHTN (tonalide, fixolide) were found
in German receiving waters at concentrations up to the µg.l-1 level. In the Wuhle, a small
stream consisting almost totally of wastewater effluent, maximum concentrations were 12.5
µg.l-1 for HHCB and 6.8 µg.l-1 for AHTN. Additionally, the polycyclic musk ADBI (celestolide,
crysolide) and musk-ketone were detected at low concentrations in the majority of samples.
Two other nitro-musks, moskene and xylene, were only detected in a single surface water
sample [Heberer et al., 1999].
The concentration of the three compounds tonalide, celestolide and galaxolide, were
measured in different watercourses in Germany. The results of this study are shown in Table
e.5. The Elbe concentrations for musk-xylene were approximately 0.2 µg.l-1.
Conclusions
There is very limited information on the health and environmental effects of personal care
products, such as the musk compounds found in perfumes. Many of these compounds have
the potential to bioaccumulate, which is why there is concern about their presence in
wastewater. Though these products may be used in large quantities there is insufficient data
though to establish whether the presence of these compounds in UWW could cause any
detrimental environmental or health effects.
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Introduction
Surfactants are the largest class of anthropogenic organic compounds present in raw
domestic wastewater. They are used in household and commercial laundry and cleaning
operations. Surfactants can be classified [Ullman’s Encyclopaedia of Industrial Chemistry,
2000] into:
The largest proportion of surfactants is used in detergents and cleansing agents for
domestic and commercial use [Falbe, 1987]. Surfactants are also used in:
Textile manufacturers uses surfactants extensively as washing agents, also for cleaning,
lubricating, bleaching, de-sizing or shrinking (where the mutual adhesion of fibres is
reduced), mercerising (cotton treatment that requires wetting agents), and finishing. Wool
washing is done with NIS, while cotton is washed with anionic surfactants. The leather
industry uses non-ionic and cationic surfactants as wetting and cleansing agents, and also
for leather conditioning. Surfactants are also used as emulsifiers and dispersants, and also
as food additives (natural substances only, such as glycerides, fatty acid salts, etc.).
Pharmaceuticals manufacturing uses surfactants, and they are also used in agricultural
applications such as crop-protection and pest control agents. Metal working and machining,
petroleum extraction and processing, ore flotation and dressing, mineral oil industry, road
construction and maintenance work, cement industry, plastics production, pulp and paper
industry and printing, electroplating, adhesives manufacturing, all use surfactants for their
unique properties.
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Section 6. Case Studies
Ionic surfactant molecules contain both strongly hydrophobic and strongly hydrophilic
groups. They thus tend to concentrate at interfaces of the aqueous system including air, oily
material and particles. The hydrophobic group is generally a hydrocarbon radical (R) of 10 to
20 carbon atoms. The hydrophilic portion may ionise or it may not. Ionic surfactants may be
either anionic or cationic. Ionic surfactants constitute approximately two-thirds of the
surfactants used. Cationic surfactants constitute less than 10% of the ionics and are used for
fabric softening, disinfection and other specialized applications. The predominant class of
anionic surfactants is linear alkylbenzene sulphonates (LAS).
The concentrations of linear alkylbenzene sulphonates (LAS) in raw wastewater range from
3 mg.l -1 to 21 mg.l-1 (Brunner et al., 1988, De Henau et al., 1989, Ruiz Bevia et al., 1989).
Although LAS and other common surfactants have been reported to be readily
biodegradable by aerobic processes, much of the surfactant load into a treatment facility
(reportedly 20-50%) is associated with suspended solids and thus escapes aerobic
treatment processes, being directed via primary sedimentation into sludge management
processes. Because LAS is not biodegraded by anaerobic biological processes usually
employed in sludge stabilization (McEvoy and Giger, 1985; Swisher, 1987), it may be found
in the gram per kilogram range in anaerobic sludges. Given these concentrations and the
major effects of surfactants in particle surface modification, deflocculation, and surface
tension reduction, it seems clear that the performance of certain treatment processes as
thickening, conditioning, and dewatering may be strongly influenced by these materials.
Thus, surfactants may induce significant extra costs in sludge handling. Increased water
content in landfilled sludges represents an additional possible impact, adding to the difficulty
of proper landfill leachate control. Surfactants may also mobilise otherwise insoluble organic
pollutants within the landfill. Similar implications exist for land application of surfactant-laden
sludges.
Feijtel et al [1995] examined five WWTS across Europe and found the influent of LAS to
WWTS in the UK to be higher than in the other plants (see Table d.1).
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Section 6. Case Studies
Table d.1 LAS in influent and effluent in the UK compared with other regions [Feijtel et
al 1995]
As it can be seen from this study, the UK plants had significantly higher influent
concentrations than in Germany, Italy and the Netherlands (Spain had a very small data set
and therefore there is uncertainty in these results, which is reflected in the large confidence
intervals, which overlap with those of the UK). Having a high influent of LAS was unrelated
to the concentration in the effluent and the UK samples had a lower concentration of LAS in
its effluent than Germany, Italy or Spain. The level of biodegradation of LAS during the
wastewater treatment process is high and also varied between the plants, with the UK
WWTS having the highest level of biodegradation breaking down greater than 99.9 percent
of the LAS.
The study above, used UK data from Holt et al [1995] in which the levels of LAS in the
influent corresponded to estimates of LAS usage in homes. However a subsequent study
[Holt et al 1996], based on usage data on the influent entering six WWTS in the Yorkshire
region, found much lower levels of LAS than expected. In no cases did the concentrations of
LAS reaching the plant approach the level predicted from consumer usage. The previous
study had been carried out in March while the second was carried out in a ‘warm dry
summer’. This study suggested there was significant biodegradation of LAS under certain
conditions in the UWW collecting systems. Even in the relatively short residence time in the
Yorkshire UWW collecting system, for a couple of hours, up to 60% of the LAS was removed
prior to the wastewater treatment plant. This was then followed by removal of between 70 to
99 percent of the remaining LAS in the treatment plants.
Given the right treatment conditions, LAS are biodegradable and more research is
necessary to compare risks associated with alternative chemicals used in detergents.
The impact of LAS in wastewater effluent has been studied on several UK and Dutch rivers
and steams sediment. In some cases (such as the small stream into which the Owlwood
WWTS discharges its effluent the LAS load in sediment upstream of the treatment plant was
higher than that downstream [Waters and Feijtel 1995] This was hypothesised to be
because that the LAS contribution upstream was due to unregulated discharges of untreated
wastewater to the aquatic environment while the input of the WWTS effluent actually served
to dilute the concentration of this pollutant downstream. A similar case was found in the
Netherlands when concentrations of LAS could be higher upstream of a WWTS due to direct
discharges from storm tanks. In other locations downstream sites were found to have very
slight elevations of LAS in sediment of between 0.49 and 3µg/g. A more careful policy of
discharges has to be followed across the EU.
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Section 6. Case Studies
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Section 6. Case Studies
Figure d.2 LAS fate in the environment (after deWolf and Feijtel, 1998)
Alkylphenol ethoxylates such as NPnEO are evidently less biodegradable than LAS with
laboratory results ranging from 0-20% based on oxygen uptake (e.g. Swisher, 1970; Steinle,
1964; Pitter, 1968) and a wider range of removals from 0-90% based on specific analyses
such as UV and IR spectroscopy (Swisher, 1970). This suggests that only partial
degradation occurs, such as conversion from polyethoxylates to nonylphenol diethoxylate
(NP2EO), nonylphenol monoethoxylate (NP1EO), and nonylphenol (NP). Mass balances
carried out on treatment plants in Switzerland (Brunner et al., 1988) support this.
The findings of Brunner et al. and other reserachers, also show that the nearly complete
removal of surfactants from treated waters is not entirely due to biodegradation. Brunner et
al. indicated that 19% of the surfactant load entering a treatment facility is associated with
suspended solids, and other studies report levels up to 27% (Rapaport and Eckhoff, 1990),
or even in excess of 50% (Bevia et al., 1989). The surfactant load linked to suspended solids
is directed into sludge treatment processes via primary sedimentation. Surfactants such as
LAS are not biodegraded by either mesophilic or thermophilic anaerobic digestion (McEvoy
and Giger, 1985; Swisher, 1987) so a large proportion of these materials simply escapes
treatment and becomes associated with sludge solids.
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Section 6. Case Studies
As stated previously, given these surfactant concentrations and the considerable effect that
surfactants can have on the properties of suspensions such as sludges, the performance of
such processes as thickening, conditioning, and dewatering may be strongly influenced by
these materials. For example, Bierck and Dick (1988) have shown that surface tension of
sludge solids is directly related to the capillary pressure available for solids compression
during the latter stages of vacuum filtration:
Ps,s = v [1/R1 + 1/R2]
Where,
Ps,s = the pressure or effective stress producing solids shrinkage,
v = the surface tension,
R1 and R2 = principal radii of curvature of the solid surface.
Thus the effect of surfactants, in lowering the surface tension, is to decrease the
compressive dewatering by allowing gas penetration of the solids cake. Campbell et al.
(1984, 1986) showed that a detergent could decrease the dewaterability of a sludge even
before the compressive phase, as indicated by capillary suction time (CST) measurements.
Household detergent added to anaerobically digested sludge at 0.2 and 0.3% by volume
caused significant increases in the CST (poorer dewaterability) which could not be
compensated for even by doubling the addition of cationic polymer used as the sludge
conditioner.
The biodegradation mechanism of LAS was described by Balson and Felix(1995). The
mechanism of breakdown of LAS involves the degradation of the straight alkyl chain, the
sulphonate group and finally the benzene ring. The breakdown of the alkyl chain starts with
the oxidation of the terminal methyl group (w-oxidation) through the alcohol, aldehyde to the
carboxylic acid as follows (see Fig. d.3a). The reactions are enzyme catalysed by alkane
monooxygenase and two dehydrogenases. The carboxylic acid can then undergo b-
oxidation and the two carbon fragment enters the tricarboxylic acid cycle as acetylCo-A. It is
at this stage that problems arise with branched alkyl chains, a side chain methyl group or a
gem-dimethyl-branched chain cannot undergo b-oxidation by microorganisms and must be
degraded by loss of one carbon atom at a time (a-oxidation, Figure d.3b). (Scott and Jones,
2000).
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Section 6. Case Studies
The second stage in LAS breakdown is the loss of the sulphonate group. The loss of the
alkyl and the sulphonate group from LAS leaves either phenylacetic or benzoic acids.
Microbial oxidation of phenylacetic acid can result in fumaric and acetoacetic acids and
benzene can be converted to catechol .
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Section 6. Case Studies
The presence of surfactants in sewage sludge may have undesirable environmental effects
if land application is the chosen disposal method. The surfactant molecules may leach to
groundwater contributing to groundwater contamination. Federle and Pastwa (1988) studied
the percolation of anionic and nonionic surfactants through a soil column. Most of the
surfactant was mineralised, but this process was found to be highly dependent on the
number of organisms present in the soil. A number of reports (e.g. Bevia et al., 1989; Holt et
al., 1989) attribute observed decreases of LAS concentrations over time in sludge-amended
soils to biodegradation, without evaluating possible migration. Marcomini et al. (1989)
reported a fraction of LAS in sludge-amended soil to be resistant to biodegradation over long
time periods. Table d.2 contains data on fate and persistence of surfactants in sludge
amended soils.
Not only may surfactants migrate to groundwater, but they may also carry hydrophobic
organic pollutants with them. The degree of partitioning of hydrophobic organic pollutants to
particles depends on the hydrophobicity of the pollutant and the amount of organic matter
contained in the particle. Dissolved organic matter tends to decrease the potential for
sorption by providing an additional aqueous phase to which the pollutant can partition
(Enfield et al. 1989). Partitioning of surfactant to sludge particles in the sewage treatment
plant would be expected to enhance the partitioning of organic pollutants to sludge. When
applied to land, desorption of surfactant could lead to pollutants also being released. Kile
and Chiou (1989) studied the effect of anionic, cationic and nonionic surfactants on the
water solubility of DDT and trichlorobenzene. The results were extremely surprising. As
would be expected, the solubility was enhanced when the surfactant was present at
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Section 6. Case Studies
concentrations greater than the critical micelle concentration. There was also a solubility
enhancement at surfactant concentrations less than the critical micelle concentration.
Recent studies have revealed that fish living downstream of wastewater treatment plants
show oestrogenic effects [Purdom et al. 1994] as a result of alkylphenol polyethoxylates
(APE) and nonylphenol (NP) present in the water. Male fish produce vitellogenin, a yolk
protein which is formed under the influence of oestradiol and therefore is typically produced
by females. Hermaphrodite fish species have been found as well. The decomposition
products of APE, are considered as a potential cause, since their decomposition products
formed in WWTS (Giger et al. 1984) show slightly oestrogenic effects (Soto et al. 1991,
Jobling and Sumpter 1993).
Alkylphenol polyethoxylates (APE) usually enter surface waters via WWTS, where they
are degraded - but not totally - by microorganisms. In a first rapid step the ethoxylate groups
are split off by hydrolysis, and the metabolites nonylphenol (NP), nonylphenol ethoxylate
(NP1EO) and nonylphenol diethoxylate (NP2EO) are formed. These metabolites are more
toxic than the original substances. Due to the hydrophobic properties of the aromatic group
the second step of biodegradation occurs much slower. The interim products can also be
biodegraded to alkylphenoxy ethoxylate carboxylic acids (APEC). The second, slower,
step of biodegradation, does not always occur, and the fact that the metabolites are more
lipophilic than the parent compounds can cause an accumulation of interim products in
sludge and sediment. Nonylphenol, for example, was determined in digested sludge in
concentrations between 0,45-2,53 g.kg-1 dry weight (Giger et al. 1984). Approximately 50 %
of the APE occurring in the wastewater are estimated to reach the sludge as NP (Brunner et
al. 1988). Before prohibition of APE in washing agents NP, NP1EO and NP2EO
concentrations between 36-202 µg/l were found in drain channels of WWTS in Switzerland.
Now NP concentrations in drain channels from WWTS, are found at concentrations between
1 and 15 µg.l-1 in Switzerland and Germany; other metabolites (NP1EO, NP2EO, NP1EC)
are normally determined to be between 1 and 40 µg.l-1 (Ahel et al. 1994a, Ahel et al. 1994b,
Giger 1990). Concentrations of 15 µg.l-1 in drain channels of WWTS were determined in the
USA. In highly polluted streams average nonylphenol concentrations are determined to be in
the range 0.3 to 3 µg.l-1 (Ahel et al. 1994a), polyphenoxy carboxylic acids products are
predominant, whereas in sediment NP was the dominating degradation product. Due to their
high octanol/water partition coefficient (log 4.0-4.6) nonylphenol, NP1EO and NP2EO show
a tendency towards bioaccumulation in organisms. This was confirmed by residue analyses
(Table d.3). The bioconcentration factor in fish is approx. 300, in one case, however it
amounts to 1300.
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Section 6. Case Studies
Prats.et.al, 1993 show significant differences between distribution of LAS homologs in water
and solids (sludges, sediments, and soils), as compared to the original distribution in
detergent formulations, yielding a lower LAS average molecular weight in water samples.
The change observed in the homolog distribution of LAS implies a reduction in the toxicity to
Daphnia, because a lower average molecular weight of LAS is less toxic. The risk
assessment of LAS to terrestrial plants and animals reported by Mieure et al. (1990) also
concludes that there are adequate margins of safety in the use of wastewater for the
irrigation of plant species. Adverse effects on plant and animal species (earthworms Eisena
foetids and Lumbricus terrestris) were observed at LAS concentration of 10 mg.l -1 , however
LAS concentrations in wastewater effluents are in a range 0.09 mg l-1 to 0.9 mg l-1 . These
figures give a safety margin in a range 10 to 100. The effect of surfactant on plant growth
from the use of sewage sludge is difficult to assess because in general the sludge promotes
plant growth. Adverse effects on plant growth were observed at 392 µg g-1 but long term
monitoring at a range of 46 environmental sites gave LAS concentrations of less than 3µg.g-1
. These figures give a safety margin of 131. For terrestrial animals the limit of no adverse
effects was 235 µg.g-1 giving a safety margin of 78. However, in looking at ecotoxicity from
WWTS effluents the less toxic surfactant residues and surfactant catabolites must be
considered and this requires analytical tests for these entities (Scott and Jones, 2000;
Schoberl, 1997).
Amounting to 2-4 g.kg-1 the acute mammalian (mouse, rat) toxicity of APE is low. Dermal
toxicity, however, is higher (500 mg.kg-1), and eye irritation is the highest with 5-100 mg.kg-1.
NP can be metabolised to a glucoronide in the body and excreted via the kidney. Nonionic
surfactants are more toxic for aquatic organisms than for mammals. The toxicity of APE
increases with decreasing number of ethoxylate units and increasing hydrophobic chain
length. Accordingly, the toxicity of the original substances is lower than the toxicity of the
metabolites NP, NP1EO and NP2EO, whereas the carboxylic acids are less toxic than the
ethoxylates. For instance the LC50 (48 hours) of NP16EO is 110 mg.l-1 for fish (Oryzias
latipes) and decreases to 11,2 and 1,4 mg.l-1 for NP9EO and NP, respectively (Yoshima,
1986). The LD50 (96 hours) for algae (Skeletonema costatum) is 27 µg.l-1, and the value for
rainbow trouts 480 µg.l-1 (Nayler 1992). The no observed effect concentration (NOEC) for
reproduction for Daphnia is in the range of 24 µg.l-1. These data show that the acute toxicity
of NP is considerably high.
In vitro toxicity studies with fish hepatocytes indicate that several decomposition products of
APE cause weak oestrogenic effects (Jobling and Sumpter 1993, White et al. 1994). Studies
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Section 6. Case Studies
based on the vitellogenin synthesis revealed that NP, NP1EO and NP1EC have the same
activity (half maximum activity: around 16 µM). The oestrogenic activity, however, is 10
times lower than that of oestradiol (Pelissero et al. 1993). Other in vitro studies give hints on
potential differences between fish and mammalia regarding the binding to the oestrogen
receptor (Thomas and Smith 1993). However, vitellogenin synthesis in fish hepatocytes is
also induced by well-known phyto-oestrogens. Studies in the UK indicate that downstream of
the drain channels of WWTS vitellogenin is formed in male fish. After 1 to 3 weeks exposure
of fish in 15 drain channels of WWTS, displayed a high increase of vitellogenin synthesis
(Purdom et al. 1994). It is supposed that the decomposition products of APE, especially NP,
are mainly responsible for this effect. The assumption is confirmed indirectly by the results of
the in vitro studies with fish hepatocytes. However, it cannot be excluded that synthetic
oestrogens are also responsible for this effect. On the one hand their concentrations are
lower than the usual concentrations of NP, but on the other hand their activity is some orders
of magnitude higher. Experimental exposure of fish to NP or metoxychlor over 7 days
induced vitellogenin synthesis in male fish (Nimrod and Benson 1995). The dose required to
induce the vitellogenin synthesis was 300 times (approx. 150 mg.kg-1) higher than the
necessary dose of oestradiol.
Further research in this field, especially the conduction of experimental in vivo studies, is
urgently required to allow for a more reliable assessment of the exposure of fish populations
to oestrogenic chemicals and their potential effects.
Field investigations indicate that downstream of the drain channels of WWTS oestrogenic
effects may be induced in fish. The in vitro studies with fish hepatocytes seem to indicate
that the oestrogenic activity of synthetic oestrogens is some orders of magnitude higher than
the activity of decomposition products of APE. On the other hand the oestrogenic potency of
NP, NP1EO, NP2EO and NP1EC is very similar. Consequently, all degradation products
have to be taken into consideration. It seems advisable to suppose that the above chemicals
have additive effects.
This public awareness and consumer choice, lead to the use of LAS in Sweden falling from
6300 tonnes a year to 260 tonnes a year. The Danish Environment Agency launched a
public campaign against LAS in September 1999. Currently about 2500 tonnes a year of
LAS are used in Denmark.
During the development of the “Swan” mark, Stockholm water company identified the need
to have an alternative for taking care of hazardous waste in the household rather than
flushing it into the UWW collecting system. Environmental stations, or collection points were
established and an extensive public information campaign was carried out about the impacts
of household products on the aquatic environment [Ulmgren, 2000a, 2000b].
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Section 6. Case Studies
also substituted with more degradable substances during the 1990s in Germany [Greiner,
1996] and is currently under scrutiny in the rest of the EU.
The eco-labelling combined with a public awareness campaign could therefore influence
consumer choice and reduce contaminant discharges in the UWW from domestic products.
Some important research gaps and necessary research are summarised as follows:
Effects of endocrinally active chemicals have not yet been systematically investigated in
amphibian and reptiles. In this field nearly no knowledge is available.
• Chemical methods for the detection of traces of synthetic oestrogens and their
metabolites must be elaborated, since only very few data are available on
environmental concentrations, especially regarding concentrations in drain channels
of wastewater treatments plants. Furthermore, data material on NP concentrations in
drinking water and organisms including humans is insufficient.
• The ecotoxicological relevance of vitellogenin production in male animals has to be
elucidated. Which interrelations exist between the problem of vitellogenin production
and further estrogenic and ecotoxicological effects of NP and other chemicals? To
answer these questions in vivo experiments using histopathological, biochemical,
endocrinological and reproduction biological methods have to be conducted.
Furthermore, insufficient information is available about the bioaccumulation of these
chemicals. In a further step the problem should be investigated by more
comprehensive field studies.
• The mechanisms of chronic effects of alkylphenols (modes of action) must be studied
in more detail.
• Finally, in vitro assays should be elaborated to identify and estimate the oestrogenic
activity of existing new chemicals in fish and other organisms.
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Section 6. Case Studies
PAM is shown to degrade by biological action and photolytic effects (Nakamiya 1995).
Experiments have shown that polyacrylamide solutions in a bottle covered with plastic film
and left outside can contain significant amounts of the monomer after two weeks exposure
(Smith et al. 1996). The polymer can also be degraded by turbulent shear stress in pumps
and pipes (Rho et al. 1996). Once the polymer degrades the monomer is also subjected to
more rapid degradation in which it is decomposed to acrylic acid and ammonia. These are
non toxic as acrylic acid degrades to CO2 and water in a day in soil (Staples et al. 2000) and
is thus not an ecological problem. The degradation of acrylamide under favourable
conditions by pseudomonas species immobilised in calcium aliginate took one day (Nawaz
et al. 1993). The EPA say that degradation of acrylamide in river water takes 4 to 12 days
and is more rapid in summer than winter. Due to its solubility adhesion of the monomer on
soil is unlikely, though it is reported that it is partially removed by secondary activated
sludge.
The general conclusion of the EPA paper is that the monomer is not an environmental
hazard when released in small quantities to the aqueous environment. Tests with fish would
indicate this. The monomer is relatively biodegradable within days compared to the time
span of years for substances such as PCB. There are two areas where there could be some
concern and these are control of effluents from acrylamide manufacturing and use in
drinking water treatment. The fact that the monomer is detected in water treatment plants
where the residence time is only a few hours suggests that the PAM flocculant could have
significant residual amounts of monomer.
• Chlorination and the presence of potentially toxic elements can stop acrylamide
degradation by passifying the bacteria present.
• Degradation of the monomer is not pH dependant
• 50% of PAM is removed in aerated sludge and trickle bed filters.
A significant drop in the percentage of monomer present in the PAM used for flocculation
has eased the likelihood of serious contamination of water. The present level of monomer
present in grades of PAM used for water treatment is 0.3% and has dropped from 0.8%.
However PAM used in grouting has a much higher monomer content and the use of this
particular grade has caused the monomer to leak into grouted sewers.
To conclude it seems that whenever water is sent into the environment it would be safe to
use PAM as a coagulant. Problems may arise when it is used in a stream which is
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Section 6. Case Studies
subsequently sterilised by chlorine or by another disinfectant. This removes the bacteria that
are needed to degrade the PAM and it would be a problem with using other organic
polymers as well. It might be concluded that a polymer grade containing just 0.3% of
monomer is very pure and improvements in purity might not be practically feasible.
Therefore in treating drinking water some intermediate step may be necessary to degrade
the monomer after flocculation and before adding the disinfection agent. This could involve a
holding lagoon or treatment using activated charcoal. In any case the case for or against the
use of PAM in flocculating drinking water lies in the conflicting aims of acrylamide
degradation and product sterilization. Its use in the treatment of drinking water needs
continuous monitoring and, if more stringent regulations are placed on the monomer
concentration in drinking water the issue will become a concern.
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Introduction
In the past treatment of leachates in WWTS were favoured but due to the effects of dilution
in the UWW system, there is little, if any information on the elimination of persistent
compounds (Alberts, 1991). In Germany, a recent requirement has been the proper
preliminary treatment of leachate before discharge either directly to surface waters or
indirectly to municipal WWTS.
With the introduction of redrafted legal conditions in Germany, strict demands have been
placed on the purification performances of leachate treatment plants. Thus, the treatment of
organic substances and nitrogen compounds using nitrification and denitrification, is required
prior to direct discharge to a receiving watercourse.
Standard values for the composition and quality of non-domestic wastewater discharged to a
public WWTS are stated in guideline/directive ATV-A 115 (worksheet for indirect
dischargers). The standard concentrations for potentially toxic elements are shown in Table
h.1.
Table h.1: Standard concentrations for soluble and insoluble inorganic substances in
wastewater from non-domestic sources [ATV-A 115, 1994].
Requirements for wastewater from landfill sites are given special attention in annex 51 of the
regulation. It is a requirement that the quantity and pollution load of landfill leachate must be
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Section 6. Case Studies
kept low by proper measures and operation at the landfill installation. The requirements
listed in Table h.2 relate to the discharge site of leachate into watercourses.
Table h.2: Requirements for wastewater quality at point of discharge (qualified sample
or 2 hour mixed sample) [AbwV, annex 51, 1999].
The requirements listed in Table h.3 below relate to leachate before mixing with other
wastewaters.
Table h.3: Requirements on leachate before mixing (qualified sample or 2 hours mixed
sample) [AbwV, annex 51, 1999
Parameter Unit
[mg/l]
AOX* 0.5
Mercury 0.05
Cadmium 0.1
Chromium 0.5
Chromium VI* 0.1
Nickel 1
Lead 0.5
Copper 0.5
Zinc 2
Arsenic 0.1
Cyanide, easily released* 0.2
Sulphide* 1
* value for the qualified sample.
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Section 6. Case Studies
Leachate can be mixed with other wastewater for common biological treatment only when:
Table h.4: Fish, indicator bacteria and Daphnia toxicity [AbwV, annex 51, 1999]
Fish toxicity GF = 2
Daphnia toxicity GD = 4
Indicator bacteria toxicity GL = 4
Landfill Leachate
Formation:
A substantial proportion of pollutant emissions from landfill sites enters percolating through
the landfill. Rain water (and other sources of water) entering unsealed sections of the landfill
undergo chemical and biological transformation in the body of the landfill to form leachates.
Pollutants are taken up by solution processes or are carried in suspension. This loaded
water, the so called leachate, is collected at the base of the landfill in a drainage pipeline.
The quantity of leachate produced depends principally on rainfall and the state of the landfill.
At new, unsealed landfill sites, the total calculated rainfall collects as leachate. During the life
of the landfill leachate quantity reduces to 10 – 20 % of total rainfall, with an increase in
superficial sealing.
Composition:
Leachate is a heterogenezous mixture, often containing a high concentration of persistent
biological and toxic compounds. The type of material deposited in the landfill determines the
composition of the leachate. Leachate composition and pollutant concentration are also
influenced by the rate of biochemical processes in the body of the landfill. After an initial
intensive phase biological and chemical reactions in the landfill slowly subside. As the age of
a landfill increases, the quota of easily degradable compounds in and the COD/BOD5 ratio
rises (Leonhard, Wilderer, 1992).
Some of the main pollutants found in landfill leachates are organic compounds, such as alkyl
phenols, chlorinated phenols, polycyclic aromatic hydrocarbons (PAH), dioxins and furans.
Leachate from special waste landfills tends to have higher concentrations of inorganic
substances compared to leachate from household refuse landfills; chlorides, sulphates and
fluorides represent the main load.
Table h.5 gives an overview of the relevant pollutant concentration in landfill leachate.
196
Section 6. Case Studies
Table h.5: Mean composition of leachate from: industrial or special waste landfills,
and household refuse landfills, in Germany [Ehrig et al., 1988]
Treatment Practices
Different methods can be used for treating leachate from landfills, consisting principally of
biological, physical and chemical processes. A specific process can only treat a particular
substance categories in wastewater. Because of the wide range of pollutants found,
leachate treatment has to be performed using a combination of suitable processes. The
choice of treatment processes depends closely on the leachate composition. A short
description of processes used in Germany for treating leachate follows below.
Biological Practices:
Biological process can be used to degrade leachate pollutants into mineral end products. To
enable degradation specialised microorganisms must be enriched in the bioreactors by
proper process conditions. Nitrogen elimination can also be obtained by nitrification and
denitrification. Biological processes, especially the aerobic ones, are efficient and cost-
effective in comparison with the chemical-physical processes (Rudolph et al., 1988). The
activated sludge process and the biofilm process are both use to biologically treat leachate
from landfills.
Activated sludge : In the activated sludge process micro-organisms aggregate in the form
of biological sludge flocs suspended in the wastewater flow, through the treatment plant. The
formation of settleable sludge is decisive for the efficient working of the activated sludge
process. Leachates though are often characterized by high salt concentrations and high
197
Section 6. Case Studies
Biofilms: Biofilm systems can be used to prevent the loss of biomass by washing-out, which
may be experienced in the activated sludge process. Biomass growth is encouraged by
attachment to support surfaces, in form of biofilm. SBBR, the so called sequencing batch
biofilm reactors, are also used for cleaning leachate with high salt concentrations and a high
percentage of persistent organic compounds. Advantages of the biofilm processes are the
small space requirement and the high flexibility in service (Wilderer et al, 1989).
Chemical-physical methods:
Flotation, precipitation and flocculation, adsorption, reverse osmosis and thermic techniques,
belong to the chemical-physical processes for treating leachate. Other chemical-physical
processes are chemical oxidation and membrane filters.
Flotation: Flotation is used for separating specific low density substances and suspended
solid constituents or liquid substances. In a leachate treatment plant they are normally the
first step of the treatment process.
Thermal treatment: In thermal treatment pollutants in leachate are separated from water
(stripping), concentrated (vapourising) and mineralized (combustion). Due to the different
volatilities of water, organic solvent and of dissolved and suspended substances, partition by
distillation can be achieved. Thus volatile hydrocarbons contained in the leachate can be
separated with a stripping step. With the vapourising process, inorganic and organic residual
substances are obtained separately in a chemically unchanged form. Then, the concentrated
organic phases must be made inert by combustion. Proper treatment of the exhaust gases
is necessary to meet air quality emission standards. During the vapourisation of critically
loaded leachate, single toxic halogen organic compounds such as polychlorinated biphenyls,
dibenzo-dioxins and dibenzo-furans can enter the distillate. In this case, post treatment with
activated carbon is essential (Leonhard, Wilderer,. 1992).
198
Section 6. Case Studies
Reverse Osmosis: In the treatment of leachate, reverse osmosis is only used for
desalination and concentration of the leachate to be treated. During operation, membrane
fouling caused by suspended and colloidal substances has to be prevented, which would
otherwise result in a regression of the treatment performance, due to reduction of the
permeate flow. At the end the accumulated concentrate must be subjected to additional
treatment. The principle advantage of reverse osmosis is the low energy cost.
Membrane filtration: The membrane technique has been successfully used for cleaning
leachates. A biological process tank is combined with post membrane filtration (nano and
ultrafiltration) for biomass retention. The activated sludge tank is in part operated by
overpressure in order to reach higher oxygen solubility and with this, a better oxygen supply
for the micro-organisms. The removal of treated water occurs continually over a cross-flow
membrane filtration plant. The membrane modules are especially capable of finely dispersed
sludge retention (Krauth,.1994).
Conclusions
In Germany, the discharge of wastewater into public WWTS and into receiving watercourses
is strictly regulated. Thus, leachate must also be treated before discharging and legal
regulations set high requirements on the performance of leachate treatment plants (ATV-
A115 1994 and AbwV 1999).
In ordinary analysis of treated and untreated leachate, only parameters such as COD, BOD
and AOX are determined. Additional quantification of high and low volatile hydrocarbons,
organic acids, phenols and single organic halogen compounds is necessary to adequately
describe the potentially hazardous impact of leachate.
In addition, it has to be taken into account that waste products loaded with pollutants
frequently arise from leachate treatment: toxic surplus sludge results from biological
treatment; charcoal is produced during adsorption processes; and polluted concentrates
form during vaporisation. To minimize the problematic emission of pollutants into the
environment, additional treatment of exhaust gases and proper disposal of the waste
residues are required.
199
Section 6. Case Studies
Sludges from conventional sewage treatment plants are derived from primary, secondary
and tertiary treatment processes. The polluting load in the raw waste water is transferred to
the sludge as settled solids at the primary stage and as settled biological sludge at the
secondary stage. Potentially toxic elements are also removed with the solids during the
primary and secondary sedimentation stages of conventional wastewater treatment. Metal
removal during primary sedimentation is a physical process, dependent on the settlement of
precipitated, insoluble metal or the association of metals with settleable particulate matter.
Minimal removal of dissolved metals occurs at this stage and the proportion of dissolved
metal to total metal in the effluent increases as a result. The efficiency of suspended solids
removal is the main process influencing the extent of metal removal during primary
wastewater treatment. However, the relative solubilities of different elements present in the
wastewater are also important (Table i.1). Thus, Ni shows the poorest removal (24 %) during
primary treatment whereas 40 % of the Cd and Cr in raw influent is transferred to the primary
sludge. Primary treatment typically removes more than 50 % of the Zn, Pb and Cu present in
raw sewage.
The removal of metals during secondary wastewater treatment is dependent upon the
uptake of metals by the microbial biomass and the separation of the biomass during
secondary sedimentation. Several mechanisms control metal removal during biological
secondary treatment including:
In general the patterns in metal removal from settled sewage by secondary treatment are
similar to those recorded for primary sedimentation. However, the general survey of removal
efficiencies listed in Table i.1 suggests that secondary treatment (by the activated sludge
process) is more efficient at removing Cr than the primary stage. Operational experience
and metal removals measured by experimental pilot plant systems provide guidance on the
overall likely removal and transfers to sludge of potentially toxic elements from raw sewage
during conventional primary and secondary wastewater treatment. This shows that
approximately 70 – 75 % of the Zn, Cu, Cd, Cr, Hg, Se, As and Mo in raw sewage is
removed and transferred to the sludge (Blake, 1979) and concentrations of these elements
in the final effluent would be expected to decrease by the same amount compared with the
influent to the works. Lead may achieve a removal of 80 %, whereas the smallest overall
reductions are obtained for Ni and approximately 40 % of this metal may be transferred to
the sludge.
The majority of potentially toxic elements in raw sewage are partitioned during wastewater
treatment into the sewage sludge or the treated effluent. However, atmospheric volatilisation
of Hg as methylmercury, formed by aerobic methylation biotransformation processes, is also
suggested as a possible mechanism contributing to the removal of this element during
secondary wastewater treatment by the activated sludge system (Yamada et al., 1959).
Whilst it some of the Hg removal observed in activated sludge may be attributed to
bacterially mediated volatilisation, it is unlikely that this is a major route of Hg loss because
of the significant quantities of Hg recovered in surplus activated sludge (Lester, 1981).
200
Section 6. Case Studies
Table i.1 PTE removals and transfer to sewage sludge during conventional urban
wastewater treatment (Lester, 1981)
201
Section 6. Case Studies
Table j.1 Effect of chemical precipitation on metal removals (%) from raw sewage after
18 h sedimentation (Stone, 1977)
Iron-based precipitants are marketed for use in wastewater treatment may be derived from
industrial by-products of titanium oxide production. Such by-products may contain significant
concentrations of potentially toxic elements (PTEs) with potentially undesirable effects on
the metal content of sludge (Thiel, 1992).
An example of the effects of Fe dosing with industrial by-product on the maximum potential
increase in the PTE content of activated sludge is shown in Table j.2. The typical dosing
rates of FeSO 4 are typically in the range is 15 – 30 mg Fe salt l-1, but may increase up to 50
mg Fe salt l-1, to comply with the discharge requirements for P in the Urban Waste Water
Treatment Directive (CEC, 1991). The calculations suggest that dosing with FeSO4 may
potentially increase the Cd content of activated sludge by approximately 300 % to 6 mg kg-1
ds from a typical background value of 1.5 mg Cd kg-1 ds, assuming the maximum likely dose
rate of 50 mg Fe salt l-1 and that secondary sludge production is equivalent to 250 mg l-1 of
total solids (UKWIR, 1997). The Ni content in activated sludge may theoretically increase by
130 % compared to sludge without Fe addition, whereas Pb and Zn concentrations may
increase by about 10 % with Fe dosing. These increases in sludge content remain well
within the current quality standards for agricultural use (CEC, 1986). However, the revision
of the Directive on land application (CEC, 2000b) will introduce more stringent limit values
for PTEs and the use of Fe salts from industrial processes could potentially penalise the
acceptability of sludge for use in agriculture under the new regulatory regime. Furthermore,
202
Section 6. Case Studies
the potential increase in the metal content of sewage sludge, resulting from the use of
industrial-grade chemical precipitants, could also be considered as unsatisfactory because it
erodes the beneficial reductions in metal inputs that have been achieved through the
successful control of trade effluent discharges.
The quality and metal content of low-grade chemical precipitants for use in wastewater
treatment should be examined to ensure that they do not significantly increase the metal
content of sludge. In Germany, for example, composition standards are recommended for
Fe and Al-based coagulants used for sewage treatment and sewage sludge conditioning
(Schumann and Friedrich, 1997). The use of potable water grade Fe salts should be
considered for sewage treatment (Thiel, 1992) to avoid potential problems associated with
contamination with potentially toxic elements. In practice, there are few published data on
the effects of chemical precipitants on sludge metal contents and Fe and Al dosing. One
example from the literature (Yeoman et al., 1993) showed no consistent effects of chemical
treatment with Al or Fe salts on potentially toxic elements in sewage sludge from Beckton
WWTS in the UK (Table j.3). However, the significance of the direct metal inputs in chemical
precipitants will increase as industrial discharges are effectively controlled and as diffuse
inputs from domestic sources and run-off become the predominant sources of potentially
toxic elements entering the wastewater collection system.
Table j.2 Metal concentrations (mg kg-1) in Fe precipitants and activated sewage
sludge (UKWIR, 1997)
Table j.3 Effect of chemical P removal on the PTE content of sludge digested sewage
sludge(1) (adapted from Yeoman et al., 1993)
Waste products from water treatment and industrial processes, incinerator ash and acid
mine drainage have potential for re-use as P precipitants in wastewater treatment processes
(Fowlie and Shannon, 1973). For example, Oostelbos et al. (1993) treated Fe-enriched
sludge from water treatment with hydrochloric acid to convert ferric hydroxide to ferric
chloride for use in sewage treatment for phosphate removal, and as a dewatering agent in
203
Section 6. Case Studies
sludge conditioning. Verberne (1992) considered that the use of water treatment sludges as
chemical precipitants for P removal was technically feasible and would depend on the
agreement and acceptance of the approach by water and sewage treatment authorities. The
recovery of Fe and Al from acid mine drainage is another source of chemical precipitants
that can be used for P removal during sewage treatment (Bouchard et al., 1996). The re-use
of secondary resources for precipitating P during wastewater treatment is intuitively
attractive and also alleviates the environmental problems and impacts associated with
disposal of those wastes. However, some product types derived from waste materials are
potentially contaminated with potentially toxic elements that accumulate in the sludge
(Fowlie and Shannon, 1973). Therefore, the metal content of waste derived products should
be established, and the potential consequences for sludge quality determined, before a
particular product is accepted for use as a chemical precipitant in wastewater treatment.
204
Section 7. Report Synopsis, Discussions and Conclusions
The European Union is introducing an integrated policy to promote sustainable water use
through the Water Framework Directive-2000/60/EC (WFD) based on a long-term
protection of water resources. A strategic aspect of this is the progressive decrease in
contaminant discharges to the aquatic environment. Allied to this water policy is the
amended proposal by the European Commission (COM/2001/17) listing 32 priority
substances to be phased out and 11 hazardous substances that will be subject to
emission controls and quality standards in accordance with Article 16 of the WFD.
Furthermore, Directive 86/278EEC concerning the use of sewage sludge in agriculture
(USSA) is undergoing major revision of the quality standards for potentially toxic
elements and organic contaminants in sludge and metal concentrations in sludge-treated
soil. The urban wastewater (UWW) collection system is one of the main facilities used for
the disposal of many types of commercial and domestic wastes that contain potentially
toxic elements and organic pollutants. It also receives unintentional diffuse inputs of
contaminants in storm run-off from paved surfaces. However, wastewater treatment
processes are effective in mitigating the discharge of many substances to surface waters
with the treated effluent. This is achieved principally through aerobic biological
transformations or because a significant proportion of the contaminant load is transferred
to the sewage sludge. Centralised collection and treatment of urban wastewater and
sewage sludge is therefore a pivotal link in defining the pathways and fate of
contaminant releases to the environment.
A major review of scientific, operational and regulatory information and literature from
published sources, research institutions, industrial operators and environmental agencies
has pooled current knowledge and developed a data-base of the sources and pathways
of pollutants in the wastewater treatment system (WWTS) within the European context.
The main objectives of this study were to determine the multiple sources of potentially
toxic elements and organic pollutants entering UWW, to determine quantitatively the
amounts of pollutants passing into the influent of wastewater treatment plant (WWTP),
and to assess the effects of treatment processes on the fate of both inorganic and
organic pollutants in sewage sludge and treated effluents. This information was to be
used to identify problems, to make recommendations and enable optimum reduction of
pollutant inputs, and to identify areas where data are lacking and where further research
is required. The significance of the inputs and types of contaminants from different
sectors connected to the wastewater collection system and potential opportunities and
practical measures to reduce the extent of contaminant discharges to sewer are
discussed. Potentially toxic elements are routinely measured in wastewater and sludge
and an extensive data-base of information has accumulated on the concentrations and
fate of these elements in environmental media. Several important groups of organic
contaminant have also received considerable attention (eg PAHs, PCBs, PCDD/Fs), but,
in general, the amount of published information on organics is limited compared with
potentially toxic elements due to the high cost of analysis, and need for specialist
analytical facilities and the absence of standardised methodologies.
More information has been identified for potentially toxic elements, which have been
subject to more detailed monitoring, as they are relatively easy to analyse using routine
and inexpensive tests and environmental or food chain impacts are much easier to
quantify where high soil loadings have occurred. Much less information is available on
organic pollutants where some six thousand or more compounds have been identified.
Many of these cannot be routinely determined in the majority of laboratories due to lack
of appropriate instrumentation, the absence of a unified methodology and expense.
The type of pollutants and the magnitude of loadings to the WWTS system are a
complex function of:
Quantitative information on both metal and organic pollutants in urban runoff arising from
anthropogenic activities is difficult to evaluate, due to the lack of information on
background levels of these substances in the environment. Background concentrations
relate to natural geochemical sources and biological sources, and include amounts in
soils, dusts and waters derived from historical pollution.
The specific potentially toxic elements (PTEs) and organic contaminants considered in
this report are listed in Table 7.1.
Table 7.1 Potentially toxic elements and organic contaminants examined in the
review of pollutants in urban waste water and sewage sludge
Other organics**
*- such as Arsenic, Silver, Molybdenum and Selenium
**- such as Adsorbable organo halogens (AOX) and chlorinated paraffins
Specific case studies on the following key issues are included in greater detail in Section
6
The review has emphasised that an assessment of the contaminants entering UWW and
sludge cannot be divorced from an understanding of their potential impacts on the
environment, and particularly in relation to the use of sewage sludge in agriculture, as
this provides the context for defining the significance of UWW and sludge contamination.
The sources of potentially toxic element contamination in the wastewater system have
been classified into three main categories:
• Domestic;
• Commercial;
• Urban runoff.
The information that was collected identified domestic inputs as the largest overall
sources of Cu, Zn and Pb entering the UWW system, whereas commercial sources
represent the major inputs of Hg and Cr (Table 7.2). Commercial discharges contribute
moderately larger inputs of Cd (30 – 60 %) compared with domestic sources (20 – 40
%). Estimates of Ni loadings from domestic sources are highly variable and this
contribution may be similar to, or greater than, the commercial input. The size of the run-
off contribution depends on climate and traffic intensity, and can be a significant
proportion (>20 %) of the total metal load for Cd and Pb, but it is a relatively minor
source of Cu and Hg. However, storm discharge was identified as an important source of
Hg in a survey of metal inputs to the river Rhine (French region), contributing 15 % of the
total load of this element to the river. Chromium, Ni and Zn represent an intermediate
group and run-off typically contributes <20 % of the total input of these elements to
UWW.
can only focus on those sources that can be identified and quantified. Therefore, given
the extent of the uncertainty in establishing the sources and inputs of certain elements, a
priority area for research would be to determine these contributions and to develop a
complete mass balance for potentially toxic elements entering to the UWW system in
different European countries.
Table 7.2 Provisional potentially toxic element load from different sources entering
UWW in EU countries (% of total input)
The ranges in Table 7.2 are estimates from various sources in this study and may not
add up to 100%. Quite a high proportion of the Zn, Ni and Cr are not identified and
attributed to certain sources, and more research is needed in calculating the mass
balances of these PTEs in the urban environment.
Table 7.3 Diffuse and point sources of potentially toxic elements entering the river
Rhine reported in 1999 (% of total input)
Despite uncertainties in identifying all the metal inputs there is ample evidence
demonstrating the significant reduction in metal discharges to the WWTS, principally due
to implementation of effective trade effluent controls, more efficient processes and
change in industrial base. This is reflected in the declining concentrations of metals
present in sewage sludge and in influent wastewaters (Section 2.1) and was reported in
all countries where data could be abstracted on temporal trends (The Netherlands,
France, UK and Sweden). Examples of the general declining trends in metal
concentrations in sludge over the past 20 years in European countries are shown in
Figure 7.1 for Zn and Cd for a major WWTP in the UK. In Sweden, Cd inputs declined by
60 % during the period 1992 – 1998 and Cr, Hg and Pb were reduced by 40 – 50 %. Zn
and Ni declined by 10 % during the same period, and there was no change in Cu
generally reflecting the importance of the domestic contribution of these elements in
UWW. Metal concentrations in rivers receiving treated UWW have also shown a marked
decline. For example, concentrations in the river Thames have declined on average by
50 % in the period 1986 – 1995.
1.6
1600
1.4
1400 1.2
1200 1
1000 0.8
0.6
800
0.4
600 0.2
400 0
1978 1983 1988 1993 1998 1978 1983 1988 1993 1998
Year
Figure 7.1 Reduction in (a) zinc and (b) cadmium concentrations (untransformed
and log 10 transformed data, respectively) in sewage sludge from Nottingham STW,
UK during the period 1978 – 1999
Faeces comprise a significant proportion (>20 %) of the load of Cd, Cu, Zn and Ni
(equivalent to 60-70 % of the total amount of these elements in domestic contribution to
wastewater). Faeces typically contain 250 mg Zn kg -1, 70 mg Cu kg-1, 5 mg Ni kg-1, 2 mg
Cd kg-1 and 11 mg Pb kg -1 dry solids. The residual sewage sludge from WWTS generally
has significantly larger concentrations of metals than those present in human faeces
because of the contributions from other sources.
For Cd, however, which is the most labile zootoxic element in UWW and sludge and its
release is of particular concern in the environment, the weighted average content in
sludge is comparable to the concentration in human faeces. Whilst other sources of this
important element can be identified, solids inputs and secondary sludge production
during WWT may have a significant dilution effect on the mass input and transfer to the
sewage sludge. Consequently, a critical balance between input concentration in
wastewater and dilution processes may control the final Cd content in sludge to within
the normal range for faeces, which represents the minimum potential background
concentration value. The precise nature of these mechanisms could be identified to
better understand the behaviour of Cd in WWTS and in relation to effects of measures to
reduce Cd inputs on sludge quality. Whilst the opportunities for further reducing Cd
inputs would generally appear to be limited, removing phosphate from detergent
formulations has successfully reduced Cd discharges from domestic sources in The
Netherlands and Sweden (Section 2.1.2).
However, the principal sources of metals in domestic wastewater are body care
products, pharmaceuticals, cleaning products and liquid wastes (eg paint). Plumbing is
the main source of Cu in hard water areas, contributing >50 % of the Cu load. It may
also be a principal source of Pb where this was used historically as a means of drinking
water conveyance, accounting for 25 % of the input to WWTS. Lead solder in copper
pipes may also be an important source.
Incomplete information regarding these sources could account for a major proportion of
the unidentified inputs of metals to UWW (Table 7.2). The identification and control of
Other investigations in Sweden and Norway confirm the importance of motor industries,
vehicle workshops and washing facilities (particularly heavy goods vehicles) as major
sources of potentially toxic elements in UWW. Oil separating devices may be fitted as a
measure to reduce wastewater contamination from these activities. However, the
formation of stable emulsions in the wastewater by detergent microemulsion formulations
used for vehicle washing tend to limit the effectiveness of these systems at reducing
pollutant emissions.
Table 7.4 Total metal loads (mean values) from artisanal activities (in discharged and segregated wastewater) in Northern Italy
Activity Zn Cu Ni Cd Pb Cr(III)(4)
(number of % total load to % total load to % total load to % total load to % total load to % total load to
enterprises(1)) WWTS (mean) WWTS (mean) WWTS (mean) WWTS (mean) WWTS (mean) WWTS (mean)
Food (52) 0.28 0.09 <LOD <LOD <LOD <LOD
Car repair (174) 6.4 8.5 0.3 6.3 34.0 1.0
Ceramic (24) 0.01 0.001 <LOD 0.14 3.1 1.1
Galvanic (17) 0.07 0.84 0.67 0.39 1.5 0.15
Printing (141) 0.24 2.0 < LOD 2.8 0.59 0.6
Wood (92) 0.29 0.46 <LOD <LOD 5.5 0.76
Metallurgist (155) 8.7 5.3 15.6 2.3 25.7 4.7
Dental (88) 0.16 0.02 <LOD 0.25 <LOD 0.05
Gold (253) 2.1 7.6 <LOD 32.2 <LOD 0.14
Hairdressing (316) 0.99 0.69 <LOD <LOD <LOD <LOD
Laundry (88) 0.49 0.09 0.04 2.3 0.45 <LOD
Total(2) 19.9 25.5 16.6 46.6 71.1 8.9
Total(3) 8.8 9.5 0.46 36.9 7.9 1.8
(1) (2)
Total number = 1579 enterprises Calculated on basis of no pre-treatment and discharge directly to UWW system.
(3)
Based on discharge of pre-treated wastewater to the UWW system (car repair, ceramic, galvanic, printing, wood processor and metallurgy enterprises
usually segregate and pre-treat process water to comply with the standards for discharge of industrial wastewater in Italy).
(4)
Cr VI was discharged in the effluent from galvinising shops, but was not detected any other sample or in the influent to the WWTS. Cr VI is rapidly
transformed to Cr III on contact with organic matter in sewage and sludge. Therefore the Cr VI input from galvanising shops was calculated as a proportion of
the total Cr load to the UWWS (as Cr III). Loadings >5 % of the total input to the UWWS system are highlighted in bold and <LOD=below limit of detection
Urban run-off
Metal inputs to WWTS in urban run-off are highly variable and depend on traffic,
surface and roofing materials and age, and environmental factors (Section 2.1.3).
The principal sources of PTEs in urban run-off include:
Roads and vehicles have been investigated as potential sources of PTEs entering
WWTS. Lead, Cu, Cd and Zn are present in high concentrations in brake linings and
amounts of Cd and Zn are also significant in tyre rubber. Tyre abrasion and brake-
lining wear appear to be more important as sources of Cd and Zn transfer to runoff
water. Whilst these metals may be released during brake-lining wear, the amounts of
Pb and Cu entering the drainage system in runoff is relatively small. Run-off is a
minor source of Cu entering the UWW compared with the domestic load from
plumbing. Nickel is the main element released from the abrasion of road surfaces.
Roofing materials influence concentrations in runoff and Zn is significantly increased
by galvanised surfaces. Lead in window frames and roof sheeting and also Pb
painted surfaces can contribute significant amounts of this element to runoff water.
Interestingly, the concentrations of Cd, Cu, Pb and Zn in roof runoff may be
comparable to, or greater than, those in road run-off suggesting that atmospheric
deposition onto paved surfaces may be more important as a source of metals in run-
off than vehicle or road related inputs. Concrete structural materials transfer
negligible amounts of potentially toxic elements to run-off. The relative size of the
inputs of different potentially toxic elements to UWW in run-off can be ranked in
increasing order as: Cd<<Ni<Cu<Pb<<Zn. Although there is more Zn in urban run-off
than any other metal, this represents a relatively minor input to the WWTS (<20 %)
compared with domestic (50 %) and commercial (<35 %) discharges of Zn to sewer
(Table 7.2).
The available mass balance information suggests that the overall contribution of
urban run-off to the metal flux in UWW is generally comparatively small, and
intermittent depending on rainfall, relative to other sources (Table 7.2). However, the
variable nature and uncertainty about the extent of these inputs could partly explain
the apparent discrepancy between the identified sources of PTEs and the actual load
entering the WWTS. The significance of potentially toxic elements in urban run-off
could be quantitatively examined by relating rainfall frequency, duration and intensity
with temporal trends in the metal content of sewage sludge sampled from WWTS
serving different catchments types (industrial, domestic, mixed). There are a number
of possible measures that can potentially reduce contaminant entry into UWW from
run-off. For industrial and other paved areas, for example, where it is practicable,
interception systems to remove contaminants bound to suspended solids by
sedimentation or filtration can reduce inputs to the WWTS. However, these are only
moderately effective because the smallest particles containing the largest
concentrations of metals do not settle efficiently. The design and management of
these systems are described in Case Study (b). In general, however, it is difficult to
practically control or minimise run-off contamination due to the diffuse nature of the
sources of metals, although targeting Pb painted surfaces for source preventive
action would further curtail inputs of this element into the environment.
Mass balance of metals in the WWTS must take into account metal contents and
their fates in sewage sludge. Detailed environmental, toxicological and
ecotoxicological assessments of metals provide assurance that the concentrations of
Cd, Cu, Ni, Cr, Hg and Pb in sewage sludge are well below values that constitute a
potential risk to soils and the environment when sludge is applied to agricultural land.
Zinc, on the other hand, presents the principal potential risk to crop yields from
phytotoxicity to affecting soil microbial processes. However, it is also an important
trace element and the environment can be protected from the potentially toxic effects
of Zn in sludge by technically based, but precautionary soil limits.
Table 7.5 Arithmetic mean metal content in sludge and maximum permissible
limits in soil and sludge (mg kg-1ds) in the EU(1)
Element Mean 86/278/EEC Proposed EU 86/278/EEC Proposed
maximum in maximum in maximum in EU
sludge sludge soil (range) maximum in
(range) soil (pH 6-7)
(2)
Zn 863 2500-4000 2500 150-300 150
Cu 337 1000-1750 1000 50-140 50
Ni 37 300-400 300 30-75 50
Cd 2.2(3) 20-40 10 1-3 1
Pb 124 750-1200 750 50-300 70
(4)
Cr 79 1000 60
Hg 2.2 16-25 10 1-1.5 0.5
(1)
Data are reported for 13 countries: Austria, Denmark, Finland, France, Germany,
Greece (Athens), Ireland, Luxembourg, Norway, Poland, Sweden, The Netherlands and UK.
(2)
Excludes Poland and Greece (represented by Athens WWTS); the mean Zn content in
Polish sludge and sludge from Athens WWTP is 3641 and 2752 mg kg-1 ds, respectively. The
-1
mean European value including Poland and Greece is 1222 mg Zn kg .
(3)
Excludes Poland; the mean Cd content in Polish sludge is 9.9 mg kg-1 value. The mean
European value including Poland is 2.8 mg Cd kg-1 ds.
(4)
Excludes Greece; the mean Cr content in sludge from Athens WWTP is 886 mg kg-1. The
mean European value including Greece is 141 mg Cr kg-1.
Theoretical calculations (Case Study (i)) suggest that typical dosing rates of FeSO4
salt may increase the Cd content of sludge by 4.5 mg kg-1. The Ni concentration in
sludge may increase by 130 % compared with national weighted average values and
Zn and Pb contents may be typically raised by 10 %. Indeed, the use of low-grade
precipitants could erode the significant progress that has been achieved in reducing
The platinum group metals (PGMs) are a group of rare elements including platinum
(Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir) and osmium (Os) and
the current status of the sources and knowledge of the fate and environmental
consequences of PGMs are described in Case Study (a). The commercial use of Pt
and Pd in particular has expanded significantly in recent years in the manufacture of
catalytic converters to reduce atmospheric emissions of carbon monoxide,
hydrocarbons and nitrous oxide from internal combustion engines. The discharge of
Pt from excreted anti-neoplastic drugs used in the treatment of cancers is another
identified source entering the WWTS. However, reliable quantitative estimates of
major Pt and Pd sources are available and show that hospitals contribute a relatively
minor input, equivalent to 6 – 12 % of Pt discharged to sewer, compared with vehicle
exhaust catalysts. Glass, electronics and jewelery manufacturing are other potential
sources of PGMs and can represent important local inputs of these elements
entering particular WWTS. The rate of removal of PGMs from UWW by sewage
treatment processes is generally within the range of most other potentially toxic
element species and approximately 70 % of the Pt in wastewater is transferred to the
sewage sludge. Reported concentrations of Pt in sludge from 2 WWTP in Munich
were in the range 86 – 266 µg kg-1 ds.
Platinum group metals emitted as autocatalyst particles behave inertly and have
limited mobility in soil so there would appear to be negligible risk to health,
groundwater and the environment. However, it is possible for transformations to
soluble, bioactive forms to occur and as the commercial use of PGMs continues to
rise, there is a case for a limited investigation of their environmental significance.
These studies should focus on the factors controlling the solubility and bioavailability
of PGMs and on the behaviour of PGMs in surface waters receiving treated sewage
effluents. Information is also needed on the uptake of PGMs by crops from the
agricultural use of sludge and direct deposition onto urban garden soils to quantify
the potential transfer by multiple exposure routes to the human foodchain.
General
Compared with the small number of PTEs of concern in wastewater and sludge
which are routinely monitored and controlled, the range of organic contaminants
present in these media, with the potential to exert a health or environmental hazard,
are significantly more diverse. For example, approximately 140 organic compounds
have been identified in UWW in Sweden and more than 330 organic substances
have been determined in German sewage sludge. Forty two organic compounds are
regularly detected in sludge.
Historic pollution levels are important for organic pollutants as well as potentially toxic
elements. For example PCBs, which are no longer used, largely result from
volatilisation from soil and are found in similar concentrations in all the WWTS. This
suggests either that sources are diffuse and spread evenly or that this is due to
general background concentrations. Soil is an effective scavenger and sorptive
medium for organic pollutants and acts as a long-term and major repository, although
biodegradation also takes place. Contemporary remobilisation by volatilisation from
soil and redeposition onto surfaces and consequential collection by UWW systems is
a major source of these compounds entering sewage sludge.
Clinical waste
Industry - processes incineration
Volatilisation from
Waste and landfills chlorophenol
Vehicle
450
Dioxin concentration (ng TEQ kg ds)
400
350 US EPA proposed
limit
300
250
200
150 German
100 limit
50
0
1944 1949 1953 1956 1958 1960 1998
Year
Figure 7.3 Dioxin content of archived samples of sewage sludge from a WWTS
in West London, UK
Emissions of other organic contaminants and entry to the WWTS are associated with
direct or indirect discharges resulting from their use in commercial and domestic
activities. For example, the principal emissions of DEHP occur from the use of
finished products and major domestic inputs to UWW are floor and wall coverings
and textiles with PVC prints. In Sweden, for example the domestic contribution was
equivalent to approximately 70 % of the total load of phthalates to Gothenburg
WWTS. Numerically, detergent surfactants and residues (LAS and NPE) are the
most significant contaminants in sewage sludge and the LAS content is typically
more than twice the proposed European limit for this pollutant in sludge (Table 7.6).
Unless action is taken to reduce the use of the surfactant LAS in detergent
formulations, the proposed standard will prevent use of sludge on agricultural land.
The UK also appears to have a particular problem with NP and NPEs as
concentrations of these compounds in UK sludge are an order of magnitude larger
than those reported in average sludges in other European countries Non-
1. Little is known about the fate and behaviour in UWW of the large number (>200) of
commercial chlorinated paraffin formulations in use as plasticisers in PVC and
other plastics, extreme pressure additives, flame retardants, sealants and paints.
2. The brominated diphenyl ethers (PBDEs) are a group of compounds used for
flame retardation in furnishings, textiles and electrical insulation and their use has
expanded due to fire regulation requirements and the increased use of plastic
material and synthetic fibres. A survey in Sweden indicated concentrations of PBDE
congeners in sludge were between 15 and 19 µg kg-1, respectively. PBDEs are on
the list of proposed priority hazardous substances.
1
for musk ketone and 75 t y-1 for musk xylene and the release of these compounds
to the environment is dominated by domestic discharges to WWTS.
resulted in their withdrawal from this application in Japan and Sweden, and stringent
controls on their use are also in place in Germany and France. These factors have
drawn attention to the possible environmental implications of sludge dewatering
practices with polyelectrolytes and long-term accumulation in sludge-treated soil.
• Volatilisation;
• Biological degradation;
• Abiotic/chemical degradation (e.g. hydrolysis);
• Extraction with excess liquors;
• Sorption onto solid surfaces and association with fats and oils.
Many sludge organics are lipophilic compounds that adsorb to the sludge matrix and
this mechanism limits the potential losses in the aqueous phase in the final effluent.
A proportion of the volatile organics in raw sludge, including benzene, toluene and
the dichlorobenzenes, may be lost by volatilisation during wastewater and sludge
treatment at thickening, particularly if the sludge is aerated or agitated, and by
dewatering. As a general guide, compounds with a Henry’s Law constant >10-3 atm
(mol-1 m -9) can be removed by volatilisation. The significance of volatilisation losses
of specific organic compounds during sewage treatment can be predicted based on
Henry’s constant (Hc) and Kow:
Lower molecular weight phthalate esters and butyl benzyl phthalate are completely
degraded in 7 days by anaerobic digestion at 35°C and should be removed by most
municipal anaerobic digesters. The extent and rate of biodegradation of organic
compounds during anaerobic digestion is apparently related to the size of alkyl side
chains and compounds with larger C-8 groups are much more resistant to microbial
attack. Therefore, di-n-octyl and DEHP are more persistent and are not removed by
conventional anaerobic treatment of sludge. Phthalate esters are rapidly destroyed
under aerobic conditions, however, and biological WWT (eg activated sludge
process) can usually achieve >90% removal in 24 h. In soil, the reported half-life of
DEHP is <50 d.
Table 7.8 Assessment of the significance of organic contaminants entering urban wastewater and sewage sludge
(1) (2) (3) (4)
Contaminant Content in Priority Destruction in treatment Accumulation Background Overall
WW/sludge hazardous (Yes, Y; No, N) inputs significance
substance (Yes, Y; No, N)
(5)
Wastewater Sludge Biological Soil (Yes, Y; No, N) Wastewater Sludge
LAS H N H L Anaerobic N N N H L
H Aerobic
NPE M-H Y M L Anaerobic N N N H L
H Aerobic
DEHP M (Y) M L Anaerobic N N N H L
M Aerobic
PAHs L-M Y L L Y Y Y L L
PCBs L N L L Y Y Y L L
PCDD/Fs L N L L Y Y Y L L
Pharmaceuticals L N M M N N N M L
Oestrogenic:
Endogenous L N M-H M-H Y N Y H L
Synthetic L N L-M L-M Y N N H L
(1)Concentration ranges for sludge: L< 1 mg kg-1 ds; M<100; H >100 mg kg-1 ds. Concentrations in wastewater are small (mg l-1) and highly
variable, but will follow a similar general pattern to sewage sludge; published values are listed in Table 3.14 in the Main Report.
(2)European Commission Amended Proposal for a European Parliament and Council Decision establishing the list of priority substances in the field of
water policy (COM(2001)17 final of 16 January 2001).
(3)Approximate indicative ranges: L < 20 %; M = 20 – 60 %; H > 60 %
(4)Significance rating: Low, L; Moderate, M; High, H
LAS Linear alkylbenzene sulphonates
NPE Nonylphenolethoxylates
DEHP Di-(2-ethylhexyl)phthalate
PAHs Polycyclic aromatic hydrocarbons
PCBs Polychlorinated biphenyls
PCDDs Polychlorinated dibenzo-p-dioxins
PCDFs Polychlorinated dibenzo-p-furans
Table 7.9 Sources and control of organic contaminants entering urban waste water and sewage sludge
The significance of the identified sources of metals entering the UWW system has been
reviewed and opportunities for further reducing metal inputs are considered. This may be
possible through, for example, controlling discharges from a number of specified commercial
sectors and the introduction of remedial measures to reduce inputs from certain domestic
and diffuse sources. Therefore, a feasibility study of the most effective approaches to further
reducing metal inputs is recommended so that appropriate remedial strategies can be
implemented.
The contributions by the three major sources of pollutants to UWW is predicted to change.
Commercial sources are expected to become less important as the regulatory control is
more widely implemented and tightened, while the percentage contribution from domestic
sources is expected to increase. This is important as it is less easy to regulate domestic
discharges to UWW. However this can be achieved to some extent by controlling the
products used in homes; for example cadmium emissions from households could be
reduced by a ban on the use of phosphates in washing powders. Increasing consumer
awareness of pollution in UWW, for example through eco labelling schemes, can lead to
reductions in load to UWW from some sources such as the domestic use of LAS, however
this requires much wider adoption by manufacturers of eco labelling schemes. Industry and
stakeholder involvement need to be encouraged. Mechanisms to provide an incentive for
reductions in pollution and alternative product development should be developed.
There is probably little scope for further reductions in the inputs and concentrations of
persistent organic contaminant types in sewage sludge. For example, it is unlikely that much
can be done to curb emissions of PAHs and PCDD/Fs from domestic coal burning, where
this is widely practiced, and incinerators are already subjected to stringent air quality
emission standards. Losses of PCBs from electrical transformers is rapidly declining as
these are phased out of use. However, the importance of soil as a repository for persistent
organic contaminants is emphasised and the focus of further investigations to minimise
inputs to sludge could be directed towards better understanding of the remobilisation and
cycling of these substances in the environment.
Due to the variability of existing data on potentially toxic elements and organic pollutants,
common methodologies and standards of chemical and statistical analysis are necessary
and should be implemented at a European level as soon as feasible.
Feasibility of reuse of treated wastewater for non-household purposes, such as for irrigation
of agricultural crops, parkland, and golf courses needs to be considered but must involve
assessment of risks to human , environmental and economic strategic issues. Reuse of
domestic grey waters in the EU needs to be re-evaluated. Development of common
standards are necessary.
Sustainable urban drainage, discussed in detail, Case Study (b), may have great potential in
terms of reduction of urban runoff pollution. However it is recommended that each case
should be assessed individually, and an incremental approach containing both high tech and
low-tech solutions is the most likely development scenario (Butler and Parkinson, 1997).
There are some areas where restrictions need to be tailored to specific uses: for example,
the urban use of pesticides may need separate guidelines, than those applicable to
agriculture. Urban use of pesticides and herbicides in gardens and allotments is often
indiscriminate and can result in major uncontrolled inputs to the UWWS.
For mercury, dentists are important sources and improved dental practices may reduce this
source, but other sources, such as chloralkali processes, can in some instances emit more.
The use of thermo-reactive liquids in thermometers has been introduced in some regions as
a replacement for mercury. Mercury recycling schemes have also been a success in many
regions and could be extended to other potential pollutants used in domestic and
commercial settings.
Adjusting the pH of tap water may be useful in reducing corrosion, for example, from
domestic and commercial heating systems, but may be limited by practical and economic
factors and it can still be a problem in drinking water in some regions. For example, lead
passing into drinking water supplies from old lead piping and then into the sewage system
can be controlled by adjusting the pH and hardness of the water supply.
This report benefits from the presentation of several specific case histories, which provide
detailed information in support of the above conclusions. Some specific potential problem
areas have been reviewed. For example, the differences in cadmium concentrations
reported in sewage sludge in the United Kingdom and Germany have been shown to be due
to different approaches to data treatment and presentation rather than real variations in
composition. (see Section 2.3)
In the WWTS the fate of compounds often differs, for example, Ni is removed less well from
treated wastewater than other metals. This means that more Ni will pass out in the effluent
from the WWTS and less will be concentrated in the SS. The behaviour of compounds
should be borne into consideration when considering acceptable levels in the influent.
It is also important to note that some of the metals in this study, for example zinc and
copper, are essential trace elements to plants and animals in low concentrations. It is
important that levels in treated UWW and SS are not set so low by regulation that mineral
deficiency could arise due to removal of these sources where UWW and SS might have
been used, for example, on nutrient deficient land.
Domestic and industrial product formulation can have an important role in determining the
nature and amount of pollutants that are likely to enter the WWTS. Risk assessment of
domestic products should be based on their input of pollutants to the urban wastewater and
the biodegradability of the pollutants. Health and environmental effects should be considered
in the risk assessment process. Efforts to remove phosphate in detergents have had a knock
on effect in lowering the cadmium input to the WWTS. NPE bans and regional LAS
reduction through eco-labelling schemes have also been proven effective. It would also be
possible to pre-treat high LAS concentration in UWW from commercial sources, which would
then reduce levels reaching the WWTP.
Advice on household refurbishment (e.g. for old lead paint, piping) and advice on disposal of
potential pollutants (e.g. down sinks) and eco-labels and public education should be
provided and extended where possible to raise awareness of ecological impacts of various
processes and products in urban wastewater.
The inclusion of Cu, Zn and LAS on the proposed list of priority substances is recommended
because they are the most limiting substances to utilising sludge in agriculture within the
limits proposed in the revision of Directive 86/278/EEC and they are ubiquitous in
wastewater. Therefore, these substances should also be the focus of measures to reduce
discharges and emissions to further improve sludge quality and support the recycling route
for sewage sludge.
In order to reduce inputs to UWW, it is important to target the sources contributing most to
the system, especially the diffuse sources. Trade effluent discharge controls have been
successful in lowering emissions but are still necessary for certain industries. Reductions of
many pollutants including lead and dioxins have been seen in sewage sludge since the
1960s. Increasing control on emissions, not only to water but also to air and land, are likely
to continue this reduction. This study concludes that small users, hospitals, garages and car
washes, dental and medical practices need a close monitoring and control for connection to
the urban wastewater systems.
Relatively few regional surveys of the sources and significance of potentially toxic element
(PTE) inputs to UWW (Section 2.1) have been reported and recently published work, in
some cases, quote data from considerably earlier studies. There is a general lack of recent,
quantitative information regarding the sources and inputs of PTEs to UWW for the EU and
this is identified as a priority area for further data gathering.
There are very few studies available on the mass balance of potentially toxic elements and
organic pollutants through WWTS. More work is needed to understand the partitioning and
speciation of pollutants, particularly for compounds, such as NPE, which may become more
toxic through wastewater treatment. Some pollutant sources still need further identification.
In fact there are also many instances where the majority of pollutants sources remain
unidentified, for example the ADEME study in France estimated that over 50% of some of
the metals came from unidentified sources.
Identification and monitoring of trace organics is still sparse and more detailed work, though
costly, is urgently required. Better source inventory data is essential. In some cases
specific industrial sources are difficult to locate. For example, platinum uses and losses from
industry into the wastewater system are subject to the protection of commercial interests.
Information on organic pollutants comes mainly from France, the United Kingdom, Benelux,
Scandinavia and Germany but is very limited from the other EU countries. More research is
needed for estimates and quantification of diffuse sources of organic pollutants especially in
Iberia, Italy and Greece. Some data especially from Iberia is not readily available and an
integrated data collection system is needed across the EU 15 for PTEs and organic
pollutants.
Information is still needed in order to asses health and environmental effects. UWW effluent
and sewage sludge use on land usually involves exposure to very small quantities of mixed
pollutants over a prolonged period of time, and there is little health data about chronic
exposure, particularly to organic pollutants. A particular area of current concern is the
possible impact of cocktail effects where several contaminants are present at the same time.
Interactions between metals, organics, and metals and organics may be synergistic or
antagonistic, are complex and far from clearly understood.
Another area where knowledge is lacking is that concerning the effects of both potentially
toxic elements and trace organics on components of the ecosystem, both in soils and in
surface and subsurface waters. The prime effects to be considered are those on sensitive
receptors, including micro-organisms, invertebrates and plants. At present there is a lack of
base line information in this area. Ecotoxocity tests that are applied are undertaken in
laboratory conditions assuming 100% bioavailability of the pollutant, and are not appropriate
for field conditions. Research into the transfer of organic pollutants through uptake into
pasture plants and into crops and thus into the food chain is limited and should be
considered.
APPENDIX A
URBAN WASTEWATER TREATMENT SYSTEMS (WWTS) AND SEWAGE SLUDGE TREATMENT (SST)-
REGIONAL ASPECTS
Figure A.1 Water and pollutant sources and pathways in urban catchments
[after Ellis, 1986, note that this figure could be extended to include sludge output from the WWTS and
also other potential inputs such as from urban use of pesticides
* a gully pot (also known as catchbasin) is a chamber or well, usually built at the kerb side, for the
admission of surface water to a sewer or sub-drain. It has a sediment sump at its base to trap grit and
detritus below the point of overflow.]
Sewage sludge consists of residues originating from mechanical, biological, chemical and
physical treatment of wastewater in sewage plants. The quantity and nature of the arising
sewage sludge are subjected to strong fluctuations depending on the wastewater
composition, the kind of wastewater purification process and the purification degree. Two
different sewage sludge types can mainly be distinguished:
Primary and secondary sludges are usually combined to create a composite sludge, which
often goes for further treatment in sludge digestion and dewatering. Residues resulting from
screening in preliminary treatment are not considered as sludge, consisting mainly of coarse
solid particles, grits, sands and grease [Magoarou, 1998].
Although the ‘nitrate’ and ‘phosphate’ ions in sewage are beyond the realm of this project, it
has to be noted that pollutants such as potentially toxic elements, organics, sulphides and
residuals, can form insoluble phosphates in the course of treatment processes. These have
great propensity for sedimentation in all stages of the sewage treatment process, thus
becoming part of the sewage sludge that has to be managed.
Figure A.2 shows the schematics of urban wastewater and sewage sludge treatment.
Prel
Prim
Adv
Secondary Treatment
Trea
Trea
Trea
imintmen
ance
arytmen
Secon
men
ary t
d t
Nutrie
Sceen
Physic
Activa
Settle
Colou
Girt&
Liquid
Basin
dary
t Separ
ing,
nt Remo
ment
al/Che
ted Sludge
Remo
Greasval
r Remo
and
ation
mical
e Trap
Solid
val,
val
SECO
TERT
PRIM
RESIDUES
SLUD
SLUD
SLUD
IARY
NDAR
ARY
GE Y
GE
GE
SludAnaer
geMesop
Sludg
Comp
obic/A
e tioning
Stabil
hilic/T
stion
Advan
osting
erobic
isation
hermo
ced ponds
REGIONAL ASPECTS:
Protection of the receiving waters from pollution by harmful effluent is the primary goal for
the treatment of urban wastewaters at WWTS. Urban wastewater is defined by the Council
Directive 91/271/EEC of 21 May 1991 concerning urban wastewater treatment (and as
amended by Commission Directive 98/15/EC of 27 February 1998) as, domestic wastewater
or the mixture of domestic wastewater with industrial wastewater and/or run-off rainwater.
The figures for water supply, consumption and treated wastewater are very variable across
the European Union. The water supply (litres/inhabitant/day) fluctuates greatly accross the
European urban areas (EUROSTAT data,1998-2000, Ginés, 1997). Not all collected
wastewater is treated; the percentage of urban wastewater not receiving treatment ranges
from 3% in Germany, up to 77% in Greece. This may include unplanned wastewater
collection, such as septic systems or leakage of UWW collection systems. Cities such as
Milan and Brussels do not yet have a centralised WWTS.
Table A.1 Population and household access to sewerage and wastewater treatment
facilities
Country Population Percentage of population with access to sewerage and public WWT
(1998) facilities
thousands Access to No treatment P P+S P+S+ Year
sewerage T
(%) (%) (%) (%) (%)
Austria 8,075 76 1 1 39 35 1995
Belgium 10,192 78 37 1997
Denmark 5,295 87 18 1996
Finland 5,147 78 0 7 71 1997
France 58,727 81 4 0 0 77 1994
Germany 82,057 92 >31 >47 1995
Greece 10,511 70 16 0 0 54 1996
Ireland 3,694 68 32 23 12 1 1995
Italy 57,563 84 16 3 38 26 1996
Luxembourg 424 88 0 19 57 11 1995
Netherlands 15,654 98 2 0 68 28 1994
Portugal 9,957 55 34 9 11 0 1990
Spain 39,348 62 13 11 34 3 1995
Sweden 8,848 86 0 0 5 81 1995
UK 59,090 96 9 9 64 14 1996
- England & - 96 10 0 0 86 1995
Wales
-N. Ireland - 83 1996
-Scotland - 94 1996
TOTAL EU 374,582 84 - - - 48 -
Table A.1 shows the data in EU15 for the total population, population access to UWW
collecting systems and to urban wastewater treatment facilities. The EU15 average shows
that 84 % of the households have access to UWW collecting systems, whereas only 48 % of
the urban wastewater is treated in primary + secondary + tertiary treatment facilities.
According to the European Waste Water Group (1997) report on urban wastewater
treatment in the EU and accession countries, there are marked differences between various
European regions in terms of primary, secondary and tertiary treatment as shown in Figure
A.3. The four represented groups of countries are: EU10 (all EU countries minus Austria,
Belgium, Denmark, Ireland and Sweden), EU south (France, Greece, Italy, Portugal, Spain),
EU north (Germany, Finland, Netherlands, Luxembourg and United Kingdom) and AC10
(accession countries, Bulgaria, Czech Republic, Estonia, Hungary, Lithuania, Latvia, Poland,
Romania, Slovenia, Slovakia).
The percentage of population not connected to the UWW collecting systems (considered
"rural") increases in the order:
EU north (4%) < EU south (18%) < AC10 (40%)
In terms of primary, secondary and nutrient removal treatment the order is:
These differences show a north-south and an west-east divide and point towards the need
for greater investment in the urban wastewater treatment in the southern region and the
accession countries.
Figure A.3 Urban wastewater treatment in EU and accession countries (minus Cyprus)
[after EEA, 1999, chapter 3.5 Water Stress]
This led to increased recognition of the need for national and international agreements to
limit local and global environmental perturbations and has led Sweden and Norway in
particular to be among the most pro-active nations in terms of setting environmental
standards and education amongst the general population.
Finland, Norway and Sweden have low population densities and there are similarities in the
commercial activities in these regions, for example the oil production, metals and
engineering and paper manufacturing industries. Denmark has a higher population density
than other countries in the Northern region and therefore more of an urban environment but
also has a high level of environmental concern about water pollution, although all the
drinking water in this region is from groundwater sources. This compares with the UK, for
example, where approximately one third of potable drinking water is abstracted from surface
water sources that receive effluent from wastewater treatment.
In addition to Germany and Austria, data are gathered where available for Switzerland and
for Central and Eastern European countries (Bulgaria, Czech Republic, Estonia, Hungary,
Latvia, Lithuania, Poland, Slovakia, Slovenia), all associated EU countries. Environmental
awareness in the Central Region is high in Germany, Austria and Switzerland whereas the
CEE countries experience a high level of environmental damage due to the long years of
neglect while part of the Soviet bloc. Transboundary pollution issues are very important in
the accession CEE countries and their neighbours. Very little data is available for the CEE
countries regarding the pollutants in UWW and SS. An inventory of organic pollutants in the
environment in the CEE countries was done by a team at Brno University, the Czech
Republic. (Persistent, Bioaccumulative and Toxic Chemicals in Central and Eastern
European Countries - State-of-the-art Report-TOCOEN REPORT No. 150, 1999). The main
organic pollutants investigated are the PAHs, PCBs, PCDD/PCDFs and their ocurrence in
the urban environments in the CEE countries. Most data available is from the Czech
Republic, Poland, Slovakia and Hungary.
The environmental awareness in the region is on the increase in the recent years. Water
resources are limited in the Southern Region and therefore recycling of treated waste water
and pollution reduction at source are important issues. Data regarding sources of pollutants
is less abundant in the 'Southern Region' especially regarding specific organic pollutants.
The region has among the lowest percentage of population access to UWW collecting
systems in the EU (70% for Greece, 84% for Italy, 55% for Portugal and 62% for Spain). The
percentage of non-treated wastewater is among the highest in the EU (16% for Greece and
Italy, 34% for Portugal and 13% for Spain) [after OECD Report, 1999, EUROSTAT, 1998-
2000].
Typically, the metal content of sewage sludge in Italy is low, according to the literature
[Garcia-Delgado et al., 1994; Lang et al., 1988] suggesting that the sludge is mainly of
domestic origin, with negligible contribution from urban and industrial wastewater. Data for
Southern Italy were gathered in a two years pilot campaign [Braguglia et al., 2000; Marani et
al., 1998; Mininni et al., 1999].
Wastewater treatment systems in Italy may treat 'non domestic' wastewater if the following
requirements are fulfilled:
- the plant has a residual capacity of treatment;
- wastewater meets the limits for discharge in UWW collecting systems;
- wastewater derives from the same territorial area;
- the same treatment tariff valid for the UWW discharge is applied.
There is very little information sources of pollutants and levels of pollutants in urban
wastewater and sewage sludge in Portugal [Palerm and Singer, 2000]. Most of the
information that exists was obtained prior to designing the wastewater treatment plants, but
this information was gathered at a local level and is not publicly available.
Data are available in Greece for sewage sludge content of potentially toxic elements, and
more limited for pollutants in urban wastewater. The Hellenic Ministry for Environment,
Physical Planning and Public works co-ordinates the data management in terms of
pollutants load in urban areas. The research studies tend to centre on the cities of
Thessaloniki or Athens.
The Western Region (UK, Ireland, France and the Benelux countries, Belgium Netherlands
and Luxembourg):
In this region, wastewater treatment is among the most advanced in the EU. France has
over 160,000 km of sewers and 11,300 treatment plants. The WWTS are operated by public
or private bodies. The ownership of WWTS and sewers are always public, owned by
municipalities or associations of municipalities. France is divided into six Water Agencies,
mainly around hydrographic areas, Adour-Garonne, Artois-Picardie, Loire-Bretagne, Rhin-
Meuse, Rhone-Méditéranée-Corse and Seine-Normandie. The municipalities operate the
sewer systems and often, private companies run the plants [EWWG, 1997].
In the Netherlands, the municipalities are responsible for collection of sewage and disposal
of sludge from sewers. The treatment of wastewater and disposal of effluent and sludge is
the responsibility of 27 waterboards. Sludge disposal is partially privatised. In Belgium, the
municipalities are responsible for the sewerage systems in both Vlanderen and Wallonie.
Similarly, in Luxembourg, the 118 municipalities are responsible for the collection and
treatment of urban wastewater and sludge. The management of sludge is partially shared
with operators of solid waste [EWWG, 1997].
In UK there are over 300,000 km sewers and 7,600 WWTS. The collection of sewage, its
treatment and disposal of effluent and sludge are the responsibility of privately-financed
water service companies in England and Wales (10), public water and sewerage authorities
in Scotland (3), and the Water Service of the Department of Environment in Northern Ireland
[EWWG, 1997]. In the Republic of Ireland, the urban wastewater collection and treatment is
the responsibility of local councils. Private-Public Partnerships (PPP) schemes are in place
for modernising and upgrading the WWTS [Dept. of Environment and Local Govt, Ireland,
1999]
In order to understand the behaviour of organic pollutants in the urban environment the
knowledge of their physical and chemical properties is very important. Vapour pressure,
boiling-point, water solubility and distribution coefficients describe the distribution between
solid, liquid and gaseous phase. The adsorption coefficient KOC is important for transitions
between soil or sewage sludge particles and water. The transition water/air is governed by
the Henry coefficient KAW. The distribution coefficient octane/water KOW is a measure for the
lipophilic or lipophobic qualities of a chemical compound. For substances with similar
physical properties, their water solubility is a crucial factor for the liquid phase transport.
CH3-CH2-CH-(CH2)8-CH3
SO3-Na+
Figure B.1: LAS structure formula.
PCCDs and PCDFs are tricyclic, aromatic, almost planar built ethers with comparable
physical, chemical and biological qualities. They differ from each other in the position and
number of chlorine atoms and the symmetry of the basic structure. Figure B.2 shows the
structure formulas of the polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo
furans (PCDD/F).
239
Appendix B
9 1
8 2
7 3
Clx Cly
6 4
PCDD
9 1
8 2
7 3
Clx Cly
6 4
PCDF
Figure B.2 PCDD/F structure formulas.
PCDD/F are extremely heavy-volatile components (high melting and boiling-points). The
vapour pressure drops with chlorine substitution, so that low-chlorinated dioxins and furans
are quite volatile. Highly-chlorinated compounds are found in solid state adsorbed on
particles. The greatest mobility is in the air. In water, PCDD/F are almost completely bound
to particles (high octane/water distribution coefficient). The affinity to organic carbon
compounds is strongly pronounced (high adsorption coefficients). Due to their physico-
chemical qualities PCDD/F are very firmly bound to soil and sediments.
PCDD/F do not react with acids and bases and are quite chemically inert. They are thermally
stable at temperatures up to 600-800 °C. The extraordinary stability and the low photolytic
reduction render them to be very persistent in the environment. Because of the long life time
and the lipophilic qualities PCDD/F can accumulate in organisms: they accumulate
predominantly in animal fatty substances [Mahnke, 1997].
The polychlorinated biphenyls (PCBs) form a group of over 209 chlorinated, aromatic
compounds with the same structural features. They differ with the degree of chlorine
substitution and with their structure. PCBs are substances with low electrical conductibility,
high thermal and chemical stability and low water solubility. They are characterised by a high
lipophilic character, so they accumulate in the food-chain. Their biological degradability in
the environment depends on the complexity and chlorination of each particular compound.
Figure B.3 shows the PCBs structure formula. The physical-chemical qualities of selected
PCBs compounds are specified in Table B.2.
3 2 2' 3'
4 4'
240
Appendix B
The polycyclic aromatic hydrocarbons (PAHs) are of major public concern because of their
ubiquitous occurrence and high carcinogenic potential. PAHs are multi-core aromatic ring
systems with 5 and 6 rings. They represent benzene condensation products. PAHs are solid,
mostly colourless compounds. They have a strong lipophilic character and their water
solubility decreases with the increase of ring numbers. Low-molecular PAHs are relatively
volatile. PAHs with a boiling-point below 400°C exist in the air in gaseous state. The higher
boiling compounds are adsorbed to particles. The physico-chemical features of some PAHs
are indicated in Table B.3 and Figure B.4 shows the structural formula of selected PAHs.
The list of 16 USEPA PAHs is shown in Table B.5.
241
Appendix B
Indeno(1,2,3-cd)pyren Dibenzo(a,h)anthracen
Benzo(b)fluoranthen Benzo(g,h,i)perylen
242
Appendix B
Di-(2-ethyhexyl)phthalate (DEHP)
C4H9
HC-C2H5
CH2
C=O
C-O-CH2-CH-C4H9
O C2H5
243
Appendix B
Nitro-musk Compounds
Properties. Nitro-musk compounds are nitro aromatic bonds with a high stability to chemical
and biochemical reduction, high persistancy and lipophillic behaviour.
Musk ambrette, musk xylene, musk ketone, musk tibetene and musk moskene belong to the
nitro-musk compounds. Trade names and formulas of the nitro-musk compounds are listed
in Table B7.
Properties. Musk xylene and musk ketone are nitrobenzene compounds. They are
persistent, lipophile and accumulate in the food chain. Musk xylene has a biological
accumulation factor (concentration in fatty tissues / concentration in the environment) of 4.1,
Musk ketone of 1.1.
244
Section Eight - References
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xxv
Section Eight - References
8.5 Abbreviations
ADBI celestolide
ADP Antecedent Dry Period (dry/wet deposition)
AHTN tonalide
AOX Adsorbable Organohalogen (Organochlorine) Compounds
APEO Alkylphenolethoxylates
AT Austria
BE Belgium
BOD Biochemical Oxygen Demand
CDO Chemically Dissolved Oxygen
CEE Central and Eastern European countries
CEP 2-Chloroethanol phosphate
CH Switzerland
DBT Dibutyltin
DE Germany
DEHP Di (2-ethylhexyl) phthalate
DEP diethyl phthalate
DK Denmark
DMDTAR Dimethyl di-tallowammonium chloride
DO Dissolved Oxygen
DSDMAC Distearyl, dimethylammonium chloride
EI Ireland
EPA or USEPA, United States Environment Protection Agency
ES Spain
EU European Union
FI Finland
FR France
g/t grams per tonne
GR Greece
HGV Heavy Goods Vehicle
HHCB galaxolide
HM Heavy Metals
IKW Industry association personal hygiene and detergents (Frankfurt)
IT Italy
kg/t kilogram per ton
LAN Long-chain alkylnitriles
LAS Linear alkyl-(dodecyl-)benzenesulphonate
LU Luxembourg
LV Light Vehicle
MBAS Methylene Blue Adsorbable Substances
MBT Monobutyltin
xxvi
Section Eight - References
xxvii
European Commission
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Pollutants in urban waste
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