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D10: Impact of Contaminants - Hydromod

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Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

Work package No. 32: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

Lead contractor: HYDROMOD<br />

Main objective: Strategies<br />

Strategic leader: Dominique Fontvieille (CAR)<br />

Responsible task leader: Kurt Duwe (HYD)<br />

Main contributor involved: Organisation and E-Mail<br />

Simon Weyrer (PuP) weyrer@pap.co.at<br />

Ulrike Sydow (HYD) sydow@hydromod.de<br />

Kurt Duwe (HYD) duwe@hydromod.de<br />

Eckard Hollan (ISF) isf.eurolakes@lfula.lfu.bwl.de<br />

Dieter Boymanns (IPT) dieter.boymanns@jrc.es<br />

Dissemination level: Confidential<br />

FP5_Contract No.: EVK1-CT1999-00004<br />

Version: 4.0<br />

Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 1 <strong>of</strong> 136


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

FP5_Contract No.: EVK1-CT1999-00004<br />

Version: 4.0<br />

Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 2 <strong>of</strong> 136<br />

1 EXECUTIVE SUMMARY<br />

Water is on one hand an irreplaceable and life-supporting element <strong>of</strong> all life, not only<br />

human, but plant and animal life as well, and <strong>of</strong> ecosystems as a whole. Undeveloped<br />

and unpolluted wetlands, in turn, are the single most important precondition for the<br />

protection <strong>of</strong> biodiversity. On the other hand water is also valued as a resource. Surface<br />

and groundwater have manifold economic uses, be it for industry, agriculture, shipping,<br />

mining and many others, and <strong>of</strong> course as a source <strong>of</strong> drinking water.<br />

Therefore any water management initiative should be founded as complete as possible<br />

on a understanding <strong>of</strong> the water resource system to which it applies. Water is first <strong>of</strong> all<br />

a natural resource and the sustainable management <strong>of</strong> that resource calls for an improved<br />

understanding <strong>of</strong> the aquatic ecosystems. Water is a resource which is essentially<br />

best managed at local water basin level but there are common grounds in water<br />

resource development across Europe, and numerous interactions – environmental, as<br />

well as socio-economic – are well beyond the scope <strong>of</strong> action taken at the local or regional<br />

level. This leads to a call for European directives and frameworks to guide management<br />

decisions at the various levels.<br />

This report <strong>of</strong> the European Fifth Framework Programme project EUROLAKES summarises<br />

the impacts <strong>of</strong> contaminants on aquatic ecosystems with respect to great deep<br />

lakes and, while the more obvious signs <strong>of</strong> water pollution, fish kills and foam floating<br />

on the surface, are fortunately seldom encountered in European lakes today, more<br />

subtle biological effects have been the focus <strong>of</strong> this study. Trace quantities <strong>of</strong> endocrine<br />

disrupting chemicals, for instance, have been shown to interfere with the hormone<br />

regulation <strong>of</strong> fish and molluscs, leaving them infertile. Hazardous chemicals such as<br />

these may be made responsible for declining fish catches in several European countries,<br />

yet the exact mechanisms <strong>of</strong> action are extremely difficult to identify. Only a precautionary<br />

approach preventing the continued release <strong>of</strong> potentially hazardous substances<br />

into the environment can solve this problem.<br />

Endocrine disrupting chemicals (EDCs) have caused particular concern because they<br />

may interfere with the normal function <strong>of</strong> the hormonal systems also <strong>of</strong> humans. Endocrine<br />

disrupting properties are found in several classes <strong>of</strong> chemicals released into the<br />

environment such as some insecticides and fungicides, some phthalate plasticizers, dioxins<br />

and anti-fouling paints. Speculation has linked exposure to EDCs to a range <strong>of</strong><br />

effects in humans and animals from falling sperm counts to increases in testicular cancer<br />

all <strong>of</strong> which has fuelled public concern. Humans are exposed daily to chemicals that<br />

have been shown or suggested to have hormone-disrupting properties. Speculation has<br />

linked this to a range <strong>of</strong> disorders. Whilst high levels <strong>of</strong> exposure to some EDCs could<br />

theoretically increase the risk <strong>of</strong> such disorders, no direct evidence is available at present.<br />

Trends in the incidence <strong>of</strong> some <strong>of</strong> these disorders are difficult to discern and,<br />

when they are found, are difficult to interpret because <strong>of</strong> inconsistencies in method.<br />

EDCs are but one <strong>of</strong> a variety <strong>of</strong> potential risk factors, both environmental and genetic.<br />

Despite the uncertainty, it is prudent to minimise exposure <strong>of</strong> humans, especially pregnant<br />

women, to EDCs.


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

FP5_Contract No.: EVK1-CT1999-00004<br />

Version: 4.0<br />

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From the eco-toxicologists viewpoint the true state <strong>of</strong> European water resources and<br />

aquatic ecosystems considering EDCs and other xenobiotics is unknown. Monitoring<br />

programmes are inadequate or partly non-existent in Member States, and where they<br />

are in place, their results <strong>of</strong>ten remain inaccessible to the public. There are no dependable<br />

assessments <strong>of</strong> the ecological status <strong>of</strong> rivers, lakes and wetlands. The Water<br />

Framework Directive 2000/60/EC 16 (WFD) will require an assessment system for the<br />

first time, delivering reliable and comparable ecological status data for all waters, regardless<br />

<strong>of</strong> the European region concerned. It may be astonishing in a rich continent<br />

like Europe to note that the EU is currently unable to indicate the extent <strong>of</strong> pollution and<br />

disruption <strong>of</strong> their aquatic resources with any sort <strong>of</strong> confidence.<br />

While e.g. the issue <strong>of</strong> EDCs is confused by serious gaps in our knowledge, policies to<br />

deal with the current concerns must be developed further and regulations cannot be<br />

‘put on hold’ until all the evidence has been collected as proposed by various economical<br />

interest groups. Development <strong>of</strong> policies and regulations must go hand in hand with<br />

ongoing research and any legislation must be able to adapt rapidly to advances in scientific<br />

knowledge. Above all, there must be a co-ordination <strong>of</strong> both research funding<br />

and policy development between the different bodies responsible international and national.<br />

Many questions about water pollutants cannot be answered yet. Continued research,<br />

with the results made openly available, is essential if the uncertainties are to be<br />

properly addressed and the risks understood.


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

Table <strong>of</strong> Contents<br />

FP5_Contract No.: EVK1-CT1999-00004<br />

Version: 4.0<br />

Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

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1 Executive Summary.............................................................................................. 2<br />

2 Introduction........................................................................................................... 6<br />

3 Background .......................................................................................................... 8<br />

3.1 THE UNDERLYING PROBLEM........................................................................................................... 8<br />

3.2 CURRENT HANDLING OF THE EDC PROBLEM IN THE EUROPEAN UNION ........................................... 9<br />

4 The Endocrine System ....................................................................................... 20<br />

4.1 THE FUNCTION OF HORMONES..................................................................................................... 20<br />

4.2 THE FUNCTIONING OF ENDOCRINE DISRUPTERS ........................................................................... 21<br />

5 Background Information to Materials with a Putative Endocrine <strong>Impact</strong>............. 22<br />

6 Methods <strong>of</strong> Determining the Endocrine Effect <strong>of</strong> Substances ............................ 25<br />

6.1 BACKGROUND ............................................................................................................................. 25<br />

6.2 TESTING STRATEGIES .................................................................................................................. 30<br />

6.3 RECENT DEVELOPMENTS ............................................................................................................. 32<br />

6.4 OUTLOOK.................................................................................................................................... 37<br />

6.5 ECOTOXICOLOGICAL RISK ASSESSMENT....................................................................................... 39<br />

7 <strong>Impact</strong>s <strong>of</strong> Hormonal Active Chemicals to Humans and Animals....................... 43<br />

7.1 THE HAZARDOUSNESS OF ENVIRONMENTAL CHEMICALS ............................................................... 43<br />

7.2 SUBSTANCES AND GROUP OF SUBSTANCES WITH A PUTATIVE ENDOCRINE DISRUPTING ABILITY ...... 44<br />

7.3 TOXIC EFFECTS TO AQUATIC ORGANISMS .................................................................................... 51<br />

8 Ecotoxicology ..................................................................................................... 53<br />

8.1 BEHAVIOUR OF CHEMICALS IN THE ENVIRONMENT......................................................................... 53<br />

8.2 REDUCTION OF FOREIGN SUBSTANCES BY MICRO-ORGANISMS ..................................................... 54<br />

9 Level <strong>of</strong> Pollution in Water and Sediment .......................................................... 58<br />

9.1 TRANSPORT AND ACTION OF TRANSPORT IN WATER ...................................................................... 58<br />

10 The Catchment Areas......................................................................................... 61<br />

10.1 CATCHMENT AREA OF LAKE CONSTANCE (BODENSEE)............................................................... 62<br />

10.2 CATCHMENT AREA OF LAKE GENEVA (LAC LÉMAN)..................................................................... 70<br />

10.3 THE CATCHMENT AREA OF BOURGET LAKE (LAC DU BOURGET).................................................. 80<br />

10.4 CATCHMENT AREA OF LOCH LOMOND........................................................................................ 84<br />

10.5 SUMMARY OF THE SITUATION AT THE LAKES .............................................................................. 89<br />

11 Elimination <strong>of</strong> <strong>Contaminants</strong>............................................................................... 90<br />

11.1 PROCESSES TO ELIMINATE CONTAMINANTS FROM WASTEWATER................................................ 91<br />

11.2 SUMMARY AND OUTLOOK......................................................................................................... 105<br />

11.3 PROCESSES TO ELIMINATE CONTAMINANTS FROM SOURCES FOR DRINKING WATER SUPPLY........ 105<br />

11.4 SUMMARY AND OUTLOOK......................................................................................................... 115<br />

12 Outlook and Recommendations with respect to hazardous substances .......... 116<br />

13 Abbreviations.................................................................................................... 118


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

FP5_Contract No.: EVK1-CT1999-00004<br />

Version: 4.0<br />

Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

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List <strong>of</strong> References................................................................................................... 120<br />

List <strong>of</strong> Figures ......................................................................................................... 129<br />

List <strong>of</strong> Tables .......................................................................................................... 130<br />

Annex 1................................................................................................................... 131<br />

Annex 2................................................................................................................... 134


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

2 INTRODUCTION<br />

FP5_Contract No.: EVK1-CT1999-00004<br />

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Often extending across one or more international boundaries, river basins and subcatchment<br />

areas play a critical role in the natural functioning <strong>of</strong> the earth. Hydrologically,<br />

watersheds integrate the surface water run-<strong>of</strong>f <strong>of</strong> an entire drainage basin. Economically,<br />

they play a critical role as sources <strong>of</strong> water, food and recreational amenities,<br />

hydropower and transportation routes. Ecologically, watersheds constitute a critical link<br />

between land and sea; they provide habitats within wetlands, rivers and lakes – for 40%<br />

<strong>of</strong> the world’s fish species, some <strong>of</strong> which migrate between marine and freshwater<br />

systems. Watersheds also provide habitats – within the terrestrial ecosystems such as<br />

forests and grasslands – for most terrestrial plant and animal species and they provide<br />

a host <strong>of</strong> other ecosystem functions – from water purification and retention to flood<br />

control, nutrient recycling and restoration <strong>of</strong> soil fertility – which are all vital to human<br />

civilisation.<br />

The protection <strong>of</strong> our water resources is an important issue today and in the future.<br />

Water protection means to preserve the natural water cycle or to restore it. A functional<br />

water ecosystem is the basis for a successful sustainable development <strong>of</strong> the environment<br />

both in local and global framework. Every day industry, trade, agriculture and<br />

households use a lot <strong>of</strong> chemical products. About the reactions and effects <strong>of</strong> these<br />

chemicals less or nothing is known. By use or waste management these products reach<br />

the waters directly via sewage or indirectly via air and soil. One <strong>of</strong> the most important<br />

measures is the protection <strong>of</strong> the water against new substances which harm water- and<br />

land organisms as well as humans already in low concentrations, therefore the reduction<br />

<strong>of</strong> the water pollution with all kinds <strong>of</strong> chemicals used by industry, trade, households<br />

and agriculture [BUWAL 1997].<br />

For reaching this aim it is necessary to write the laws and directives in rigid and precise<br />

forms and additionally amend them in the field <strong>of</strong> water protection and fishing, e. g. according<br />

to a protection from endocrine disrupters. Therefore investigations and evaluation<br />

<strong>of</strong> the condition <strong>of</strong> the waters must take place and the public has to be informed<br />

about the results. The risks for the waters must be recognised in time and the associated<br />

need for further research, too, if necessary.<br />

The workpackage WP 32 “<strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong>” <strong>of</strong> the EUROLAKES project is projected<br />

to deliver information to workpackage WP 35 “substantiated ecological targets”.<br />

In this category ecological and ecosystem quality targets and criteria will be adapted to<br />

great deep lakes and their catchment areas. The objectives and the input to WP 35 are<br />

the investigations on the implications <strong>of</strong> considering toxicological contaminants like<br />

relevant organic compounds (endocrine disrupters) and heavy metals for the long-term<br />

management <strong>of</strong> the lake ecosystem which are objective <strong>of</strong> this report. Here the relationship<br />

betwen the lakes as drinking water reservoirs with the rural and urban use in<br />

the catchment areas has to be considered.<br />

Waters being polluted by selective pollution like waste water inflows <strong>of</strong> sewage treatment<br />

plants and diffuse inputs like surface run<strong>of</strong>f from agriculture areas, do not persist


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

FP5_Contract No.: EVK1-CT1999-00004<br />

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on the pollution level even if no dilution by pure inflows happens. Bacteria and ciliates<br />

withdraw permanent organic protective substances by their metabolic activity from the<br />

water in which they thrive [JAEGER 1994]. Thus, micro-organisms have the potential to<br />

eliminate protective substances and to purify the waters in a certain period.This selfpurification<br />

capacity <strong>of</strong> waters is used in sewage treatment plants. Nowadays waste<br />

water is <strong>of</strong>ten contaminated with substances which cannot be eliminated or can only be<br />

eliminated in an inadequate quantum by these plants. Thus, the receiving water is<br />

loaded exceedingly. With respect to "new contaminants" and the economic efficiency <strong>of</strong><br />

treatment, the minimisation and further processing <strong>of</strong> treatment by-products, improvements<br />

in water treatment technologies are needed. A special problem are pharmaceutical<br />

products and pathogenic germs, passing partly intact through the treatment plants.<br />

Here exists a great risk <strong>of</strong> generating resistances so that new purification levels and an<br />

upgrade <strong>of</strong> the treatment plants are needed. With regard to these new purification levels<br />

specific options for deep lakes are analysed in this report to reduce future input <strong>of</strong><br />

pollution to a minimum. The above mentioned anthropogenic load <strong>of</strong> aquatic ecosystems<br />

is not only a result <strong>of</strong> sewage treatment plant effluents and the introduction <strong>of</strong> only<br />

moderate pre-treated waste waters. The rainwash from agricultural areas and the animal<br />

husbandry contaminate the water <strong>of</strong> lakes, rivers and partly the groundwater significantly.<br />

A protection <strong>of</strong> great deep lakes being drinking water reservoirs is important because<br />

they have to comply with a certain standard to guarantee the postulated drinking water<br />

quality. Moreover, pollutants affecting the drinking water quality are also able to have a<br />

negative impact to the aquatic ecosystem. For this reason, these reservoirs have to be<br />

monitored to detect impairments in time. Information on pollutants, pollutant sources,<br />

pathways and impacts with respect to great deep lakes were compiled in this report.<br />

The qualitative and quantitative vulnerability <strong>of</strong> the investigated deep lakes with relevant<br />

organic contaminants and heavy metals were also to be named. The main objective <strong>of</strong><br />

this task, however, was a survey <strong>of</strong> relevant contaminants, their threshold values and/or<br />

limit values with respect to the European Drinking Water Directive. But also the current<br />

valid threshold values <strong>of</strong> relevant substances and compounds in regard to other European<br />

and national directives like the Drinking Water Directive and the Bathing Water Directive<br />

are considered. In doing so, the relevance <strong>of</strong> the list <strong>of</strong> priority substances determined<br />

on European level concerning the investigated areas was considerdd. The<br />

behaviour <strong>of</strong> the detected substances in the aquatic environment is described and the<br />

possibility <strong>of</strong> (new) detection methods as standard test is shown.


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

3 BACKGROUND<br />

FP5_Contract No.: EVK1-CT1999-00004<br />

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3.1 THE UNDERLYING PROBLEM<br />

In [LEISEWITZ 1996] it is mentioned that the consumption and the use <strong>of</strong> synthetic<br />

substances – which cannot be found in the nature - have an enormous influence on the<br />

ecological balance. These xenobiotics are usually persistent and there impact may be<br />

felt on the whole globe caused by world-wide use and/or atmospheric long-distant<br />

transport. In addition, they are already effective in relatively small dosages. Their accumulation<br />

in organisms, the food chain, the soil, waters and sediments (from where they<br />

can be mobilised) have the consequence <strong>of</strong> a long-term effect even at a very low input.<br />

Furthermore they are not recoverable from the biosphere. Most <strong>of</strong> these contaminants<br />

are dissolved in water. Via rivers and the atmosphere they enter the oceans. Therefore<br />

particularly the aquatic systems <strong>of</strong> the estuaries, the coastal area and the marginal<br />

seas have to be concerned besides the inland waters. [LEISEWITZ 1996] continued<br />

that through predator-prey-relationships these substances can be transmitted also.<br />

Thus, their concentration in the organism increases rapidly (biomagnification). Even<br />

children and their parents are connected with each other through the food chain. The<br />

application <strong>of</strong> man-made substances can be effected over the blood supply <strong>of</strong> a growing<br />

embryo, over the suckle or substances being included in the egg. Such a passing<br />

on <strong>of</strong> one generation to the next, causes an accumulation in the organisms <strong>of</strong> the affected<br />

individuals and have a negative influence on the <strong>of</strong>fspring's early stages <strong>of</strong> development,<br />

especially on organs and control mechanisms developing in a fast and intensive<br />

metabolic process at the growing germ, the embryo and baby. This metabolic<br />

process where genetic and the hormone system work together is part <strong>of</strong> a complicated<br />

control mechanism being still unknown in many respects. If it comes to a disorder, development<br />

disturbances, deformations, erroneous trends and the dying <strong>of</strong> the germ<br />

could be the consequences.<br />

In the past the main attention to check health damages caused by environmental<br />

chemicals was a possible toxic, carcinogenic or teratogenic effect. Since the 1990s the<br />

hormone effect <strong>of</strong> contaminants is known. The hormonal regulation is decisive for the<br />

tissue differentiation /proliferation <strong>of</strong> the crotch and the spermatogenesis. This regulation<br />

will be deranged by hormone-like substances or substances which are able to disturb<br />

the balance <strong>of</strong> the hormone system. This means the same substances operate<br />

also reproduction-damaging as endocrine disrupters [LEISEWITZ 1996].<br />

On the basis <strong>of</strong> today’s incomplete knowledge final statements about the effects <strong>of</strong><br />

pesticide residues on the human health respectively on the water ecology can not be<br />

made. The risk lies in the complex effect <strong>of</strong> small dosages <strong>of</strong> different active substances<br />

and not on the toxicity <strong>of</strong> a single substance. On the one hand pollutants reach<br />

waters directly via sewage treatment plants and on the other hand diffusely. The input<br />

<strong>of</strong> pesticides into the ground water depends on the application practice, soil conditions<br />

as well as the mobility and degradability <strong>of</strong> the substance. The use <strong>of</strong> herbicides on railroad<br />

installations is a problem if the substances trickle away directly through the track<br />

ballast without passing an active soil layer where they at least partly be metabolised<br />

[BUWALa].


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

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Today, nearly 100,000 synthetic chemical substances are in use. If they are hardly biodegradable<br />

these substances flow with the sewage in water basins. Most <strong>of</strong> the chronic<br />

environmental disturbances were not predictable and are recognised only with the first<br />

damages. Several laws and regulations control the use <strong>of</strong> such problematic substances<br />

to protect the waters [BUWALa]. Because the chemical structure <strong>of</strong> every substance is<br />

different, it has different properties and must be assessed individually. Therefore, the<br />

large and constantly growing number <strong>of</strong> substances causes a huge amount <strong>of</strong> work for<br />

the licensing authorities. In the environmental impact assessment <strong>of</strong> a substance the<br />

important factors are - in addition to its properties - the way in which it is used and disposed<br />

and the consumed quantity. A priority is given in Germany to the 2,000 substances<br />

which are produced in quantities <strong>of</strong> over 1,000 t/a ("high production volume<br />

chemicals") [BUWAL b]. For a preventive health protection, however, it would be necessary<br />

to avoid such substances being suspected having hormonal effects.<br />

3.2 CURRENT HANDLING OF THE EDC PROBLEM IN THE EUROPEAN UNION<br />

In December 1999 the Communication on a "Community Strategy for Endocrine Disrupters,<br />

a range <strong>of</strong> substances suspected <strong>of</strong> interfering with the hormone systems <strong>of</strong><br />

humans and wildlife" COM (1999) 706 final was published by the European Commission.<br />

The objectives <strong>of</strong> this paper are two-fold. On the one hand the identification <strong>of</strong> the<br />

endocrine disrupting problem, its causes and consequences, on the other hand the<br />

identification <strong>of</strong> appropriate policy action an the basis <strong>of</strong> the precautionary principle in<br />

order to respond quickly and effectively to the problem, thereby alleviating public concern.<br />

Four key elements are identified on the basis <strong>of</strong> which an appropriate set <strong>of</strong> actions<br />

is recommended. These are: the need for further research, the need for international<br />

co-ordination, the need for communication to the public and the need for policy<br />

action.<br />

With regard to the need for further research it is said in the paper COM (1999) 706 final,<br />

that for substances suspected to be endocrine disrupters a list is to be compiled.<br />

To identify the selection criteria used to place substances on this list further scientific<br />

data collection and research is necessary. In addition, it is necessary to assess the<br />

quantities <strong>of</strong> these substances in the environment, based on an examination <strong>of</strong> the<br />

material flow <strong>of</strong> each substance. This includes production volumes, consumption in<br />

further processing and final products and import/export volumes. It is essential to carry<br />

out further research in these areas and to investigate the need for refinement <strong>of</strong> current<br />

risk assessment methodologies to address endocrine disrupters. Because, while no<br />

agreed test methods and no effective screening and testing strategy are available the<br />

communication continues, many substances, for which little information is currently<br />

available, may escape attention when compiling a list <strong>of</strong> potential ED substances.In order<br />

to support a rapid development <strong>of</strong> test methods, the EU may consider necessary to<br />

implement a research effort into the mechanisms <strong>of</strong> action <strong>of</strong> the endocrine system and<br />

the range <strong>of</strong> effects, including the role <strong>of</strong> hormones at key stages <strong>of</strong> life circles. In addition,<br />

further investigations are required into the links between adverse health effects in<br />

humans and wildlife and exposure to specific substances or mixtures <strong>of</strong> substances.<br />

Here are included the health consequences <strong>of</strong> phytoestrogens and hormones used as<br />

growth promoters.


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

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FP5_Contract No.: EVK1-CT1999-00004<br />

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The communication COM (1999) 706 final points at the financing <strong>of</strong> several research<br />

works aimed at the development and validation <strong>of</strong> test methods for the identification <strong>of</strong><br />

endocrine disrupters by the Commission. Last but not least there is also a need to develop<br />

and validate appropriate environmental monitoring tools. Existing Community<br />

provisions <strong>of</strong> law on environmental and human health aspects <strong>of</strong> chemicals are based<br />

on a three-stage approach. This approach is also described in COM (1999) 706 final. In<br />

the first stage, the hazard identification, a substance's inherent capacity to cause adverse<br />

effects on human health and the environment is identified, on the basis <strong>of</strong> the intrinsic<br />

properties <strong>of</strong> a substance. The second stage is a risk assessment where the<br />

risks in conjunction with the exposition <strong>of</strong> a chemical substance are evaluated. In the<br />

third stage, the risk management, strategies for the management <strong>of</strong> risks are developed.<br />

The directives being the basis for the hazard identification, the risk assessment<br />

and the risk management are listed in Annex I <strong>of</strong> COM (1999) 706 final.<br />

The Water Framework Directive Concerning the EDC Problem<br />

It is beyond the scope <strong>of</strong> this chapter to give a comprehensive view <strong>of</strong> the WFD and the<br />

authors have attempted to identify and focus on the key issues <strong>of</strong> the WFD that are related<br />

to chemicals, analyse its provisions, point out weaknesses and ambiguities and<br />

derive from them a number <strong>of</strong> political options which are crucial for the improvement <strong>of</strong><br />

European waters.<br />

In September 2000, after a decade <strong>of</strong> political struggle, the European Parliament and<br />

Council adopted the Water Framework Directive (WFD). There is no doubt that this new<br />

framework for EU water legislation is a most complex package <strong>of</strong> objectives, instruments<br />

and obligations. Two <strong>of</strong> the main goals <strong>of</strong> the Water Framework Directive are the<br />

protection and improvement <strong>of</strong> the aquatic environment and the contribution to sustainable,<br />

balanced and equitable water use. The Directive should also contribute to<br />

achieving the objectives <strong>of</strong> relevant international agreements (e.g. OSPAR,<br />

BARCELONA and HELCOM). This is important since some <strong>of</strong> the objectives laid down<br />

by these international agreements are far-reaching and might ask for more stringent<br />

measures than those currently required under the WFD. New instruments are introduced<br />

in the EU water policy to protect and improve all European waters: an ecological<br />

and holistic water status assessment approach; river basin planning; a strategy for<br />

elimination <strong>of</strong> pollution by dangerous substances; public information and consultation<br />

and finally, financial instruments. Despite these important additions to EU water policy<br />

instruments, a number <strong>of</strong> problems are emerging from the directive. They need to be<br />

dealt with as soon as possible to achieve clear and consistently positive results for EU<br />

waters.<br />

Some <strong>of</strong> the main weaknesses identified are:<br />

- complicated and wide-ranging exemption and derogation conditions for the environmental<br />

objectives for ‘heavily modified’ waters or for new physical modifications<br />

for example;


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- new implementation problems, also due to legal uncertainty - for example the<br />

situation before and after the repeal <strong>of</strong> existing water legislation;<br />

- a shift <strong>of</strong> important decisions to subsequent political processes – like the criteria<br />

for assessing groundwater quality, or the environmental quality standards and<br />

emission limit values for surface waters.<br />

One may say that the WFD follows a two-level approach, which differs from existing EU<br />

water legislation:<br />

- Co-ordination <strong>of</strong> measures at national or Community level (with the WFD).<br />

- The definition <strong>of</strong> exact objectives, guidelines and measures is left to subsequent<br />

political processes (through daughter directives, experts' committees).<br />

The success <strong>of</strong> this approach will strongly depend on political will and future hard work,<br />

on the full participation <strong>of</strong> all stakeholders as well as on the exploitation <strong>of</strong> synergies<br />

between the various legislative instruments provided for under the WFD.<br />

Chemicals Policy under the WFD<br />

With respect to the regulation <strong>of</strong> water pollution, the Water Framework Directive requires<br />

action at Member State level and Community-wide uniform standards for certain<br />

chemicals.<br />

At Member State Level: Environmental quality standards (EQSs) for all pollutants<br />

‘identified as being discharged in significant quantities’ into bodies <strong>of</strong> surface water<br />

have to be set at Member State level (an indicative list <strong>of</strong> the main pollutants is provided<br />

in Annex VIII). Compliance with these EQSs is required for the achievement <strong>of</strong><br />

the objective <strong>of</strong> ‘good ecological status’ (defined in Annex V) by Dec 2015. For ‘High<br />

Status’ surface water bodies, Member States must with regard to the non-deterioration<br />

provision (article 4.1.a.i):<br />

- prevent non-synthetic pollutants discharged in significant quantities from reaching<br />

concentrations in the water body above the range normally associated with<br />

undisturbed conditions;<br />

- and prevent synthetic pollutants discharged in significant quantities from reaching<br />

concentrations above the limits <strong>of</strong> detection.<br />

At Community Level: EU sets Community-wide standards, which have to be met as<br />

part <strong>of</strong> the objective <strong>of</strong> achieving ‘good chemical status’. The more stringent standards<br />

described above apply to high status waters.<br />

The existing Community standards (laid down in the daughter directives to the Dangerous<br />

Substances Directive (76/464/EEC)) are listed in Annex IX. For bodies <strong>of</strong> surface<br />

water, environmental objectives established under the first River Basin Management<br />

Plan required by this Directive shall, as a minimum, give effect to quality standards at<br />

least as stringent as those required to implement Directive 76/464/EEC. However, the


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Dangerous Substances Daughter Directives must be reviewed by the Commission, and<br />

revised control measures proposed, including the possible repeal <strong>of</strong> controls on the<br />

substances covered by these Directives but not included in the Water Framework Directive’s<br />

list <strong>of</strong> priority substances The Water Framework Directive’s list <strong>of</strong> priority substances<br />

will be identified under the procedures laid down in Article 16. Priority hazardous<br />

substances will be selected from this list. The priority list will be reviewed every 4<br />

years. The list replaces the list <strong>of</strong> 129 substances prioritised in the Commission Communication<br />

to the Council <strong>of</strong> 22 June 1982. For priority substances a progressive reduction<br />

in pollution is to be achieved by establishing Community-wide environmental<br />

quality standards and source controls by the procedure laid out in Article 16. For socalled<br />

priority hazardous substances, the cessation <strong>of</strong> discharges, emissions and<br />

losses shall in principle be achieved within 20 years at the latest. There is no derogation<br />

provided in the Directive from these obligations.<br />

Priority Hazardous Substances<br />

Community-wide standards will specifically apply to so-called priority hazardous substances,<br />

a sub-group <strong>of</strong> the WFD list <strong>of</strong> priority substances. This class <strong>of</strong> substances<br />

has been established against fierce resistance at the request <strong>of</strong> the European Parliament.<br />

It is the first time in EU law that the cessation <strong>of</strong> inputs <strong>of</strong> certain chemicals into<br />

surface waters has been made a legal requirement. For priority hazardous substances,<br />

defined in a similar way to ‘hazardous substances’ under the OSPAR agreement on the<br />

protection <strong>of</strong> the Northeast Atlantic, cessation <strong>of</strong> discharges, emissions and losses shall<br />

be achieved within 20 years at the latest. Priority hazardous substances are identified<br />

by the Commission amongst the substances on the priority list (Article 16(3)). To this<br />

end, the Commission will have to assess which <strong>of</strong> the substances on the WFD priority<br />

list fulfil the criteria <strong>of</strong> bioaccumulation, toxicity and persistence set out in Article 2(29)<br />

or are giving rise to an equivalent level <strong>of</strong> concern (e.g. endocrine disrupters, certain<br />

metals, etc.). In that process, the selection <strong>of</strong> hazardous or dangerous substances under<br />

relevant Community legislation (e.g. (EEC) No. 793/93, 91/414/EEC 76/464/EEC)<br />

and international agreements (OSPAR, UN ECE POPs Convention etc.) has to be<br />

taken into account. The identification process does not specifically require full risk assessments<br />

in accordance with Council Regulation (EEC) No. 793/93, which is crucial in<br />

order to follow a precautionary approach.<br />

In a second stage, ‘controls for the cessation or phasing-out <strong>of</strong> discharges, emissions<br />

and losses’ <strong>of</strong> priority hazardous substances have to be adopted by the Council and<br />

EP. The timetable for cessation shall not exceed 20 years as from the adoption <strong>of</strong> these<br />

measures. These controls are again proposed by the Commission as daughter directives,<br />

and have to be adopted by the Council and Parliament. Controls may include<br />

bans <strong>of</strong> certain substances, restrictions in terms <strong>of</strong> use, or a requirement to limit the application<br />

<strong>of</strong> a substance to zero-emission, closed-cycle installations. If the Council and<br />

EP do not adopt the necessary measures for cessation <strong>of</strong> specific priority hazardous<br />

substances (Article 16(8)), Member States are required under Article 4(1)(a)(iv) to take<br />

the appropriate measures to achieve cessation or phasing-out <strong>of</strong> such substances ‘according<br />

to Articles 16(1) and 16(8)’, without a specific deadline provided. It is unlikely,<br />

however, that a Member State will be able to ignore the 20-year deadline, once a priority<br />

substance has been identified as hazardous at Community level.


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The First WFD Priority List<br />

A proposal for a first priority list has been tabled by the Commission in February 2000<br />

(COM (2000) 47 final/2 - 2000/0035 (COD)). It consists <strong>of</strong> 32 substances selected as a<br />

result <strong>of</strong> a simplified risk-based procedure (Article 16.2) with the so-called COMMPS<br />

procedure, which takes account inter alia <strong>of</strong> monitoring results and intrinsic substance<br />

properties. 32 is an arbitrary number and is intended to reflect the Commission’s limited<br />

administrative potential. It does not indicate that there are no more than 32 substances<br />

<strong>of</strong> concern, but that the list <strong>of</strong> substances should be manageable, adding some new<br />

ones every four years. Nevertheless, a number <strong>of</strong> shortcomings can be reported, requiring<br />

improvements under COMMPS for its future application. For example, a great<br />

number <strong>of</strong> substances for which no data were available at Community level from the<br />

national monitoring programmes were left out. This situation applies to:<br />

- about 60% <strong>of</strong> pesticides which are currently in use;<br />

- all industrial chemicals which no company in the EU produces or imports in<br />

quantities <strong>of</strong> over. 1,000 tonnes per year. This concerns about 8,000 to 10,000<br />

substances for which appropriate data were not available in the IUCLID databank<br />

when the COMMPS procedure was carried out;<br />

- industrial chemicals produced or imported by fewer than four undertakings in the<br />

EU in quantities superior to 1,000 tonnes per year (confidentiality <strong>of</strong> market<br />

data).<br />

As a consequence, the COMMPS procedure covered only 95 substances on the basis<br />

<strong>of</strong> monitoring data and 123 substances on the basis <strong>of</strong> modelling data.<br />

Amongst the 32 WFD priority substances, 3 are classified as UNECE POPs, 13 as<br />

hazardous by OSPAR, which means that they are either POP-like substances or highly<br />

toxic, persistent and bioaccumulative. Another 16 are selected under OSPAR 1998 and<br />

2000 for priority action for a cessation <strong>of</strong> their releases by 2020. It should be very clear<br />

that the priority substances that fulfil one <strong>of</strong> these selections should be identified as priority<br />

hazardous substances. The Community has internationally committed itself to<br />

cease emissions <strong>of</strong> these substances by 2020. 21 priority substances are in one <strong>of</strong> the<br />

above-mentioned ‘hazardous’ categories and most <strong>of</strong> them are on different lists established<br />

in Community legislation on dangerous/hazardous substances. At least these 21<br />

substances should be identified as priority hazardous substances. The Parliament’s<br />

rapporteur has pointed out that a further 7 substances prioritised by OSPAR in 2000<br />

should be added to the WFD priority list, thus totalling 39 priority substances, 28 <strong>of</strong><br />

which are priority hazardous substances.<br />

Repeal <strong>of</strong> Existing Standards<br />

The Dangerous Substances Directive (76/464/EEC) will be repealed 13 years after the<br />

date <strong>of</strong> entry into force <strong>of</strong> the WFD. Article 22(6) states that the quality standards established<br />

under the Water Framework Directive shall be at least as stringent as those<br />

required for implementation <strong>of</strong> the Dangerous Substances Directive. It is unclear, however,<br />

whether this clause guarantees an identical level <strong>of</strong> water protection under the


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WFD once the Dangerous Substances Directive has been repealed. The five daughter<br />

directives to the Dangerous Substances Directive (listed in WFD Annex IX) will be reviewed.<br />

For those substances, which are found on the first WFD priority list, quality<br />

standards and emission limits will be updated. For those which are not on the first priority<br />

list, standards shall be reviewed with an option for entire repeal (Article 16(10)).<br />

Combined approach<br />

In general, under the Water Framework Directive, specific environmental quality standards<br />

(EQSs) for pollutants (i.e. concentrations <strong>of</strong> pollutants, not to be exceeded in the<br />

receiving waters) and more general ecological-status objectives must be met by applying<br />

controls on pollutant discharges. For certain activities and certain pollutants, a different<br />

form <strong>of</strong> combined approach applies whereby emission controls based on BAT,<br />

relevant emission limit values or, in the case <strong>of</strong> diffuse impacts, Best Environmental<br />

Practices must be applied first. If these are inadequate for meeting an environmental<br />

quality standard or objective, more stringent emission controls must be set accordingly.<br />

This true form <strong>of</strong> combined approach not only achieves the required environmental<br />

standards and objectives, but may even reduce inputs below these targets. The BAT<br />

and Best Environmental Practice requirements drive polluters to audit and improve their<br />

overall environmental efficiency. Such a combined approach applies to substances and<br />

processes controlled by the Nitrates Directive, the IPPC Directive, the Urban Waste<br />

Water Directive, directives adopted for priority substances and also the existing<br />

daughter directives to the Dangerous Substances Directive (Article 10). For priority substances<br />

(regulation at EU level), both environmental quality standards and uniform<br />

emission limit values should be set. However, Article 16(6) merely states that the<br />

Commission should "take account <strong>of</strong> Community-wide uniform emission limit values". It<br />

remains to be seen whether this is a binding requirement. In the absence <strong>of</strong> Community-wide<br />

measures on priority substances (i.e. if the Council and Parliament are unable<br />

to agree on measures), Member States have to act on these substances anyway. Article<br />

16(8) states that Member States have to establish environmental quality standards<br />

(EQS) and "controls on the principal sources <strong>of</strong> such discharges, based inter alia on<br />

consideration <strong>of</strong> all technical reduction options". This statement implies that Member<br />

States must apply the strong form <strong>of</strong> the combined approach, with application <strong>of</strong> Best<br />

Available Technologies first, and stronger controls if necessary. After all, this is the regime<br />

that applies in the event <strong>of</strong> Community-wide measures being agreed.<br />

Derogation and Extensions <strong>of</strong> Deadlines Regarding Chemicals<br />

Article 4(4) allows Member States to extend the deadline for achieving good status by<br />

up to twelve years beyond 2015. Such a rule is justified by the need to take account <strong>of</strong><br />

adverse natural conditions or insurmountable technical difficulties. However, there is<br />

also a more problematical clause allowing extensions on the grounds <strong>of</strong> disproportionate<br />

expense. Fortunately, the reasons and justification for making use <strong>of</strong> an extension<br />

<strong>of</strong> the deadline must be included in the River Basin Management Plan, for which public<br />

consultation is required at all stages. It should therefore be possible to ensure that extensions<br />

are only used when it can be shown that achievement <strong>of</strong> the objectives is impossible<br />

within the agreed timetable.


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Less Stringent Objectives<br />

Article 4(5) may cause even more problems. Member States are allowed to exclude<br />

specific bodies <strong>of</strong> water from achieving the objectives because they are "so affected by<br />

human activity … that the achievement <strong>of</strong> the objectives would be unfeasible or disproportionately<br />

expensive’. The weakness is that this paragraph not only applies to past<br />

human activities, but possibly also to ongoing ones. Potentially, this clause might be<br />

used to permanently exclude very polluted sites from the scope <strong>of</strong> the Directive’s good<br />

status objectives (though not from the objective <strong>of</strong> progressively reducing pollution by<br />

priority substances/priority hazardous substances). The formulation <strong>of</strong> Article 4(8) requiring<br />

effects on other bodies <strong>of</strong> water to be taken into account should also be noted.<br />

However, there are many steps requiring public consultation in the process <strong>of</strong> applying<br />

such a derogation. Furthermore, a lot <strong>of</strong> conditions have to be met. Given sufficient<br />

public scrutiny, it should be rather difficult for a Member State to abuse this clause.<br />

Summarised Comments on WFD with Respect to Chemicals<br />

1. Quick adoption <strong>of</strong> the list is necessary, but list is not complete<br />

All the 32 substances proposed by the Commission on the list <strong>of</strong> priority substances are<br />

well known. They pose a major threat to the environment and public health and should<br />

be dealt with as soon as possible. We welcome the Commission’s quick prioritisation<br />

process for substances under the WFD. However, to ensure consistency with the Union’s<br />

OSPAR commitments, the Commission should have included more substances in<br />

the list. Particularly, the substances identified as hazardous by the OSPAR Strategy<br />

and which are also on the “List <strong>of</strong> Chemicals for Priority Action” under the OSPAR Convention,<br />

should be added to the list <strong>of</strong> priority substances.<br />

2. Identification <strong>of</strong> priority hazardous substances must not be compromised by<br />

socio-economic considerations<br />

The identification <strong>of</strong> priority hazardous substances should be based:<br />

- on the selection <strong>of</strong> priority substances by the COMMPS procedure, which is taking<br />

account <strong>of</strong> substance properties, uses, market volumes and environmental<br />

occurrence and leads to the list <strong>of</strong> priority substances; and<br />

- on available “hazard assessments” and “best available knowledge”.<br />

This widely accepted procedure in the EU and OSPAR does by definition NOT take socio-economic<br />

considerations into account.<br />

3. Identification <strong>of</strong> priority hazardous substances for the precautionary protection<br />

<strong>of</strong> EU waters<br />

The WFD’s overall environmental objective for the measures against pollution by priority<br />

hazardous substances is “the aim <strong>of</strong> ceasing or phasing-out <strong>of</strong> discharges, emissions<br />

and losses <strong>of</strong> these substances” targeted at the precautionary protection <strong>of</strong><br />

freshwaters and the oceans.<br />

Discharges, emissions and losses <strong>of</strong> priority hazardous substances can occur through<br />

many pathways: Direct use in the environment (e.g. pesticides); direct use <strong>of</strong> the sub-


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stance in certain products (e.g. flame retardants or mercury) from which after or during<br />

use emissions <strong>of</strong> the substance into the environment occur; priority hazardous substances<br />

can also occur as by-products <strong>of</strong> certain processes (e.g. PAHs from combustion<br />

processes) and as metabolites in the breakdown <strong>of</strong> other substances. It is clear<br />

that this multitude <strong>of</strong> pathways calls for a whole package <strong>of</strong> different measures to<br />

achieve the objective <strong>of</strong> the Water Framework Directive. While a substance ban is the<br />

appropriate measure to achieve the required protection against priority hazardous substances,<br />

which are directly used in the environment or in products, this might not necessarily<br />

be the case for by-products <strong>of</strong> manufacturing processes, which are isolated<br />

from the environment.<br />

The assumption put forward by some industry associations that there is only one<br />

measure – namely a substance ban – is simplistic and does not reflect the flexibility <strong>of</strong><br />

the WFD. The overriding objective <strong>of</strong> the Water Framework Directive is the precautionary<br />

protection <strong>of</strong> European waters, an objective that does not ask the impossible <strong>of</strong> either<br />

the European Union or its Member States. Unintentional releases, for instance due<br />

to accidents and undetected leaks etc., can never be ruled out entirely, and are accounted<br />

for by the WFD. However, where priority hazardous substances consistently<br />

occur as by-products <strong>of</strong> industrial production, or are identified as breakdown products<br />

(metabolites) <strong>of</strong> other substances, or evaporate and leach from consumer products,<br />

measures have to be taken with the aim to end their releases into the environment. It<br />

should be kept in mind that the Water Framework Directive provides for up to 20 years<br />

to achieve the environmental objective <strong>of</strong> cessation <strong>of</strong> releases, which allows ample<br />

time for the development <strong>of</strong> new technologies and substitute substances.<br />

List <strong>of</strong> Priority Substances<br />

The European Union pay attention to the subject “endocrine disrupter” already discussed<br />

in 2.1. Now it is described how the selection and classification <strong>of</strong> contaminants<br />

are effected at the moment and in the near future.<br />

The definition <strong>of</strong>t “hazardous substances” have been contentious for a long time. According<br />

to the OSPAR agreement, hazardous substances are toxical, persistent, and<br />

bioaccumulative (bioakkumulierbar). That means, according to their intrinsic properties<br />

measurable in laboratory tests they are classified to be toxic, persistent and bioaccumulative<br />

(bioakkumulierbar) [FRAUNHOFER INSTITUTE (98/788/3040/DEB/E1) 1999].<br />

At the moment the Council Directive 76/464/EEC on pollution caused by certain<br />

dangerous substances discharged into the aquatic environment <strong>of</strong> the Community<br />

and the included individual directives is the most important instrument to control the<br />

emissions <strong>of</strong> hazardous substances from diffuse and selective sources into the surface<br />

waters. In 1982 the Commission submitted a communication to the council about hazardous<br />

substances according to list I <strong>of</strong> council directive 76/464/EEC. Here 130 substances<br />

are listed to be regular by the community. The selection <strong>of</strong> these substances<br />

took place according to a high production capacity and the toxicity, persistence and<br />

bioaccumulation. After the publication <strong>of</strong> this list 17 substances were regulated in individual<br />

directives [FRAUNHOFER INSTITUTE (98/788/3040/DEB/E1) 1999].


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The water framework directive (2000/60/EC) is the directive <strong>of</strong> the European Parliament<br />

and the Council establishing a framework for community action in the field<br />

<strong>of</strong> water policy. In Article 10 and 16 a community strategy with regard to the establishing<br />

<strong>of</strong> harmonised quality objectives and control <strong>of</strong> emissions <strong>of</strong> hazardous substances<br />

is described. After a transitional period this strategy will be replace the directive<br />

76/646/EEC and the directives passed in this framework [COM (2000) 47 final].<br />

The water framework directive demand the control <strong>of</strong> emissions at their sources and the<br />

fixing <strong>of</strong> quality standards to gauge the success <strong>of</strong> the taken measures. Article 16 describes<br />

for the first time a legal framework and a unambiguous methodical basis for the<br />

allocation <strong>of</strong> priorities to substances for which quality objectives and emission controls<br />

are going to lay down on community level. In article 16 section 2 <strong>of</strong> the water framework<br />

directive a scientific method to identify priority substances is established. The basis for<br />

that are the risks for the aquatic ecosystem and the risks for humans originate via the<br />

aquatic environment. In accordance with article 16 the Commission proposed a first list<br />

with priority substances. This list is the most important fundament for the identification<br />

<strong>of</strong> emission controls and harmonised quality objectives to protect the aquatic environment<br />

in the European Union [2000/60/EC (23. October 2000), FRAUNHOFER<br />

INSTITUTE (98/788/3040/DEB/E1) (1999)].<br />

The Fraunh<strong>of</strong>er institute environmental chemistry and ecotoxicology from Germany developed<br />

a procedure called COMMPS-procedure (combined monitoring-based and<br />

modelling-based priority setting). The COMMPS-procedure (98/788/3040/DEB/E1) is a<br />

dynamic instrument which can be changed and improved constantly. The selection criterion<br />

at the COMMPS-procedure was the disposal <strong>of</strong> data, the classification according<br />

to the relative risk to the aquatic environment and the opinion <strong>of</strong> experts<br />

[FRAUNHOFER INSTITUTE (98/788/3040/DEB/E1) (1999)].<br />

The COMMPS-report is a recommendation for a selection <strong>of</strong> priority substances from<br />

the list <strong>of</strong> candidates. For every substance standing on this list, the Commission had to<br />

state quality objectives and emission controls and the member states had to create<br />

monitoring programs. Afterwards effective programs are compiled and realised to improve<br />

the water quality with regard to the selected priority substances. The revision<br />

should take place at least every six years and on demand more <strong>of</strong>ten [FRAUNHOFER<br />

INSTITUTE (98/788/3040/DEB/E1) (1999), COM (2000) 47 final].<br />

In the COMMPS procedure substances were taken from the following lists:<br />

— List I and II <strong>of</strong> Council Directive 76/646/EEC,<br />

— Annex 1A and 1D <strong>of</strong> the third North Sea Conference (3. NSC),<br />

— Priority lists 1-3 identified under Council Regulation No 7693/93,<br />

— OSPAR list <strong>of</strong> individual candidate substances,<br />

— HELCOM list <strong>of</strong> priority substances,


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— Pesticides prioritised under Council Directive 91/414/EEC (and specified under Council Regulation<br />

3600/92),<br />

— Monitored substances not mentioned on any <strong>of</strong> the lists above (based on the monitoring data obtained<br />

from Member States.<br />

For the second run <strong>of</strong> COMMPS substances which are suspected to restrictions or not<br />

used in the member states so-called "historic pollutants" were deleted from the list.<br />

The following selection procedure obtained:<br />

— Risk assessment for existing chemical substances according to Council Regulation (EEC) No. 793/93<br />

(recent [draft] reports), the Council Directive 91/414/EEC about plant protective agents and the Council<br />

Directive 98/8/EU about biocides,<br />

— Targeted risk-based assessment in accordance with Council Directive No. 793/93/EEC with solely<br />

survey on aquatic ecotoxicity and human toxicity via the aquatic environment,<br />

— Or, where this proves impracticable within the time scale to simplify a risk-based assessment procedure<br />

based on scientific principles taking particular account <strong>of</strong>:<br />

— Evidence regarding the intrinsic hazard <strong>of</strong> the substances concerned, in particular its aquatic ecotoxicity<br />

and human toxicity via aquatic exposure routes,<br />

— Evidence from monitoring <strong>of</strong> widespread environmental contamination, and<br />

— Other proven factors indicating the possibility <strong>of</strong> widespread environmental contamination, such as<br />

production or use volume <strong>of</strong> the substance concerned as well as use pattern.<br />

Because <strong>of</strong> basic differences between metals and organic compounds the position table<br />

for metals are compiled independent from the lists for organic compounds.<br />

The final result for the COMMPS value <strong>of</strong> the impacts to the aquatic environment describes<br />

the relative risk for the aquatic area. At the COMMPS procedure the value is<br />

calculated as the product <strong>of</strong> the exposure <strong>of</strong> the aquatic environment and <strong>of</strong> the impacts<br />

to the aquatic environment. Because a substance with a high tendency to accumulate<br />

in the sediment occurs in the water only in smidgens a separate list had to be<br />

compiled.<br />

At the compilation and revision <strong>of</strong> the list <strong>of</strong> priority substances the Commission will be<br />

take into account any available information. That particularly apply for recommendations<br />

from the Scientific Committee on Toxicity, Ecotoxicity and the Environment<br />

(CSTEE), the Member States, the European Chemicals Bureau (ECB) and the industry<br />

and other stakeholders. As mentioned before the COMMPS list will replace the list I <strong>of</strong><br />

the Council Directive 76/646/EEC and after its publication it will became to the Annex X<br />

<strong>of</strong> the Water Framework Directive [2000/60/EC (23. October 2000), FRAUNHOFER<br />

INSTITUTE (98/788/3040/DEB/E1) (1999), COM (2000) 47 final].<br />

In the Annex <strong>of</strong> the Proposal for a European Parliament and Council decision establishing<br />

the list <strong>of</strong> priority substances in the field <strong>of</strong> water policy (COM (2000) 47 final) is<br />

a list with 32 substances especially groups <strong>of</strong> substances. This list is compiled on the<br />

basis <strong>of</strong> the COMMPS procedure after a publicly and transparent discussion with the<br />

interested parties.<br />

CAS<br />

EU<br />

Name<br />

number<br />

number<br />

1 15972-60-8 240-110-8 Alachlor<br />

2 120-12-7 204-371-1 Antracene


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3 1912-24-9 217-617-8 Atrazine<br />

4 71-43-2 200-753-7 Benzene<br />

5 n.a n.a. Brominated diphenylether<br />

6 7440-43-9 231-152-8 Cadmium and its compounds<br />

7 85535-84-8 287-476-5 C10-13-chloralkanes<br />

8 470-90-6 207-432-0 Chlorfenvinphos<br />

9 2921-88-2 220-864-4 Chlorpyrifos<br />

10 75-09-2 200-838-9 Dichlormethane<br />

11 107-06-2 203-458-1 1,2-Dichloroethane<br />

12 117-81-7 204-211-0 Di(2-ethylhexyl)phthalate (DEHP)<br />

13 330-54-1 206-354-4 Diuron<br />

14 115-29-7 204-079-4 Endosulfan<br />

959-98-8 n.a. alpha-endosulphan<br />

15 118-74-1 204-273-9 Hexachlorbenzene<br />

16 87-68-3 201-765-5 Hexachlorobutadiene<br />

17 608-73-1 210-158-9 Hexachlorocyclohexane<br />

58-89-9 200-401-2 gammer-isomer, Lindane<br />

18 34123-59-6 251-835-4 Isoproturon<br />

19 7439-92-1 231-100-4 Lead and its compounds<br />

20 7439-97-6 231-106-7 Mercury and its compounds<br />

21 91-20-3 202-049-5 Naphthalene<br />

22 7440-02-0 231-111-4 Nickel and its compounds<br />

23 25154-52-3 246-672-0 Nonylphenols<br />

104-40-5 203-199-4 4-(para-)-nonylphenol<br />

24 1806-26-4 217-302-5 Octylphenols<br />

140-66-9 n.a. para-tert-octylphenol<br />

25 n.a.<br />

n.a. Polyaromatic hydrocarbons<br />

50-32-8 200-028-5 Benzo(a)pyrene<br />

205-99-2 205-911-9 Benzo(b)flouroanthene<br />

191-24-2 205-883-8 Benzo(g,h,i)pyrene<br />

207-08-9 205-916-6 Benzo(k)flouroanthene<br />

206-44-0 205-912-4 Flouroanthene<br />

193-39-5 205-893-2 Indeno(1,2,3-cd)pyrene<br />

26 608-93-5 210-172-5 Pentachlorobenzene<br />

27 122-34-9 204-535-2 Simazine<br />

28 87-86-5 201-778-6 Pentachlorophenol<br />

29 688-73-3 211-704-4 Tributyltin compounds<br />

36643-28-4 n.a. Tributyltin-cation<br />

30 12002-48-1 234-413-4 Trichlorobenzenes<br />

120-82-1 204-428-0 1,2,4-Trichlorobenzene<br />

31 67-66-3 200-663-8 Trichloromethane (Chlor<strong>of</strong>orm)<br />

32 1582-09-8 216-428-8 Trifluralin<br />

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4 THE ENDOCRINE SYSTEM<br />

All vertebrates have an endocrine system. The endocrine system is a complex network<br />

<strong>of</strong> glands and hormones that regulate and control many long and short term bodily<br />

functions [WWF CANADA 1999]. The physiological mechanisms are distinctive along<br />

with the nervous and immune system in the endocrine system and allow the communication<br />

between cells and organs. The function <strong>of</strong> the endocrine system is multifaceted<br />

and comprises the regulation <strong>of</strong> long-term processes like reproduction, growth as well<br />

as the homeostasis <strong>of</strong> essential systems such as the water and electrolyte supply and<br />

the energy metabolism [KLINKE and SILBERNAGEL 1994]. Serious diseases could be<br />

the consequence <strong>of</strong> interference <strong>of</strong> the hormone system, for example by the failure or<br />

overproduction <strong>of</strong> hormones [KLINKE and SILBERNAGEL 1994].<br />

In many instances specific hormones and the biological process they control are<br />

chemically identical in animals and humans. This is an amazing fact considering the<br />

years <strong>of</strong> evolution and differences in physical structure between animal species. Estradiol<br />

for instance, a hormone critical to sexual development and behaviour, is chemically<br />

identical in turtles and humans. Even compared with insects there exist identical features.<br />

This means that a chemical which affects some components <strong>of</strong> the endocrine<br />

system <strong>of</strong> an insect can be expected to have similarly effects in mammals [WWF<br />

CANADA 1999].<br />

4.1 THE FUNCTION OF HORMONES<br />

For the co-ordination <strong>of</strong> the function <strong>of</strong> organs and organism the cells <strong>of</strong> a collective<br />

have to communicate with each other. One way to communicate is the communication<br />

with messengers so-called hormones, which are part <strong>of</strong> the endocrine system. Hormones<br />

- produced and released into the bloodstream by endocrine glands - are essential<br />

for the regulation <strong>of</strong> numerous biological processes in the body. Some <strong>of</strong> the endocrine<br />

glands are the testes, the ovaries, the pancreas, the adrenal glands, the thyroid,<br />

the pituitary gland, the hypothalamus and the pineal gland [WWF CANADA, KLINKE<br />

and SILBERNAGEL 1994].<br />

Hormones also play an important part in the development <strong>of</strong> a growing foetus. In the<br />

womb or the egg, hormones guide the development <strong>of</strong> sexual characteristics, the immune<br />

and the nervous system, the brain, behavioural characteristics and the growth<br />

[WWF CANADA 1999]. Thyroid hormones, for example, are essential for the brain development<br />

and testosterone, progesterone and estrogen are essential for reproductive<br />

organ development and functioning [WWF CANADA 1999].<br />

To transmit the hormone effect the signal substances have to reach the target cell over<br />

the transport in the blood or paracrine diffusion where they are "identified". This identification<br />

<strong>of</strong> all hormones is the result from receptors. The hormone and its receptor have<br />

an intricate and precise fit. The hormone-receptor complex then binds to specific regions<br />

<strong>of</strong> DNA in the cell to activate specific genes. Hormones do not alter or damage<br />

genes. The cell-activation take place by sending a signal inside the cell. If the binding is<br />

disrupted at certain stages, normal hormonal signals are derailed [WWF CANADA<br />

1999, KLINKE and SILBERNAGEL 1994, DEVITT 1997].


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4.2 THE FUNCTIONING OF ENDOCRINE DISRUPTERS<br />

If the hormone system works properly, the right message is sent and is received by<br />

genes <strong>of</strong> several cells. If something damages the hormone system, the wrong message<br />

or no message is sent to the cell [WWF CANADA 1999]. Such a disruption can be<br />

caused by xenobiotics with an endocrine effect like e.g. several environmental chemicals.<br />

Points <strong>of</strong> attack for such endocrine active substances are <strong>of</strong>fered on a physiological (=<br />

hormonal) and biochemical (= metabolical) level [STEINBERG et al. 1995].<br />

[LEISEWITZ 1996, WWF CANADA 1999] stress that due to their endocrine activity environmental<br />

chemicals are named endocrine or hormone disrupters respectively EDCs<br />

(endocrine disrupter chemicals). EDCs are synthetical chemicals with the potential to<br />

disrupt the balance <strong>of</strong> the endocrine system. Hormones are involved in just about every<br />

biological process: immune function, reproduction, growth, even controlling other hormones.<br />

They are already effective in very low concentrations (ppm or ppb) which is the<br />

reason for the hazardousness <strong>of</strong> very low dosages <strong>of</strong> endocrine disrupters [DEVITT<br />

1997].<br />

EDCs may mimic, block or interfere the synthesis, release, transport, elimination and<br />

binding <strong>of</strong> natural hormones. They may also temporarily or permanently alter the feedback<br />

function <strong>of</strong> the brain, pituitary, gonads, thyroid gland and other organs [WWF<br />

CANADA 1999]. Unlike easily detected effects <strong>of</strong> toxic chemicals such as death, birth<br />

defects, cancer and genetic damage, the results <strong>of</strong> endocrine disruption are subtle.<br />

They are not necessarily verifiable on the exposed individuals but rather on their <strong>of</strong>fspring<br />

[WWF CANADA 1999].


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5 BACKGROUND INFORMATION TO MATERIALS WITH A PUTATIVE<br />

ENDOCRINE IMPACT<br />

Persistent Organic Pollutants — POPs<br />

In the technical terminology the name "Persistent Organic Pollutants" (POPs) is used.<br />

POPs are synthetical chemicals composed <strong>of</strong> organic chemical compounds and mixtures.<br />

Industrial chemicals like PCBs and pesticides like DDT belong to the POPs.<br />

POPs are primary products or also involuntarily by-products <strong>of</strong> the industry and combustion<br />

processes. All POPs are effective in very low concentrations, are extremely<br />

persistent and hydrophobic. Due to their affinity for body fat they accumulate themselves<br />

in the environment and the food chain up to a very high level with a dramatic<br />

concentration increase in the respective organisms to the final consumer<br />

[GREENPEACE AUSTRIA, WWF CANADA, WWF US].<br />

The existence <strong>of</strong> POPs is relatively recent, since the industrial production started after<br />

World War II. Today POPs are found almost everywhere - in our food, soil, air and<br />

water. Some POPs exceptionally accumulate themselves. The content <strong>of</strong> POPs in the<br />

water <strong>of</strong> the North Sea growths up to the content in the zooplankton about a 5 million<br />

times and up to the fishes and birds body fat a 100 million times enrichment is<br />

found [Greenpeace Austria, WWF US]. Both organisations refer that impairments <strong>of</strong> the<br />

development and the physical health <strong>of</strong> humans, mammals, fishes, birds etc., indicated<br />

by POPs, are numerously documented. Particularly in the case <strong>of</strong> humans an accurate<br />

allocation to one cause is not usually possible. Due to the mixture <strong>of</strong> POPs and the humans<br />

individual way <strong>of</strong> life with other factors <strong>of</strong> risk are the cause for this situation.<br />

Apart from the ingestion, workers and residents <strong>of</strong> townships near POP-emission<br />

sources for example can be exposed by inhalation and skin contact.<br />

The persistent pollutants have the ability - when released into the environment - to be<br />

transported on air currents or the water to places far away from their point <strong>of</strong> origin. In a<br />

cold climate and at low solar radiation POPs are break down slowly and they scarcely<br />

evaporate at very low temperatures. In consequence <strong>of</strong> that, a particularly strong accumulation<br />

in the coldest regions <strong>of</strong> the earth, e. g. Greenland, Arctic and Antarctica takes<br />

place [GREENPEACE AUSTRIA, WWF US]. In Austria, dioxins especially accumulate<br />

in barrier effects in the mountains. An increase <strong>of</strong> the dioxin concentration in soil with<br />

increase <strong>of</strong> the Sea level was ascertained [GREENPEACE AUSTRIA].<br />

Global Spread<br />

[LEISEWITZ 1996, WWF CANADA] refer to the ban <strong>of</strong> some substances (e. g.<br />

DDT),which led to a decrease <strong>of</strong> the concentration in the water and also in organisms.<br />

The high remaining base concentration at organochlorine compounds however is based<br />

on the further input <strong>of</strong> substances from residual waste in the respective regions, the<br />

remobilization <strong>of</strong> persistent materials from depots e. g. sediment, its accumulation in<br />

organisms themselves and from the long-distance haulage from regions where they are<br />

still used. Streams <strong>of</strong> the oceans, air currents and rivers, which pass the agriculture<br />

run<strong>of</strong>f and industrial discharges into the oceans are important POP transport pathways.


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Therefore particularly the aquatic systems <strong>of</strong> the estuaries, the coastal area and the<br />

marginal seas are concerned beside the inland waters.<br />

Figure 5-1: Grasshopper effect with consequences to Canada [WWF Canada]<br />

Because organochlorine compounds are volatile, they are able to be prevalent by air<br />

currents over both hemispheres to places far away from their point <strong>of</strong> origin. With diminishing<br />

temperature they condense at different latitudes and are precipitated. Such a<br />

transport can consist <strong>of</strong> a number <strong>of</strong> "hops" from one place to another. Each hop consists<br />

<strong>of</strong> three stages: evaporation, transport in the atmosphere and condensation at<br />

lower temperatures. Scientists have called this phenomenon the "grasshopper effect".<br />

Because evaporation is minimal in colder regions, POPs tend to build up in arctic and<br />

mountain ecosystems (cf. 0).<br />

Figure 5-1 shows the grasshopper effect at the example <strong>of</strong> Canada which is impaired<br />

by POP-sources resided beyond the state boundary [LEISEWITZ 1996, WWF<br />

CANADA].<br />

Detection Problems<br />

Environmental chemicals are trace elements which occur only in very low concentrations<br />

in the water or in organic material. Their detection is costly. The weak activity <strong>of</strong><br />

these substances is well balanced by the persistence and accumulation capacity. The<br />

detection <strong>of</strong> material is not the detection <strong>of</strong> their impact. From the observation <strong>of</strong> harmful<br />

patterns and the simultaneously existence <strong>of</strong> suspicious substances there does not<br />

exist a unequivocal causal connection. For the detection <strong>of</strong> the impact experiments are<br />

necessary. Moreover, today it is not possible to derive or predict the hormonal impact <strong>of</strong><br />

contaminants from their structure [LEISEWITZ 1996]. He continues that tests <strong>of</strong> materials<br />

are necessary but they give only limited information. The reason therefore is, that<br />

the test results normally contain no information about the impacts <strong>of</strong> the material on


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the organisms or not at all <strong>of</strong> a population's vitality. The same test results had been<br />

obtained for tests which check the receptor binding <strong>of</strong> environmental chemicals and<br />

those which should determine the estrogene potential. New test methods has been developed<br />

in the recent years which are based on the sensitivity <strong>of</strong> human tumour cells for<br />

estrogens.


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6 METHODS OF DETERMINING THE ENDOCRINE EFFECT OF SUBSTANCES<br />

6.1 BACKGROUND<br />

For regulatory purposes toxicological tests have to be carried out according to internationally<br />

accepted test guidelines. However, in several recent workshops and publications<br />

it has been discussed whether the current test guidelines are suitable for identifying<br />

endocrine disrupters:<br />

• SETAC-Europe/OECD/EC Expert Workshop on Endocrine Modulators and Wildlife:<br />

Assessment and Testing (EMWAT), Veldhoven, Netherlands, 10-13 April<br />

1997;<br />

• the OECD is at the moment finalising the Detailed Review Paper (DRP): “Appraisal<br />

<strong>of</strong> Test Methods for Sex-Hormone Disrupting Chemicals”. The document<br />

has been prepared by the United Kingdom as a proposed basis on which to assess<br />

the suitability and availability <strong>of</strong> existing test methods used both by OECD<br />

member states and the research community. This document was circulated to<br />

the OECD National Test Guidelines Co-ordinators in April 1997 and has been<br />

recently revised to take account <strong>of</strong> comments received. A final document has yet<br />

to be published;<br />

• a draft report from February 1998 <strong>of</strong> the activities <strong>of</strong> the Endocrine Disrupter<br />

Screening Testing and Advisory Committee (EDSTAC) <strong>of</strong> the US-EPA;<br />

• a publication in Environmental Toxicology and Chemistry by [ANKLEY et al.<br />

1998] entitled “Overview <strong>of</strong> a workshop on screening methods for detecting potential<br />

(anti-) oestrogenic/androgenic chemicals in wildlife”.<br />

A summary <strong>of</strong> all tests available at the moment - including the recommendations for<br />

their enhancement with respect to endocrine disrupters - discussed in EMWAT, DRP<br />

and EDSTAC was presented by the OECD in a background paper <strong>of</strong> the first meeting <strong>of</strong><br />

the OECD Endocrine Disrupter Testing and Assessment Working Group (EDTA),<br />

March 10-11, 1998. Test guidelines for invertebrates (OECD 202), fish (OECD 203,<br />

204, 210 and 212 and the draft 28-days juvenile growth) and birds (OECD 205 and<br />

206) and several tests with mammals like the OECD 407 and 416 are discussed<br />

therein. It is stated that none <strong>of</strong> the current OECD ecotoxicology test guidelines are<br />

specifically designed to detect endocrine disrupters. The same can be argued for the<br />

EU test guidelines as only regulatory test guidelines are available for acute tests with<br />

fish and daphnia’s, with non-specific endpoints, including growth and mortality.<br />

The need for revision <strong>of</strong> existing OECD test guidelines and the development <strong>of</strong> new test<br />

guidelines specifically to address the potential adverse effects arising as a result <strong>of</strong> endocrine<br />

disruption, has been proposed by several organisations, such as EDSTAC, and<br />

in workshops on endocrine disrupters, such as EMWAT. Rather than discussing all ex-


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isting test guidelines in the present document, it is decided to refer to the documents<br />

above.<br />

For the environment, both, the hazard identification and the effect evaluation part <strong>of</strong> risk<br />

assessment is constructed as a combination <strong>of</strong> the results <strong>of</strong> ecotoxicity tests and several<br />

fate-related physical-chemical and biological properties. This methodology is scientifically<br />

sound and in agreement with the present state <strong>of</strong> the art <strong>of</strong> ecological risk assessment<br />

procedures. Nevertheless, before going in a detailed evaluation <strong>of</strong> the capacity<br />

<strong>of</strong> this strategy to detect hazards related to endocrine disruption it is necessary to<br />

clearly identify its aims and the concerns considered under this system.<br />

Ecotoxicological evaluations try to assess the effects <strong>of</strong> chemical substances at the<br />

ecological level. In scientific literature [e.g., BRO-RASMUSSEN et al., 1994], this level<br />

is commonly defined as “effects on the structure and function <strong>of</strong> the ecosystems” while<br />

due to the difficulties arising from the definition <strong>of</strong> the term ecosystem at the regulatory<br />

level [e.g., GONZALEZ, 1996] the normative goal for ecological/environmental protection<br />

is frequently modified and other terms, such as “the protection <strong>of</strong> living organisms,<br />

environmental elements and their interactions” are used. In any case from a scientific<br />

point <strong>of</strong> view both definitions clearly represent the aim to protect higher ecological levels<br />

<strong>of</strong> organisation than individuals-populations, such as communities and their interactions<br />

with the abiotic components <strong>of</strong> each environmental compartment.<br />

However, it is not always easy to combine this theoretical “aspiration” with the “real”<br />

data source usually employed in ecotoxicological assessments, which in most cases is<br />

reduced to a limited number <strong>of</strong> laboratory single-species tests. This limitation is based<br />

on both technical and economic arguments. The technical arguments mostly focus on<br />

the difficulties for the interpretations <strong>of</strong> higher tier tests, e.g. aquatic mesocosms or terrestrial<br />

model ecosystems while the economic arguments do not require further explanation.<br />

The relevance <strong>of</strong> laboratory single-species (eco-)toxicity tests has been discussed<br />

elsewhere (e.g., CROSSLAND, 1992). It can be considered as a pragmatic approach<br />

which is, nevertheless, widely employed as a cost/effective alternative (i.e., SETAC,<br />

1994). From a methodological point <strong>of</strong> view is quite clear that these “ecotoxicity” tests<br />

are not “ecological” at all. In principle, we can assume that the test conditions <strong>of</strong> singlespecies<br />

(eco-)toxicity tests do not provide more “ecological information” than any (noneco-)toxicity<br />

test on rats, mice, dogs, etc., which use a non-parenteral (i.e., oral or inhalation)<br />

route. A fish in a glass aquarium or an algae in an artificial reconstituted medium<br />

are not more, not less, ecologically relevant than a mouse in a box eating contaminated<br />

food.<br />

In spite <strong>of</strong> these drawbacks, appropriate interpretation <strong>of</strong> these ecotoxicity tests results<br />

can lead to conclusions that are ecologically relevant. There are a number <strong>of</strong> factors<br />

that make this possible:<br />

• the organisms used have been selected trying to represent key taxonomic<br />

groups <strong>of</strong> relevant environmental compartments for example:<br />

- fish, invertebrates and algae for the aquatic environment,


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- plants, soil invertebrates and soil micro-organisms for the soil compartment <strong>of</strong><br />

the terrestrial environment.<br />

- vertebrates, pollinators and foliar dwelling invertebrates for the above soil<br />

compartment <strong>of</strong> the terrestrial environment.<br />

- top predators for biomagnification assessments.<br />

• the toxicity endpoints are specifically selected to be considered as “ecologically<br />

relevant”, i.e., reproduction, growth rate inhibition, etc. depending on the organisms<br />

and their ecological role.<br />

• the interpretation <strong>of</strong> the laboratory information considers the “ecological goal”<br />

using either deterministic or probabilistic approaches to extrapolate the laboratory<br />

data to ecosystem effects. These interpretations require a specific discussion.<br />

At the present state <strong>of</strong> the art <strong>of</strong> ecological risk assessment, deterministic or probabilistic<br />

approaches (based on laboratory single-species tests) can be justified not only as an<br />

economically feasible alternative, but can also be justified from a scientific point <strong>of</strong> view<br />

when a set <strong>of</strong> basic conditions, such as those included below, are fulfilled:<br />

• these methods are part <strong>of</strong> a tiered approach, and constitute the first step <strong>of</strong> the<br />

process (lower tier), to determine if higher tier assessment are required. Their<br />

results are over-ruled when information at a higher tier level becomes available.<br />

• the uncertainty <strong>of</strong> these assessments is quite high, and therefore requires the<br />

application <strong>of</strong> an appropriate level <strong>of</strong> precaution.<br />

• the transparency <strong>of</strong> the process must be guaranteed.<br />

• the decision schemes must be oriented to the reduction <strong>of</strong> type I-errors (minimising<br />

the risk for false negatives even by assuming a higher risk for false positives).<br />

A validation criteria for this condition is that higher tier values must show a<br />

clear tendency to reduce or at least to maintain the ecotoxicological thresholds<br />

estimated from the single-species toxicity data. The agreement between the recommended<br />

protocol and this validation criteria has been observed for several<br />

substances in the EU industrial and pesticide programmes.<br />

Taken these and other considerations into account the use <strong>of</strong> this approach is widely<br />

extended at the international level [i.e, OECD, 1989]. The deterministic approach is<br />

nowadays the most commonly used alternative in Europe. The ECETOC revision<br />

[ECETOC, 1993] compared methods developed in Switzerland, Germany, The Netherlands,<br />

the EC-JRC, UK, AIS and the OECD which were the basis for the development<br />

<strong>of</strong> the EC Technical Guidance Document (TGD). The ecotoxicological threshold is obtained<br />

by applying a factor (usually named as safety factor, uncertainty factor or application<br />

factor) to the lowest “relevant” toxicity value. This application factor depends on<br />

the significance and uncertainty <strong>of</strong> the available information. It should cover the extrapolation:<br />

• from acute to chronic toxicity when acute toxicity data are considered,<br />

• from laboratory to field conditions (unless laboratory conditions should be specifically<br />

designed to maximise the bioavailability),<br />

• from the chronic effects observed for the most sensitive tested species to the<br />

long-term effects predicted for species-species interactions,


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• from multi-species effects to the protection <strong>of</strong> the structure and function <strong>of</strong> ecosystems.<br />

Typical examples <strong>of</strong> this approach are the derivation <strong>of</strong>:<br />

• the EU Water Quality Objectives [BRO-RASMUSSEN et al., 1994].<br />

• the Predicted No Effect Concentrations in the TGD for risk assessment <strong>of</strong> industrial<br />

chemicals [EC, 1996c].<br />

• the OSPAR Ecotoxicological Assessment Criteria [OSPAR, 1994]<br />

• the proposed Environmental Quality Standards in the Water Framework Directive<br />

(which follow the TGD estimation for PNECs)<br />

Summaries <strong>of</strong> the application factors employed by the different methods can be found<br />

in [ECETOC, 1993; OSPAR, 1994; TARAZONA, 1998]. The probabilistic approach use<br />

the available information to produce a probabilistic distribution for the species sensitivity<br />

for each chemical. Obviously, the uncertainty in the estimation will depend on the<br />

amount and quality <strong>of</strong> the information employed to create the distribution. The ecotoxicological<br />

threshold is then calculated as the concentration which is safe for a predetermined<br />

percentage (e.g., 95%) <strong>of</strong> the species (or other levels <strong>of</strong> taxonomic organisation).<br />

A classical example for this procedure is the Dutch Maximum Tolerable Concentration<br />

procedure [i.e, VAN STRAALEN AND DENNEMAN, 1989]. Combination <strong>of</strong> deterministic<br />

and probabilistic approaches are possible in different ways, i.e. by applying a safety<br />

factor to the concentration which protect a certain percentage <strong>of</strong> the species [i.e., for<br />

the USEPA Water Quality Criteria, USEPA, 1995].<br />

Nowadays, the tendency is to considered probabilistic approaches as a higher tier step<br />

in the tiered scheme. Several proposals for the incorporation <strong>of</strong> probabilistic methods in<br />

the EU Ecological Risk Assessment programmes for industrial chemicals and for pesticides<br />

have been presented.<br />

It must be pointed out that in any case this approach tries to protect individuals or even<br />

species. If there is a concern for the effects on single species or even for the protection<br />

<strong>of</strong> individuals within a species (e.g. relevant for certain endangered species) then, the<br />

ecotoxicological approach is not valid and environmental (e.g. wildlife) toxicological<br />

methods are required. The outcome <strong>of</strong> this approach can be either more or less severe<br />

than the ecotoxicological method (e.g. requiring either higher or lower threshold values<br />

to obtain acceptable margins <strong>of</strong> safety), but in any case it can be assumed that individuals<br />

are protected by ecotoxicological thresholds.<br />

The role <strong>of</strong> single-species ecotoxicity tests in the assessment <strong>of</strong> endocrine disrupters:<br />

In theory the basic concepts discussed above are general and not related to the mode<br />

<strong>of</strong> action <strong>of</strong> the chemical. Therefore any mechanism is expected to be covered in the<br />

extrapolation from laboratory data to the ecotoxicological threshold. This conceptual<br />

approach can be justified unless:<br />

• due to technical problems the toxicity test/endpoints can be regarded as unable<br />

to detect the effects related to this mechanisms


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• the uncertainty factors/probabilistic cut-<strong>of</strong>f do not minimise type I-errors in the<br />

extrapolation from single species data to ecotoxicological thresholds (i.e. at the<br />

acute/chronic or chronic/multi-species ratio).<br />

For some endocrine disruption mechanisms these “unless” clauses represent a potential<br />

problem which cannot at present be quantified due to the lack <strong>of</strong> available information<br />

not only regarding the 4 catchment areas but, rather in general. As an example <strong>of</strong><br />

technical problems, chronic studies on Daphnia’s (female populations with partenogenetic<br />

reproduction) and algae may not detect effects <strong>of</strong> oestrogenic pollutants, and the<br />

same can said for some (not all) chronic tests on fish such as the fish growth inhibition<br />

tests. However, the same chronic Daphnia test should be, in theory a perfect candidate<br />

for the detection <strong>of</strong> androgenic pollutants.<br />

Regarding the second clause, the most common extrapolation factor from acute to<br />

chronic effects (acute/chronic ratio) is 10, while not enough information is available to<br />

determine the ratio between mortality due to endocrine disruption and long-term ecologically<br />

significant effects due to endocrine disruption mechanisms.<br />

In conclusion, although the conceptual approach is appropriate, and laboratory single<br />

species toxicity tests can be considered as either screening, lower tier or cost/effective<br />

alternatives for the prediction <strong>of</strong> ecological effects and independent, not related, to the<br />

specific mechanisms <strong>of</strong> action, due to the particularities <strong>of</strong> the acute and chronic toxicity<br />

tests and endpoints currently selected, the hazard <strong>of</strong> some endocrine disrupters could<br />

not be identified by some widely used Ecotoxicity tests batteries.<br />

Obviously the problem only appears when endocrine disruption is the only or the most<br />

sensitive and ecologically relevant mechanisms <strong>of</strong> toxicity and the effects cannot be directly<br />

or indirectly detected by the selected test endpoints in the scheduled time. Further<br />

information is required to estimate the magnitude <strong>of</strong> this problem.<br />

The development <strong>of</strong> tests specifically designed to measure endocrine disruption is not<br />

suitable for ecological effects because: a) the consequences must be evaluated at the<br />

population level, and b) even the smaller taxonomic groups (mammals, reptiles, amphibians)<br />

have thousands <strong>of</strong> different species with physiological and ecological differences<br />

which highly affect both the sensitivity and the ecological relevance <strong>of</strong> the effects<br />

observed at the individual level.<br />

Particularly for endocrine disruption, our understanding on hormonal physiology is<br />

mostly limited to vertebrates, with some additional examples for some specific taxonomic<br />

groups. But even for vertebrates, it is difficult to predict the population consequences<br />

<strong>of</strong> individual endocrine alterations such us increases <strong>of</strong> vitellogenin levels or<br />

reductions in thyroid activities, until these alterations impair reproduction, growth or survival<br />

potentials. Therefore, the detection <strong>of</strong> these impairments must be the endpoints in<br />

ecotoxicity tests. Therefore, the ecotoxicological consequences <strong>of</strong> endocrine disrupters<br />

must be assessed by general, non specific endpoints but assuring that the employed<br />

tests and result interpretations fully cover the potential consequences <strong>of</strong> the hormonal<br />

alterations.


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A potential solution should be to incorporate a procedure to identify the relevance <strong>of</strong><br />

endocrine alterations. e.g. using the data produced on mammals. This hazard identification<br />

will be useful to select those tests which can produce the adequate response,<br />

e.g. to define which chronic toxicity tests on fish is required. This information should<br />

also be very useful for the assessment <strong>of</strong> secondary poisoning, this part is described as<br />

provisional in the current EU protocol for ecological risk assessment and although the<br />

potential for bioaccumulation is obviously included, additional efforts should be allocated<br />

for a better understanding <strong>of</strong> the risk related to the bioaccumulation potential <strong>of</strong><br />

persistent chemicals and particularly for an appropriate characterisation <strong>of</strong> the potential<br />

for biomagnification through the food chains. A combination <strong>of</strong> potential for biomagnification<br />

and effects on reproduction and/or immunological capacity increase in an exponential<br />

way the risk for top predators, as can be clearly observed from the examples<br />

provided in the chapter on wildlife.<br />

Finally, methods for an adequate characterisation <strong>of</strong> the potential risks <strong>of</strong> endangered<br />

wildlife requiring protection at the individual (for example Iberian lynx or Iberian imperial<br />

eagle) or population levels should be developed. These methods, to be developed as<br />

specific scenarios for the local risk assessment, should be applied on certain areas, in<br />

addition to the general ecological risk assessment, when endangered species are expected<br />

to be at risk.<br />

6.2 TESTING STRATEGIES<br />

Scheme 1 displays the current and future options for defining endocrine disrupters. The<br />

studies required for a particular agent will be influenced by the extent <strong>of</strong> any existing<br />

toxicity database for it. The various screening assays available for use in each tier have<br />

been discussed above.<br />

The sequence <strong>of</strong> conducting tests and the point <strong>of</strong> entry into Scheme 1 will be influenced<br />

by many factors. At one extreme, an agent may have been adequately evaluated<br />

for reproductive effects, e.g. in a one- or two-generation study. In such cases, it may be<br />

possible to classify the agent as inactive as an endocrine disrupter, irrespective <strong>of</strong> any<br />

activities it may be shown to have in in vitro assays. At the other extreme, it may be important<br />

to study analogues <strong>of</strong> a confirmed endocrine disrupter in order to prioritise analogues<br />

for testing in vivo or to eliminate similarly active members <strong>of</strong> the chemical class.<br />

In such situations, structure-activity relationship (SAR) or in vitro assays may prove<br />

valuable in cases where the mechanism <strong>of</strong> action <strong>of</strong> the lead chemical is known and<br />

where appropriate in vitro assays responsive to it are established. In most cases, however,<br />

a single agent with few toxicity data available on it, will be under consideration. In<br />

these cases, four possible testing strategies are possible (A-D, Scheme 1):


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Figure 6-1: Approaches to identify endocrine disrupting substances (EDS). Dotted arrows<br />

represent entries to the sequence <strong>of</strong> testing that require further research before they can<br />

be endorsed or eliminated [WEYBRIDGE REPORT, 1996]<br />

Option A<br />

Until the problem <strong>of</strong> metabolism is solved, negative responses observed in vitro will still<br />

require follow-up testing in vivo. Positive responses in vitro may be <strong>of</strong> value but they are<br />

insufficient to define an endocrine disrupter. In vitro assay may be <strong>of</strong> value to study<br />

mechanisms <strong>of</strong> action <strong>of</strong> a confirmed endocrine disrupter, but still, the problem <strong>of</strong> metabolism<br />

will complicate such studies. A major research need is, therefore, to solve the<br />

problem <strong>of</strong> metabolism in vitro. There is also the need to devise assays for the metabolic<br />

disturbances likely to occur in whole organisms. There is also the research need<br />

to build up SARs in conjunction with the acquisition <strong>of</strong> new data.<br />

Option B<br />

Limited studies in rodents are a possible method to evaluate endocrine disruption. The<br />

available assays are discussed above. However, it is unclear at present whether it will<br />

be necessary to include assays in which pregnant animals are studied, together with<br />

the study <strong>of</strong> their <strong>of</strong>fspring. There is therefore a research need to acquire data on a<br />

range <strong>of</strong> endocrine disrupters in order to establish two things:<br />

a) the hierarchy <strong>of</strong> sensitivities between the several available endpoints,<br />

b) the possible need to study the effects <strong>of</strong> chemicals on embryos and neonates.<br />

Until such data are available it is not possible to prescribe a preferred battery <strong>of</strong>


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assays. A few current precedents suggest that it may be necessary to include<br />

studies in utero for an adequate evaluation <strong>of</strong> endocrine disruption.<br />

Option C<br />

It may be decided that it is important to study the effects induced in animals exposed in<br />

utero. The possible endpoints that currently exist are detailed above.<br />

Option D<br />

In some cases expected exposures may dictate that testing commences in wildlife species.<br />

The choice <strong>of</strong> test species will be mandated by the particular emission condition<br />

prevailing. In general, however, endocrine disrupters defined in mammals will be selectively<br />

evaluated in wildlife species in order to evaluate their relative sensitivity and to<br />

establish no-effect levels. A research need is to select a range <strong>of</strong> sentinel species and<br />

endpoints for situations where the study <strong>of</strong> endocrine disruption commences in wildlife.<br />

6.3 RECENT DEVELOPMENTS<br />

Many initiatives have been taken in (inter)national fora to develop new test guidelines<br />

(in vitro screening as well as in vivo screening and comprehensive in vivo tests) and/or<br />

enhancement <strong>of</strong> existing test guidelines (additional parameters/endpoints in existing<br />

test guidelines). The most important initiatives are discussed below:<br />

OECD Endocrine Disrupter Testing and Assessment (EDTA) Working Group:<br />

EDTA has been established jointly by the OECD Risk Assessment Advisory Body<br />

(RAAB) and the OECD National Co-ordinators <strong>of</strong> the Test Guidelines Programme (NC-<br />

TGP) in December 1997. The EDTA is the focal point for current OECD work on endocrine<br />

disrupters. In the draft report <strong>of</strong> the first EDTA meeting it is stated: “that specifically<br />

EDTA will provide (1) a forum to mutually inform national and regional activities,<br />

(2) develop appropriate OECD test guidelines and (3) where possible harmonise risk<br />

characterisation and assessment approaches”. EDTA recommends on the priority and<br />

future need for OECD work on endocrine disrupters by:<br />

• “identifying and prioritising enhancements and modifications to existing OECD<br />

test guidelines to facilitate the detection <strong>of</strong> endocrine disrupting substances;<br />

• developing a workplan for the development <strong>of</strong> top priority enhancements as indicators<br />

<strong>of</strong> endocrine disrupting effects, including an evaluation <strong>of</strong> their sensitivity<br />

and reliability;<br />

• identifying and prioritising needs for new test guidelines and developing a workplan<br />

for future OECD work, including the validation <strong>of</strong> new test guidelines;<br />

• developing a harmonised testing strategy for the screening and testing <strong>of</strong> endocrine<br />

disrupting chemicals taking into account the consequences <strong>of</strong> such a testing<br />

strategy on the development and validation <strong>of</strong> test guidelines, and on existing<br />

regulatory systems for new and existing substances”.<br />

The following non-mammalian tests were discussed in the first EDTA meeting:


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• Mammals: several tests - from in-vitro screening assays to higher tier tests like the<br />

two-generation reproductive toxicity study - were discussed. It was agreed that possible<br />

enhancements to detect chemicals capable <strong>of</strong> causing endocrine disruption<br />

should be considered.<br />

• Birds: It was noted by EDTA that the avian reproduction test (OECD 206) was currently<br />

in the process <strong>of</strong> being revised. It was agreed that possible enhancements to<br />

detect chemicals capable <strong>of</strong> causing endocrine disruption should be considered in<br />

the revision process.<br />

• Fish tests: A proposal to develop a fish full life-cycle test has been agreed by the<br />

NC-TGP. It was noted by EDTA that also the early life-stage test (OECD 210) has<br />

the potential to be able to identify an endocrine disrupter, provided the test is sufficiently<br />

enhanced. EDTA agreed that chronic testing for fish should be the subject <strong>of</strong><br />

separate in depth discussions with appropriate experts. These discussions would<br />

aim to consider the various proposals for further fish tests - screening as well as<br />

confirmatory - and to recommend a suitable approach. As a first step an OECD<br />

Validation Management Group will be established, which will organise the development<br />

<strong>of</strong> fish test guidelines. EDTA agreed that a reference set <strong>of</strong> chemicals with a<br />

range <strong>of</strong> potencies for endocrine disruption should be identified for validation studies.<br />

• Invertebrates: It was concluded that no specific tests were available for endocrine<br />

disrupters in invertebrates. The outcome <strong>of</strong> a SETAC-Europe and North American/EC<br />

Expert Workshop entitled “Endocrine Disruption in Invertebrates: Endocrinology,<br />

Testing and Assessment”, hold in December 1998 highlight the importance<br />

<strong>of</strong> this taxonomic group, as invertebrates represent about 95 % <strong>of</strong> the known animal<br />

species. The need for better understanding <strong>of</strong> invertebrate endocrinology and the<br />

large physiological diversity, which makes it scientifically unrealistic to select a “representative”<br />

species, were also stated. Regarding toxicity testing, the generation <strong>of</strong><br />

data on several species is required, considering full life-cycle studies as the ideal<br />

bioassay. It was also pointed out that existing tests can be implemented for the detection<br />

<strong>of</strong> EDS effects by simply adding additional endpoints.<br />

• The CSTEE considers that the development <strong>of</strong> cost-effective multispecies laboratory<br />

tests, in which multiple reproduction strategies would be assessed simultaneously,<br />

will cover the identified needs and is realistic according to the current state <strong>of</strong> the art<br />

<strong>of</strong> invertebrate testing, and therefore requires priority.<br />

• Amphibia: EDTA concluded that there are no international accepted test guidelines<br />

available for amphibia. As EDSTAC has included a proposed amphibian development<br />

and reproduction test, it was agreed that the US would take the lead in developing<br />

a proposal for an amphibian test. As a follow-up to the first EDTA meeting the<br />

“OECD workshop on the Validation <strong>of</strong> Endocrine Disrupters Screening and Testing<br />

Methods” was organised on August 10-11 <strong>of</strong> 1998 in the USA.


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One objective <strong>of</strong> the meeting was the selection <strong>of</strong> new test methods or enhancement <strong>of</strong><br />

existing methods to be considered for validation. With respect to test methods the following<br />

was agreed:<br />

• mammals: validation work has the highest priority for the 3-day uterotrophic, 5-7<br />

day Hersberger assay and the OECD 407 repeated dose oral toxicity test in rodents<br />

(in general, the EU experts at the workshop were in favour <strong>of</strong> extension <strong>of</strong><br />

the existing OECD 407, and not <strong>of</strong> the selection <strong>of</strong> new test methods). The second<br />

EDTA meeting <strong>of</strong> November 12-13, 1998 focussed on tests with mammals.<br />

Protocols for OECD 416 (two-generation), enhanced OECD 407, uterotrophic<br />

and Hershberger assay were discussed. These will now be part <strong>of</strong> an OECD<br />

validation programme. A Validaton Management Group has in the meantime<br />

been established.<br />

• wildlife: expert workshops will be organised for fish testing (October 1998 in the<br />

UK) and mysid testing. In this OECD Expert Consultation meeting on Testing in<br />

Fish (28-29 October 1998, London, UK) the following was concluded: work underway<br />

in various fora with respect to the development <strong>of</strong> methods for the detection<br />

<strong>of</strong> endocrine disrupters in fish is still at the level <strong>of</strong> “pre-validation”. Test<br />

protocols for further guideline development could probably be submitted to a<br />

second expert consultation to be hold in September 1999<br />

Endocrine Disrupter Screening Testing and Advisory Committee (EDSTAC)<br />

The Safe Drinking Water Act (SDWA) Amendments <strong>of</strong> 1996 and the Food Quality Protection<br />

Act (FQPA) required US-EPA to “develop a screening program, using appropriate<br />

validated testing systems and other scientifically relevant information, to determine<br />

whether certain substances may have an effect in humans that is similar to an effect<br />

produced by naturally occurring oestrogen, or such other hormonal effect as the Administrator<br />

may designate”. As a result <strong>of</strong> this EDSTAC was established. In October<br />

1998 the final report was published. With respect to testing and test guidelines three<br />

phases - a tiered approach - are distinguished by EDSTAC:<br />

• Pre-screening: consists <strong>of</strong> use <strong>of</strong> (Q)SARs, information from the US-EPA Endocrine<br />

Disrupter/Disruptor Priority Setting Database and High Throughput Pre-Screening<br />

(HTPS). In the HTPS 15,000 substances will be tested in an in vitro assay on oestrogen,<br />

androgen and thyroid receptor binding with and without metabolic activation.<br />

• Tier 1 testing: consists <strong>of</strong> the following tests: (1) in vitro: oestrogen receptor binding<br />

or reporter gene assay, androgen binding or reporter gene assay, steroidogenesis<br />

assay with minced testis; (2) in vivo: rodent 3-day uterotrophic assay, rodent 20 day<br />

pubertal female assay with thyroid, rodent 5-7 day Hersberger assay, frog metamorphosis<br />

assay and fish gonadal recrudescence assay. Possible substitutes are: (1) in<br />

vitro: placental aromatase assay; (2) in vivo: modified rodent 3-day uterotrophic assay,<br />

rodent 14-day intact adult male assay with thyroid and rodent 20-day thyroid/pubertal<br />

male assay.


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• Tier 2 testing: consists <strong>of</strong> the following tests: (1) two-generation mammalian reproductive<br />

toxicity study or a less comprehensive test (alternative mammalian reproductive<br />

test or one-generation test); (2) avian reproduction; (3) fish life cycle; (4)<br />

mysid life cycle; and (5) amphibian development and reproduction.<br />

The non-mammalian tests recommended by EDSTAC are discussed below:<br />

• Fish gonadal recrudescence assay: there are essential endocrine differences between<br />

fish and mammals: (1) fish differ in steroid pr<strong>of</strong>iles (11-ketotestosterone versus<br />

testosterone); (2) differences in oestrogen receptor; (3) steroid receptors in eggs<br />

for vitellogenin are unique for oviparous animals. In this assay fish <strong>of</strong> both sexes<br />

maintained under simulated winter conditions are exposed to an increasing photoperiod,<br />

temperature and test substance to determine effects on maturation from the<br />

regressed position (recrudescence). EDSTAC recommends the fathead minnow<br />

(Pimephales promelas) as test species.<br />

• Avian reproduction: EDSTAC recommends the EPA Avian Reproduction Test<br />

Guideline – test species are the mallard duck and northern bobwhite quail - to be<br />

enhanced with some additional observations: steroid titrestiters, organ and gland<br />

weights, histochemistry and histopathology, and reproductive capability <strong>of</strong> the <strong>of</strong>fspring.<br />

• Fish life cycle test: EDSTAC recommends the fathead minnow (Pimephales promelas)<br />

or the sheepshead minnow (Cyprinodon variegatus) as test species, depending<br />

on whether the substances will lead to exposure <strong>of</strong> freshwater or estuarine/marine<br />

systems, respectively. Test organisms will be continuously exposed from fertilisation<br />

through development, maturation and reproduction, and early development <strong>of</strong> the<br />

<strong>of</strong>fspring (test duration up to 300 days).<br />

• Mysid life cycle test: endocrine disrupters can interfere with ecdysteroid activity, being<br />

an important steroid in arthropods. In this test the effects on development,<br />

moulting, growth and sexual reproduction are studied.<br />

• Amphibian development and reproduction: in this test the effects on amphibians exposed<br />

from the larval stadium through metamorphosis and reproduction is studied.<br />

With respect to the validation status <strong>of</strong> the tests recommended EDSTAC distinguishes<br />

5 categories:<br />

Category I: tests which have been fully validated and standardised;<br />

Category II: tests which have been in use for a sufficient period <strong>of</strong> time<br />

and have gained sufficient general acceptance. Standardisation<br />

should be accomplished.<br />

Category III: tests which have been used sufficiently broad to be generally<br />

considered relevant or reliable. Further validation and standardisation<br />

is necessary.<br />

Category IV: tests which may be relevant, but have not been used very <strong>of</strong>-


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ten. Method development, validation and standardisation is<br />

necessary.<br />

Category V: tests which have actually not been conducted yet. Research<br />

should be carried out to determine whether these tests can be<br />

developed, and determine which purpose they can have in the<br />

endocrine disruption screening and testing program.<br />

The following non-mammalian tests were placed in these categories:<br />

Category II: avian reproduction, fish life cycle and mysid life cycle;<br />

Category IV: fish gonadal recrudescence;<br />

Category V: avian androgenicity screening test, invertebrate screening<br />

tests, avian multi-generation test, amphibian development and<br />

reproduction test and reptilian test.<br />

Endocrine Modulator Steering Group<br />

In June 1996 the chemical industrial organisation in Europe CEFIC (Conseil Européen<br />

de l’Industrie Chimique) - established the Endocrine Modulator Steering Group (EMSG).<br />

After a public call in The Lancet for tenders, a research programme was announced in<br />

a press release on 14 May, 1998. The EMSG programme is part <strong>of</strong> a global programme<br />

<strong>of</strong> the chemical industry, in which the Chemical Manufacturers <strong>of</strong> America (CMA) and<br />

the Japanese Chemical Industry Association (JCIA) are the other key players. With respect<br />

to wildlife EMSG will focus on fish, while the CMA concentrates on birds and reptiles.<br />

At the EDTA meeting in March 1998 the EMSG presented three proposals on<br />

tests with fish:<br />

• In vivo screening test: juvenile fathead minnows (Pimephales promelas) will be exposed<br />

for 21 days. Endpoints are induction <strong>of</strong> the egg yolk precursor vitellogenin<br />

and sex steroid levels.<br />

• Modified early life-stage (ELS) tests (enhanced OECD 210): randomly selected<br />

fathead minnow will be held without further exposure until maturity and subsequent<br />

egg-laying. In addition histological analyses <strong>of</strong> the gonads (presence <strong>of</strong> oocytes in<br />

testicular tissue and incorporation <strong>of</strong> yolk into oocytes) and biochemical analyses<br />

(vitellogenin, sex steroids and analysis <strong>of</strong> genetic sex) will be performed.<br />

• Partial life cycle test: sexually mature adult fathead minnow will be exposed for 28<br />

days. Biological observations (daily counting <strong>of</strong> fertilised/unfertilised eggs) and histological<br />

analysis <strong>of</strong> the gonads (see above) will be carried out. On one occasion<br />

eggs will be collected. Eggs and hatched fry will then be exposed for 28 days posthatch<br />

and then follow the same procedure as described above for the ELS test.<br />

In the EDTA meeting it was discussed that also other fish species than the fathead<br />

minnow could be used for this type <strong>of</strong> toxicity testing.


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6.4 OUTLOOK<br />

Many questions must be addressed before the overall magnitude, extent, and specific<br />

causes <strong>of</strong> this environmental concern can be resolved. Information is needed on what<br />

chemicals or class <strong>of</strong> chemicals can be considered to be genuine endocrine disrupters.<br />

The quantity (dose) <strong>of</strong> a chemical that is necessary to cause an adverse effect is important.<br />

Next, there is a need to know whether chemicals that are suspected <strong>of</strong> being<br />

endocrine disrupters act in an additive, synergistic, or antagonistic manner. While there<br />

are several available tests that are capable <strong>of</strong> evaluating a chemical for possible unique<br />

endocrine system disruption in some animal species, it is unclear which one or ones<br />

are the most useful. Therefore, it is important to determine how well current screening<br />

assays predict an adverse ecological effect due to endocrine disruption. Methods need<br />

to be (further) developed and validated to test for a cause-and-effect and a doseresponse<br />

relationship to allow for sound risk assessment and regulatory decisions to be<br />

made. Additional research is needed to<br />

(1) determine whether a (new) chemical or its metabolites have hormonal activity,<br />

and if so, what the mechanism <strong>of</strong> action is;<br />

(2) prioritise chemicals in relative potency terms <strong>of</strong> toxicity;<br />

(3) determine whether organisms are exposed to the chemical in the environment;<br />

(4) ascertain whether there are sensitive species and individuals, and<br />

(5) predict effects in the environment, including the effects on organisms, populations,<br />

communities, and ecosystems;<br />

(6) integrate the development <strong>of</strong> SAR in endocrine disruption with new data acquisition;<br />

(7) devise a source <strong>of</strong> auxiliary metabolism suitable for use with in vitro assays<br />

(8) To assess if in vitro assays can be developed to predict changes to the biosynthesis<br />

and degradation <strong>of</strong> hormones in whole organisms, and to predict changes<br />

to thyroid gland function;<br />

(9) devise novel whole organism assays for endocrine disruption in birds, fishes and<br />

invertebrates, both for their use to assess hazards to those species and to act as<br />

a possible replacement for rodent studies;<br />

(10) establish if endocrine disruption effects observed in neonates or weanlings<br />

can be predicted by measurements made in the exposed parent. Such research<br />

will resolve the question <strong>of</strong> whether there is an absolute need to conduct<br />

exposures in utero and during lactation;<br />

(11) establish a hierarchy <strong>of</strong> sensitivities for the markers <strong>of</strong> endocrine disruption<br />

in mammals, fish and birds, using a set <strong>of</strong> appropriately selected endocrine<br />

disrupters;<br />

(12) select sentinel wildlife species and endpoints for use in situations where<br />

the evaluation <strong>of</strong> an agent’s endocrine disrupting activity will most usefully commence<br />

in wildlife species.<br />

Specifically, test methods are needed to identify potential endocrine disrupters, quantify<br />

the potency <strong>of</strong> such action, and demonstrate any adverse outcome. "Sentinel" species<br />

(organisms used to detect effects <strong>of</strong> hazardous exposures) have been used to identify<br />

environmental contaminants. Therefore, there is a need to determine whether current<br />

sentinel species are adequate surrogates for identifying endocrine disrupters in wild and


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aquatic life or if other sentinel species should be identified and validated for assessing<br />

the state <strong>of</strong> ecosystems. Perhaps the development, validation, and use <strong>of</strong> amphibian<br />

and/or reptilian models would be appropriate in view <strong>of</strong> their widespread distribution and<br />

lack <strong>of</strong> information on these classes <strong>of</strong> vertebrates. Evaluations <strong>of</strong> ecological effect<br />

generally do not consider factors such as disease resistance (immune system dysfunction),<br />

behaviour (mating disruption), or reproductive viability <strong>of</strong> <strong>of</strong>fspring (transgenerational<br />

effects). Consequently, there is a need to determine whether existing ecological<br />

effects/endpoints are adequate for assessing endocrine system perturbation. If not,<br />

then additional effects/endpoints are needed. Finally, there is a need to know what effects<br />

that occur at the earliest response threshold are relevant for further risk characterisation<br />

and what are the population, community, or ecosystem consequences <strong>of</strong> the<br />

effects observed in fish and wildlife.


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6.5 ECOTOXICOLOGICAL RISK ASSESSMENT<br />

The word risk coming from the insurance industry means the occurrence probability <strong>of</strong> a<br />

damage event. A modern risk assessment <strong>of</strong> chemical substances not only have to<br />

take account on humans but also on the environment. The aim <strong>of</strong> the ecotoxicological<br />

risk assessment is the estimation <strong>of</strong> the hazardous impact to the ecosystem regarding<br />

the toxicological data <strong>of</strong> chemicals and the exposition. In doing so, both, the effects on<br />

organisms and populations and the pollution <strong>of</strong> environmental compartments like the<br />

ground water have to be estimated and evaluated [FENT 1998].<br />

Exposition assessment<br />

Use<br />

Amount <strong>of</strong> input<br />

Characteristic <strong>of</strong> input<br />

Behaviour in the environment<br />

— Spread<br />

— Degradation<br />

— Metabolism<br />

Hazard evaluation<br />

Risk analysis<br />

Risk assessment<br />

Effect evaluation<br />

Ecotoxicological effects<br />

— Acute toxicity<br />

— Chronic toxicity<br />

— Toxicity to populations and ecosystem<br />

— bioaccumulation<br />

Occurrence probability<br />

Figure 6-2: hazardous evaluation <strong>of</strong> substances [FENT 1998]


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For a detailed exposition assessment information about the amount <strong>of</strong> input, characteristic<br />

<strong>of</strong> input like temporary trend, frequency and spatial distribution) as well as data<br />

about the behaviour <strong>of</strong> a substance in the environment are necessary. Moreover assumptions<br />

like sewage quantity and dilutive factor between sewage treatment plant<br />

run<strong>of</strong>f and receiving water must be made. If no precise information about the kind and<br />

the location <strong>of</strong> the entry as well as the prevailing environmental condition are known, an<br />

exposition assessment based on scenarios are made. In this situation both a typical input<br />

and dilution scenario and the worst case situation are proved. From these data the<br />

predicted environmental concentration (PEC) can be assessed [FENT 1998].<br />

The hazard or risk potential <strong>of</strong> a substance is its potential to harm humans and environment<br />

based on disadvantageous characteristics. This potential is specified by the<br />

physical-chemical and toxicological characteristics <strong>of</strong> the substance and the ecotoxicity.<br />

At the effect evaluation it is checked if the substance is hazardous to humans and<br />

nature. This evaluation is based on the acute toxicity not until higher toxical compounds<br />

the chronical toxicity is integrated. The bioaccumulation is not yet regarded much but is<br />

an important criterion. The aim <strong>of</strong> the evaluation <strong>of</strong> the ecotoxicological hazardousness<br />

<strong>of</strong> a substance is the derivation <strong>of</strong> values for environmental concentrations at which a<br />

damage <strong>of</strong> the ecosystem is less probable [FENT 1998]. The author continues that the<br />

hazard evaluation is a result <strong>of</strong> the combination <strong>of</strong> exposition evaluation (amount and<br />

exposition) and the effect evaluation. It contains an evaluation <strong>of</strong> the environmental<br />

risks by using a substance based on input and substance characteristics determining<br />

the exposition concentrations and possible effects.<br />

If the hazard evaluation shows that a substance with endocrine characteristics reaches<br />

the environment in relevant amounts a risk assessment must be done. Here the possible<br />

dimension, the frequency and the consequences <strong>of</strong> a contamination based on a<br />

detailed exposition assessment are estimated. The risk assessment considers the occurrence<br />

probability [FENT 1998].


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input effects<br />

destiny, dispersion extrapolation<br />

environmental concentration<br />

(PEC)<br />

PEC/PNEC<br />

effect concentration<br />

(PECEC)<br />

< 1: no risk assessment<br />

> 1: risk assessment is necessary<br />

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Figure 6-3: Concept <strong>of</strong> the environmental or ecotoxicological risk assessment <strong>of</strong> chemical<br />

substances [FENT 1998].<br />

The PEC/PNEC-concept (see Figure 6-3) is a comparison <strong>of</strong> environmental concentrations<br />

(exposition) with the effect concentrations (effects). Due to the lack <strong>of</strong> data about<br />

the input and the behaviour <strong>of</strong> the substances in the environment, about the exposure<br />

concentrations can <strong>of</strong>ten be made only an approximate estimate. This uncertain state<br />

<strong>of</strong> data causes certain difficulties because there are <strong>of</strong>ten only a few experimentally<br />

found NOEC or LOEC values. Often it is only possible to estimate upper bounds <strong>of</strong><br />

LOEC values or sphere <strong>of</strong> actions. Beyond this, the extrapolation and safety factors did<br />

not base on strongly scientific criteria. The highness <strong>of</strong> this factors depend on the quality<br />

and quantity <strong>of</strong> the existing ecotoxicological data. The fixing <strong>of</strong> such factors concerning<br />

endocrine effecting substances is not clear [BÄTSCHER et al 1999].<br />

The authors emphasise the great importance <strong>of</strong> clarification <strong>of</strong> the loading situation <strong>of</strong><br />

humans and wildlife, the environmental behaviour <strong>of</strong> the substances, the effects <strong>of</strong> different<br />

species and populations as well as the clarification <strong>of</strong> effect mechanisms for a<br />

risk assessment. At the moment an established risk assessment and evaluation is due<br />

to the lack <strong>of</strong> data (insufficient exposition and effect data) hardly be made. A closing <strong>of</strong><br />

the existing research gaps should be made possible a risk analysis and assessment for<br />

endocrine effects. But it is necessary that the research activities and question formula


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tions be straightened to that aim and the results <strong>of</strong> the studies (e. g. NOEC, LOEC, effect<br />

thresholds) be part <strong>of</strong> the risk assessment in accordance to their importance.<br />

The used models like the PEC/PNEC model described above are for the evaluation <strong>of</strong><br />

single substances. The effects caused by different substances are unconsidered.<br />

Therefore it is necessary to develop new models where combination effects <strong>of</strong> different<br />

hormonal active substances could be integrated in the risk assessment [BÄTSCHER et<br />

al 1999].


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7 IMPACTS OF HORMONAL ACTIVE CHEMICALS TO HUMANS AND ANIMALS<br />

Substances where an endocrine effect to several organisms is evidenced or supposed<br />

mainly are pesticides and so-called industrial chemicals [LEISEWITZ 1996]. They are<br />

part <strong>of</strong> the in 0 pictured group <strong>of</strong> POPs. A list <strong>of</strong> environmental chemicals with an endocrine<br />

effect is shown in appendix 1. Chloroganical materials have a great importance<br />

but not all in this context suspected environmental chemicals are chlorinated (phthalates,<br />

surfactants, heavy metals etc.) [LEISEWITZ 1996].<br />

7.1 THE HAZARDOUSNESS OF ENVIRONMENTAL CHEMICALS<br />

The effects <strong>of</strong> xenobiotics are intensively cross-linked at the different biologicalecological<br />

levels, shown in the Figure 7-1.<br />

immediatlysome<br />

days<br />

hoursweeks<br />

weeksmonths<br />

monthsyears<br />

monthsdecades<br />

timetable<br />

attitude change<br />

Neurological and endocrinesymptomsbalance/orientation,locomotion,<br />

motivation/ability to learn<br />

contaminant<br />

biological-molecular reaction<br />

Enzym and metabolism activity<br />

induktion <strong>of</strong> xenometabolism-enzyms<br />

changes <strong>of</strong> membranes, DNA-mutation<br />

physiological changes morphological changes<br />

Oxigen depletion, ions-regulation,<br />

photosynthesis<br />

integration <strong>of</strong> food, digestion, excretion<br />

changes in the individual life cycle<br />

Embryonic development growth rate,<br />

reproduction, regenerative capacity<br />

changes in the population<br />

Reducted number <strong>of</strong> individuals, change in the age distribution,<br />

generally modified <strong>of</strong> ressources gene pool<br />

ecological consequences<br />

Changes in the biocoenosis/ecosystem<br />

with regard to dynamics, structure and function<br />

Histological and cytological<br />

changes<br />

Figure 7-1: Cross-linked effects to different biological-ecological levels, according to<br />

[FENT 1998]


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Environmental chemicals impairing the reproduction <strong>of</strong> animals have a great ecotoxicological<br />

relevance because they affect the whole population and could have an effect<br />

on the surviving <strong>of</strong> whole species. At wildlife various chronical impacts are known. They<br />

are based on the variety <strong>of</strong> the organisms and the complex neuro-endocrine system.<br />

The effects reach from the change <strong>of</strong> the reproduction behaviour over impacts on the<br />

neuro-hormonical system and balance-deviations at sex hormones, the missing <strong>of</strong> sexual<br />

cells up to sterility and sexchange. Organical compounds with high persistence belong<br />

to the most important ecotoxicological chemicals [FENT 1998]. Examples describing<br />

the effects <strong>of</strong> endocrine disrupters at humans and wildlife are performed in Appendix<br />

2.<br />

7.2 SUBSTANCES AND GROUP OF SUBSTANCES WITH A PUTATIVE<br />

ENDOCRINE DISRUPTING ABILITY<br />

In the following sections some special chosen substances and group <strong>of</strong> substances are<br />

introduced. Their use and characteristics like ecotoxicologic effects and their (putative)<br />

endocrine disrupting abilities are described. The selection based on their hazard to the<br />

aquatic environment and humans on the one hand and the fact that they are measured<br />

during investigation programs in the catchment areas. For the selection it was not important<br />

if the substances have been found in concentrations being hazardous for humans<br />

and wildlife or only in concentrations near the detection limit reps. in concentrations<br />

being tolerated by special directives like the drinking-water directive. The decision<br />

for acting like this was the "sneaking" hazard <strong>of</strong> this substances which have been discussed<br />

in the previous chapters.<br />

Heavy Metals - Use and Mode <strong>of</strong> Action<br />

As trace elements some heavy metals are essential but in higher concentrations they<br />

partly have toxicological effects. Heavy metals were emitted by several industrial processes,<br />

through corrosion, in the mining and on waste dumps. Especially lead, cadmium<br />

and mercury are regarded as being toxic. As dust, heavy metals can be transported<br />

over a long distance through the atmosphere and reach this way waters and soil. In<br />

aquatic environments they were diluted fast and partly they precipitate as low-soluble<br />

carbonates, sulphates or sulphides. Therefore they accumulate in the sediments. But if<br />

the sediment's adsorption capacity is effete the concentration in the water increases.<br />

The cycle <strong>of</strong> the metals (air, soil, atmosphere, biosphere) strongly depends on the element's<br />

transformation process. The biomethylation by micro-organisms has a special<br />

importance, because metal organical compounds built in this way have a high toxicity<br />

[DIEFENBACH].<br />

• Copper: For all organisms copper is an essential trace element. With a yearly production<br />

<strong>of</strong> over 7 million tonnes, copper is one <strong>of</strong> the economically most important<br />

metals. Beside its main application area - the chemical industry - copper is also<br />

added to dyes and pesticides (fungicides, algaecides, molluscicides). The industrial<br />

copper input per year into the biosphere exceeds the natural input through weathering<br />

processes nearly about three times. Just as non-essential metals, it has in<br />

higher concentrations a toxic effect. At humans it hardly comes to damages caused<br />

by copper but for fishes it is very toxic [KÖCK 1996].


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• Cadmium: Cadmium is a non-essential element and for humans and fishes already<br />

in low concentrations very toxic. In the nature it occurs very seldom and mostly appears<br />

as an impurity in ores. The anthropogeneous cadmium emissions into the atmosphere<br />

com to 7600 t/a and exceed the natural emissions (1400 t/a) many times<br />

over. Cadmium is regarded as mutagenic, carcinogen, teratogenic and results in<br />

kidney and bone damages [KÖCK 1996].<br />

• Mercury: In the nature mercury is ubiquitous. It exists in many physical and chemical<br />

shapes. Besides different industrial applications, mercury is also added to pesticides<br />

[KÖCK 1996]. The use as a fungicide (seed protective substance) is interdicted<br />

[FRITSCHE 1998].<br />

• Looking at the world-wide human mercury emissions (3600 t/a) they considerable<br />

exceed many times the natural emissions (2500 t/a) [KÖCK 1996] .<br />

• The authors continue that it comes in the body to a fast accumulation <strong>of</strong> mercury<br />

and it is only be decomposed very slowly. Chronic expositions with mercury results<br />

in a damage <strong>of</strong> the nervous system and many enzyme systems. Moreover it is<br />

known to be carcinogen, mutagenic and teratogenic.<br />

• Chrome: For many organisms chrome is an essential trace element but in higher<br />

concentrations it is toxic. The metal-processing and the chemical industry are the<br />

main fields <strong>of</strong> application for chrome. At humans an accelerated chrome exposition<br />

results in the damage <strong>of</strong> internal organs and allergical skin reactions. Further it is<br />

regarded as carcinogen, mutagenic and teratogenic [KÖCK 1996].<br />

• Nickel: For some organisms nickel is an essential trace element. In the nature it occurs<br />

relatively <strong>of</strong>ten. The anthropogeneous nickel emissions (52000 t/a) considerably<br />

exceed the natural emissions (29000 t/a). In water dissolved bivalent nickel concentrations<br />

have a relative low toxicity for fishes and mammals. Nickel expositions<br />

(especially inhalation) results in allergic skin reactions, lung damages, suppression<br />

<strong>of</strong> enzymes and cancer. Moreover the metal is regarded as teratogenic and mutagenic<br />

[KÖCK 1996].<br />

• Lead: Anthropogeneous lead emissions amount to 2.03 million t/a and exceed the<br />

natural emissions about the 345fold. In the atmosphere lead is mainly found as suspended<br />

particles, transported over long distances because <strong>of</strong> their small size [KÖCK<br />

1996]. Both, lead and its anorganic compounds are toxic. Acute lead toxications are<br />

infrequent but a continuous intake <strong>of</strong> small amounts is dangerous. The anorganic<br />

lead compounds accumulate themselves into the bones, teeth and hairs. The toxic<br />

effect primarily concerns kidneys, testis, gastro-intestinal tract, the nervous system<br />

and the biosynthesis <strong>of</strong> the haemoglobin. Because <strong>of</strong> their high fat solubility, organic<br />

lead compounds are fast reabsorbed over the skin and lungs and finally reach the<br />

brain. Plants are more resistant against lead than humans. Therefore it must be attended<br />

that lead does not accumulate in plants used as foodstuff [DIEFENBACH].<br />

• Zinc: For all organisms zinc is vital and as an essential trace element it plays an important<br />

part in enzymatic processes. In the nature zinc is <strong>of</strong>ten be found and with a<br />

yearly production <strong>of</strong> about 6 million tonnes it belongs to the economically most im-


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portant metals. The anthropogeneous zinc emissions (840000 t/a) exceed the natural<br />

emissions about the 23fold . For humans the toxic effect <strong>of</strong> the metal is low,<br />

apart from the inhalation <strong>of</strong> great zinc amounts. Quantities <strong>of</strong> 30 mg/l could cause<br />

sickness and vomiting. Further more zinc interrupts the zinc-copper resorption which<br />

can result in a copper scarcity [KÖCK 1996].<br />

Description <strong>of</strong> Substances - Use and Mode <strong>of</strong> Action<br />

Because <strong>of</strong> the multiplicity <strong>of</strong> substances, only a few are chosen and described in the<br />

following paragraphs.<br />

• Polychlorinated Biphenyles (PCB): PCBs are chemically inert and difficult inflammable.<br />

Therefore they are multifaceted used as technical composites [FENT<br />

1998]. For the new use PCBs are forbidden in Germany but it is still found in technically<br />

outmoded plants (transformers, condensers, refrigerant and insulating material)<br />

and come into the environment [LEISEWITZ 1996]. Today PCB is sorbed on organical<br />

materials <strong>of</strong> soils and sediments and can be remobilised out <strong>of</strong> it. PCB is lipophilic<br />

and stable in the environment.On the basis <strong>of</strong> biomagnification in fishes,<br />

birds and marine mammals standing at the top <strong>of</strong> food chains maximum amounts <strong>of</strong><br />

PCB concentrations are found. This is relevant for higher chlorinated congeners,<br />

because lower chlorinated congeners are metabolised.The chronical toxicity <strong>of</strong><br />

PCBs has a bigger human- and ecotoxicological relevance as the acute one. To<br />

mammals and humans the chronical impacts <strong>of</strong> PCBs are carcinoma <strong>of</strong> the liver,<br />

immunotoxicity and impairment <strong>of</strong> the reproduction [FENT 1998].<br />

• DDT and other organo-chlorine compounds: DDT was the first synthetical produced<br />

insecticide [SCHRENK-BERGT and STEINBERG 1998]. It belongs to the<br />

heavy volatile chlorinated hydrocarbons and is still used in several developing countries<br />

in spite <strong>of</strong> the ban in western Europe. DDT is heavy volatile, hydrophobic and<br />

lipophilic. So a great accumulation in the food chain and sediments <strong>of</strong> water bodies<br />

take place. In the depositions <strong>of</strong> rivers and lakes DDT is frequently about 10 000fold<br />

higher concentrated as in the water [LEISEWITZ 1996]. DDT and its metabolite<br />

DDE are especially accumulated in the fatty tissues, liver and the brain. It is active<br />

as a nerve toxin with neurotoxical effects moreover it results in an increase <strong>of</strong> the<br />

thyroid gland.<br />

• Dioxines: Dioxine is a collective name for polychlorinated dibenzodioxines and furans<br />

[LEISEWITZ 1996]. Polychlorinated dibenzo-1,4-dioxines and dibenz<strong>of</strong>uranes<br />

(PCDD and PCDF) are unwelcome by-products <strong>of</strong> incineration and production processes.<br />

On the basis <strong>of</strong> their chemically-physically and biologically persistence they<br />

are staying a long time in the environment and accumulate and absorb themselves<br />

in reservoirs. Further more they are resistant against chemical and biological decomposition<br />

(cf. chapter 0). Their lipophility supports their bioaccumulation in the lever<br />

and the fatty tissues <strong>of</strong> animals. The toxicity <strong>of</strong> different congeners must be differentiated.<br />

Chlorinated dibenzo-1,4-dioxines are not only carcinogen but also have


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a high potential for chronical effects to the development, the reproduction and the<br />

immune and hormone system [FENT 1998].<br />

• Light volatile chlorinated hydrocarbons: Perchloroethylene, trichloroethylene and<br />

methylene chloride have low boiling points, high vapour pressures and are light volatile.<br />

They are lipophilic and are used for defatting <strong>of</strong> metals, paints and as an extracting<br />

agent for the laundering [LEISEWITZ 1996]. After the inhalation or swallowing<br />

this materials are quick reabsorbed. They can pass through the blood-brain<br />

barrier, so at an acute toxication <strong>of</strong>ten a narcotic effect appears. Chronical toxications<br />

are able to cause irreversible neurological harms. Perchloroethylene can also<br />

be reabsorbed over the skin. In the Ames test the carcinogenic and mutagenic effect<br />

is evidenced [LEISEWITZ 1996].<br />

• Lindane: Lindane is an insecticide and is also added to wood conserving agents.<br />

The scientific name for lindane is γ-hexachlorocyclohexane (γ-HCH) [LEISEWITZ<br />

1996]. Lindane is very volatile and accumulates in the organism's fatty tissue. In its<br />

mode <strong>of</strong> action it is similar to DDT whereas the effect set in faster. For mammals<br />

lindane is more toxic as DDT. For the chronical effect <strong>of</strong> lindane the accumulation in<br />

the fatty tissue, the kidneys in the nervous system and the brain are significant. Lindane<br />

is considered to be carcinogen and affects the human reproductiveness<br />

[WACKER].<br />

• Hexachlorbenzene (HCB): Hexachlorbenzene belongs to the heavy volatile chlorinated<br />

hydrocarbons and is highly lipophilic. It arises as a by-product at different production<br />

and incineration processes, is a plasticizer in synthetic materials and is used<br />

as a fungicide. In Germany the use as a fungicide is prohibited [LEISEWITZ 1996].<br />

Hexachlorbenzene is considered to be carcinogen and because <strong>of</strong> the hormonal impact<br />

it reduces the male reproductiveness. Moreover it affects the immune system<br />

[LEISEWITZ].<br />

• Pentachlorphenol (PCP): PCP is used for the protection <strong>of</strong> wood, textiles and<br />

leather due to it's fungicidal and bactericidal impact. The production and the use <strong>of</strong><br />

products including PCPs is prohibited in Germany [LEISEWITZ 1996]. Pentachlorphenol<br />

operates as a cytotoxin. An exposition with PCP causes eye and skin irritations<br />

(chlorine acne).Typical symptoms <strong>of</strong> a PCP exposition are universal lassitude,<br />

sickness, regurgitation, headache, strong sudation and as well mental disorientation<br />

[LEISEWITZ 1996]. PCP is member <strong>of</strong> the category <strong>of</strong> carcinogen occupational<br />

substances [WACKER].


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Atrazine is used as a nonselective herbicide [EXTOXNET]. Atrazine inhibits the photosynthesis<br />

in plants. The plants ingest the substance by the roots and the leaves<br />

[FEDERAL ENVIRONMENT AGENCY, AUSTRIA]. In 1987 the estimated world-wide<br />

production amounted 70 000 t [FEDERAL ENVIRONMENT AGENCY, AUSTRIA]. In<br />

1990 more than 64 million acre <strong>of</strong> cropland were treated with atrazine in the USA<br />

[EXTOXNET].<br />

Field <strong>of</strong> Application: In agriculture atrazine is used in agriculture for the weed control<br />

in corn and millet for more than 30 years [FEDERAL ENVIRONMENT AGENCY,<br />

AUSTRIA]. Primarily it is used in corn cultivation and the main input takes place between<br />

May and June. In Switzerland 60 t/a are used, in the catchment <strong>of</strong> the Mississippi<br />

20 000 t and in the whole USA together 30 000 t [FENT 1998]. In Austria the increase<br />

<strong>of</strong> atrazine occurs with the enlargement <strong>of</strong> the corn cultivation. In former times, atrazine<br />

was used in amounts <strong>of</strong> 8 kg/ha. It was used in mixture with other herbicides for the<br />

weed control at rail facilities, industry and traffic areas. Here, the dosages mounted up<br />

to more than 20 kg/ha. This was a significant reason for the pollution <strong>of</strong> waters with<br />

atrazine and its metabolites [FEDERAL ENVIRONMENT AGENCY, AUSTRIA].<br />

Elimination from the Sewage: Most <strong>of</strong> the communal sewage treatment plants does<br />

not eliminate atrazine out <strong>of</strong> the water. But by means <strong>of</strong> activated carbon filters they can<br />

be eliminated trouble-free [COMFORT and ROETH 1996].<br />

Pollution Sources: Atrazine reaches the environment from agricultural areas (corn<br />

cultivation) during the application between May and June. Because <strong>of</strong> a great mobility<br />

atrazine reaches the ground water via infiltration and the surface waters via surface<br />

rainwash [FENT 1998]. A long distance transport <strong>of</strong> atrazine is possible by dust particles,<br />

fog and rain [FEDERAL ENVIRONMENT AGENCY, AUSTRIA]. In consequence <strong>of</strong><br />

driftage or evaporation it attains the atmosphere and with the rainfall it reaches the waters<br />

and ground again [FENT 1998].<br />

Environmental behaviour: In Austria's waters atrazine and its by-product desethylatrazine<br />

cause important residual problems. It was detected in the rain, ground water,<br />

surface water and the soil. The main problems <strong>of</strong> the atrazine usage are caused in the<br />

great prevalence in the environment and the persistence <strong>of</strong> atrazine an its metabolites<br />

in the ground water and the soil [FEDERAL ENVIRONMENT AGENCY, AUSTRIA]. In


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the soil atrazine is predominantly metabolised microbial but also abiotically e. g. by sunlight<br />

and hydrolysis [FEDERAL ENVIRONMENT AGENCY, AUSTRIA]. The hydrolysis<br />

is fast in acidic or basic environments and rather slower in a neutral pH range. The average<br />

half-life period is 45 days. In soils with a low part <strong>of</strong> loam or low content <strong>of</strong> organic<br />

substances atrazine is moderate to highly volatile [EXTOXNET]. Under moist and<br />

warm conditions, the half-life period <strong>of</strong> atrazine in the topsoil is about 60 days. In subsurface<br />

soil or in water the half-life period is generally longer [COMFORT and ROETH<br />

1996]. Under dry or cold conditions atrazine can persist more than a year. Because it<br />

does not adsorb strongly at soil particles atrazine has a high potential to contaminate<br />

the ground water despite its moderate water solubility [EXTOXNET]. The biodegradation<br />

in water and ground water is slower because here atrazine and its metabolites are<br />

very persistent [FEDERAL ENVIRONMENT AGENCY, AUSTRIA]. By the feeders the<br />

herbicide attains the epilimnion where it is subject to the different processes <strong>of</strong> water<br />

mixing. Between April and November (stratified lake) atrazine is spread in the epilimnion<br />

within some days. A continuos elimination takes place by the lake outflow. The<br />

vertical water mixing is significantly slower and transports a small amount into the<br />

metalimnion and the hypolimnion. During the winter circulation between December and<br />

March the residual amount <strong>of</strong> atrazine is spread in the whole lake [FENT 1998]. He also<br />

points out, that some by-products have also a small herbicide effect. Due to the low vapour<br />

pressure and a small henry-constant the volatility into the atmosphere is negligible.<br />

The relatively high water solubility <strong>of</strong> atrazine and the small distribution coefficient<br />

causing a relative high mobility from the soil into surface and ground water. Therefore<br />

atrazine sorbs hardly at sediment and soil particles. The microbial degradability is low.<br />

Atrazine is relatively persistent but there is no important bio-accumulation in organisms.<br />

Because the photochemical and biological degradation is also low, the disposition <strong>of</strong><br />

atrazine in the lake is caused by the disposition and transport processes.<br />

Concentration in the Environment: During the application period highest values are<br />

measured. In the 1980's atrazine was measured in concentrations <strong>of</strong> more than 0.1 µg/l<br />

in many drinking water reservoirs. In the period <strong>of</strong> three weeks 0.5 - 9.1 µg/l and maximum<br />

values <strong>of</strong> 23 µg/l are measured in American rivers. Here the medium atrazine<br />

concentrations lie between 0.3 - 4.7 µg/l. In small lakes the values are specifically high.<br />

Surface run<strong>of</strong>f from agricultural fields continue approximately one month after the use<br />

and have values up to 250 µg/l. In May/June up to 0.15 µg/l are measured in the rain in<br />

Switzerland [FENT 1998].<br />

Ecotoxicological Effects: For birds, beneficial animals (e. g. bees) and soil-dwelling<br />

organisms atrazine is extensively harmless. Atrazine does not accumulate itself in the<br />

food chain. The acute toxicity <strong>of</strong> atrazine for humans is low. Sporadically irritations <strong>of</strong><br />

skin, eyes and the respiratory tract are recognised. Human toxicologically it is almost<br />

harmless. It is not safe to say that atrazine has a mutagenic res. teratogenic effect. In<br />

long-term studies an increased rate <strong>of</strong> breast cancer has been recognised. The EPA<br />

classified atrazine to be a "Possible Human Carcinogen". It is suspected to have an<br />

unwanted estrogene effect [FEDERAL ENVIRONMENT AGENCY, AUSTRIA].<br />

Atrazine represses the photosynthesis and is an environmental chemical with a herbicide<br />

effect. In the water it mainly impairs algae and water plants but between related<br />

groups <strong>of</strong> organisms high species differences occur [FENT 1998]. For fishes atrazine is


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acute moderate toxic but negative long-time effects like reproductive interference and<br />

malformation have been observed at low atrazine dosages ( aquatic makrophytes > benthic organisms > zooplankton > fishes<br />

LD50-values (96 h) <strong>of</strong> fishes lie in the range <strong>of</strong> 3.5 - 20 mg/l but chronic values lie at 0.5<br />

- 1.0 mg/l. The author continues that atrazine is very persistent and represses the primary<br />

production in stagnant water at a concentration <strong>of</strong> ≥ 20 µg/l. First effects occur in<br />

the phytoplankton and periphyton. In plant communities no effects are determined at<br />

low values but concentrations <strong>of</strong> 1 - 5 µg/l impair single algae. An impairment <strong>of</strong> the<br />

photosynthesis and a change in the range <strong>of</strong> species take place at concentrations <strong>of</strong><br />

100 µg/l. The displacements <strong>of</strong> species are different in the experiments but it tends to<br />

result in an expansion <strong>of</strong> resistant species in those niches where sensible species are<br />

eliminated. Also at 100 - 500µg/l indirect effects like changes <strong>of</strong> the water quality and<br />

the reduction <strong>of</strong> herbivore populations are recognised. This causes a change in the diet<br />

<strong>of</strong> fish. Although chronic effects to aquatic animals have an important relevance only a<br />

few are known. 4 - 5 µg/l causes histological changes at the kidneys and 80 µg/l causes<br />

cell damages [FENT 1998].<br />

Model System Measuring Parameter Effect<br />

specific single algae<br />

marine phytoplankton<br />

microcosm (pond)<br />

photosynthesis<br />

primary production<br />

phytoplankton productivity<br />

mesocosm (pond) phytoplankton productivity<br />

micro- res. mesocosm phytoplankton productivity<br />

(pond)<br />

makrophytes abundance<br />

Inhibition<br />

Reduction<br />

reduction<br />

green algae reduced<br />

chlorophyll-values increased<br />

reduction<br />

substitute <strong>of</strong> sensitive breeds<br />

Table 7-2: Atrazine-Effects at Concentrations till 50 µg/l [FENT 1998]<br />

Lowest Effect-<br />

Concentration<br />

(µg/l)<br />

1<br />

6<br />

15<br />

20<br />

50


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Ban: Since 1992 a statutory limitation (BGBI Nr. 97/1992) <strong>of</strong> 0.5 kg agent/ha and year<br />

is obtained in Austria. In 1995 atrazin containing compounds are disbarred in Austria<br />

which is like a prohibition. The use <strong>of</strong> atrazine is also forbidden in Germany, Denmark,<br />

Sweden and Finland. In some EU member states like France, Holland and Spain atrazine<br />

is still used as a herbicide. There is no agreement about a consistent restriction <strong>of</strong><br />

atrazine in the whole EU so it is possible to readmit atrazine in Austria [FEDERAL<br />

ENVIRONMENT AGENCY, AUSTRIA].<br />

Regulations<br />

laws, bye-laws, drinking wa- ground water food<br />

directives ter<br />

Austria BGBl. Nr. Grenzwert seit<br />

448/1991 1. Juli 1994:<br />

(i.d.g.F.): Trinkwasser-Pestizidverordnung<br />

0,1 µg Atrazin/l<br />

BGBl Nr.<br />

Schwellenwert<br />

502/1991<br />

seit 1. Juli<br />

Grundwass-<br />

1994: 0,1 µg<br />

erschwellenwerteverordnung<br />

Atrazin/l<br />

BGBl. Nr.<br />

Allgemeiner<br />

747/1995<br />

Höchstwert:<br />

(i.d.g.F.):<br />

0,1 mg/kg; für<br />

Schädlingsbekä<br />

Mais: 0,5<br />

mpfungsmittel-<br />

Höchstwerteverordnung<br />

mg/kg<br />

EU-law 80/778/EWG: Höchstkon-<br />

Richtlinie des zentration: 0,1<br />

Rates vom 15.<br />

Juli 1980 über<br />

µg/l<br />

Qualität von<br />

Wasser für den<br />

menschlichen<br />

Gebrauch<br />

7.3 TOXIC EFFECTS TO AQUATIC ORGANISMS<br />

The table below is showing the toxic effect <strong>of</strong> environmental chemicals to aquatic organisms<br />

in the different biological levels.<br />

Thereby denote: OT = organo-tin compounds, PAH = polycycylic aromatic hydrocarbons;<br />

PCDD = polychlorinated dibenzo-1,4-dioxins; PCB = polychlorinated biphenyls;<br />

HM = heavy metals [FENT 1998].


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Level Effect Place <strong>of</strong> action (organism) Environmental<br />

chemicals<br />

Molecule Mutation, cancer<br />

Lever tumours (fishes)<br />

PAH<br />

Inhibition <strong>of</strong> enzymes<br />

Cytochrom P450 (fishes)<br />

OT, HM<br />

ATP-asen, oxidat. Phosphorylierung OT, HM<br />

Blocking <strong>of</strong> ion channels Neurones (fishes, arthropods) Pyrethroide<br />

Cells Cytotoxicity<br />

Cell membranes<br />

OT, HM, radicals<br />

nerve membrane<br />

Inhibition <strong>of</strong> the nerve irritation PCDD<br />

Organism Damage <strong>of</strong> organs<br />

Necrosis, apoptosis<br />

Several<br />

Growth and development Metamorphose at amphibians OT<br />

Failure <strong>of</strong> the development (fishes) Several<br />

Change <strong>of</strong> behaviour<br />

Search for food, enemy prevention OT, solvents<br />

Immuntoxicity<br />

Reduced immune response<br />

OT, HM, PCB,<br />

(fishes and mammals)<br />

PCDD<br />

Neurotoxicity<br />

Nervous system<br />

Pyrethriode,<br />

Carbamate,<br />

Organophosphates<br />

Physiological effects<br />

Metabolic disturbance<br />

(hormones, enzymes)<br />

Several<br />

Reproduction<br />

Estrogenic impact<br />

Alkylphenols<br />

(fishes and amphibia)<br />

Pesticides<br />

Androgenic impact (molluscan) Tributyltin<br />

Early stage <strong>of</strong> fishes<br />

OT, HM<br />

Thinning <strong>of</strong> eggshells (birds) DDT<br />

No reproduction at otters<br />

PCB<br />

Population Age and size structure Stagnant and sluggish waters<br />

(Phyto- and zooplankton, fishes)<br />

Several<br />

Community<br />

Ecosystem<br />

Formation and frequency<br />

<strong>of</strong> species<br />

Communities <strong>of</strong> plankton,<br />

communities <strong>of</strong> invertebrates,<br />

loss <strong>of</strong> species<br />

Pesticides, HM,<br />

Acid<br />

Depositions<br />

Table 7-3: Toxic effects <strong>of</strong> environmental chemicals to aquatic organisms in the different<br />

biological levels [FENT 1998].


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8 ECOTOXICOLOGY<br />

The ecotoxicological impact <strong>of</strong> a substance depends on its chemical-physical attributes,<br />

biological availability and activity as well as its doses. The effects are considered as a<br />

whole at all biological levels - from the molecule to the ecosystem. The effects at the<br />

molecule and organism level are <strong>of</strong> central importance because here basic principals <strong>of</strong><br />

operation are shown which affect to higher population and ecosystem levels. Beside the<br />

direct effects also indirect effects are analysed resulting from ecological reciprocities<br />

[FENT 1998]. He also states that all environmental fields are linked with dynamical<br />

transport and transfer processes. In this way environmental chemicals are spread and<br />

altered. The ecotoxicological effects <strong>of</strong> chemicals at organisms and the ecosystem can<br />

only be understood in connection with the exposition. If the features high persistence,<br />

high lipophility and bad metabolism are combined, it is dealt with ecotoxicological hazardous<br />

chemicals (e. g. PCDD, PCB, DDT). The chronic effect as a result <strong>of</strong> the load<br />

with low dosages over a long period is <strong>of</strong> a great ecotoxicological importance at environmental<br />

chemicals occurring in low concentrations, says the author. To turn away the<br />

chemical's harmful effect to organisms and ecosystems, basics for the practice must be<br />

created. Here test systems are used determining the toxicity at single organisms. But<br />

the testing <strong>of</strong> chemicals must not be restricted to test systems.<br />

8.1 BEHAVIOUR OF CHEMICALS IN THE ENVIRONMENT<br />

All chemicals reaching the environment are subject to strongly networked circles. In<br />

these circles natural biogenic procedures are linked to anthropogeneous flows <strong>of</strong> material.<br />

In the different compartments the chemicals exist unbalance. Therefore physical<br />

transfer processes and biological transformation processes between the environmental<br />

fields are important. The chemicals are determined by concentration gradients. During<br />

transport and transfer processes the substance is unchanged but at chemical and biological<br />

transfer processes the structure <strong>of</strong> the substance is changed [FENT 1998].<br />

Table 8-1 shows the processes responsible for the destiny <strong>of</strong> environmental chemicals:<br />

Category Process Chemicals<br />

Transport Advection, diffusion, dispersion,<br />

Crude oil, atrazine<br />

transport by particles<br />

PAH<br />

Transfer Solution in the water body<br />

Surfactant<br />

Sorption at particles, sediment and soil (sedi- Heavy metal<br />

mentation)<br />

Tetrachlorethene (PER)<br />

Evaporation into the atmosphere<br />

Sulphur and nitric ox-<br />

Atmospherical deposition<br />

ide, PCDD<br />

Transfor- Abiotic (Hydrolyse, photolysis, redox reac- Pesticide<br />

mationtions) (Organophosphate)<br />

Biotic (aerobe and anaerobe reduction) Methyl mercury, pesticide<br />

Table 8-1: Processes responsible for the destiny <strong>of</strong> environmental chemicals [FENT 1998]


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8.2 REDUCTION OF FOREIGN SUBSTANCES BY MICRO-ORGANISMS<br />

[FRITSCHE 1998] mentions, that the biological reduction (biodegradation) is the reduction<br />

<strong>of</strong> the complexity <strong>of</strong> an organic compound. Normally, a total mineralisation does not<br />

happen in the nature because a part <strong>of</strong> the organic compounds are used for the cell<br />

growth. Natural materials are metabolised by micro-organisms. During the evolution micro-organisms<br />

had developed a multiplicity <strong>of</strong> enzymes for the metabolism <strong>of</strong> natural<br />

materials. Because <strong>of</strong> the industrial development during the last 50 years microorganisms<br />

have an added contact with new organic substances. Several <strong>of</strong> this xenobiotics<br />

are metabolised if they are similar to natural materials. If the organisms have<br />

any respective enzymes, the reduction stays away. Because <strong>of</strong> mutation and genetic<br />

recombination the evolution is proceeding. In this manner micro-organisms regenerate<br />

themselves with new, changed or advanced metabolic efficiencies for the metabolism <strong>of</strong><br />

foreign matter. But it must be allowed that the evolution takes place slowly and need a<br />

pressure <strong>of</strong> selection. A pressure <strong>of</strong> selection is also only infrequent at contaminated<br />

locations because beside the persistent environmental chemicals other organic compounds<br />

exists [FRITSCHE 1998].<br />

Microbial Elimination <strong>of</strong> Heavy Metals<br />

[FRITSCHE 1998] refers that heavy metals can not be metabolised but oxidised or reduced<br />

and converted into other compounds. For the elimination <strong>of</strong> heavy metals from<br />

the environment three mechanisms are important: the biotransformation, the biosorption<br />

and the sulphide precipitation.<br />

At the methylation by fungi and Methanobacterium for the micro-organisms detoxification<br />

functions happen but for the environment they mean the relocation from one medium<br />

into the gaseous phase connected with the formation <strong>of</strong> more toxic compounds for<br />

human and animals. Toxic chromates and dichromates are reduced by bacteria into<br />

lower toxical trivalent chrome. The fixation at metallothioneines (Metallthioneine) at<br />

bacteria is evidenced for copper, zinc and cadmium. Metallothioneines are lower molecular<br />

rich in cystein polypeptides where heavy metals are bounded at SH-groups<br />

[FRITSCHE 1998]. He points out that, in contrast to the bioaccumulation the biosorption<br />

is not bounded to living cells. With bacillus-cells preparations were made adsorbing<br />

cadmium, chrome, copper, mercury and zinc not selective. The sorption results from<br />

highly dilutions. Through stripping the separation <strong>of</strong> the heavy metals results and<br />

through alkali-treatment the biomass is reactivated. In soils a fixation <strong>of</strong> heavy metals in<br />

melanin results through fungi. The fixation <strong>of</strong> metals were proved with the high in melanin<br />

"black yeast" Aureobasium pullans. Due to H2S-fixation through sulphide reducing<br />

bacteria in anaerobic sediments heavy metal sulphide precipitation takes place.<br />

Reduction <strong>of</strong> Chlorinated Aromatic Substances<br />

[FRITSCHE 1998] refers that there are only a few specialists which are able to use single<br />

and twice chlorinated aromatic substances as C and energy sources under selective<br />

conditions. The cometabolic turnover to hydroxylated metabolites is more common.<br />

They are able to receive more or less bound residues with the soil matrix. If a dehalogenation<br />

<strong>of</strong> the chlorine aromatic substances take place, a mineralisation is possible.<br />

For determinably single and twice halogenated aromatic substances four mechanisms<br />

are evidenced. The de-chlorination after ring splitting is the most important one. The


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other mechanisms are the oxidative de-halogenation, the hydrolytic de-halogenation<br />

and the reductive de-halogenation [FRITSCHE 1998]. He describes, the prerequisite at<br />

the de-chlorination after ring splitting is, that the enzymes preparing and realising the<br />

ring splitting are such non-specific that they can also transform chlorinated analogous<br />

substances. This low specificity is infrequent at bacteria and only with some efforts<br />

such strains can be concentrated. Obviously they are infrequent in the nature. On one<br />

hand strains with non-specific enzymes must be found on the other hand it must be<br />

minded that no enrichment <strong>of</strong> toxic metabolite take place. The reduction reaction and<br />

the regulation <strong>of</strong> the respective enzymes result very specific. For this reason it is difficult<br />

to get a strain which is able to use productive a wide spectrum <strong>of</strong> chlorinated aromatic<br />

substances for the growth.<br />

Failure to pressure <strong>of</strong> selection makes sure, that e. g. the metabolism <strong>of</strong> the phenoxy<br />

acid herbicide 2,4-D (2,4-dichlorophenoxy acetic acid) is unrealised. Moreover substances<br />

can arise, which are further metabolised only with difficulty and by their reactivity<br />

they are bound to the soil matrix. As an example dichlorinebrenzcatechin is mentioned<br />

which arises through oxidation from 3,4 dichlorophenol. Soil fungi like penicillium<br />

have a relative non-specific working phenol-hydroxylase. It transform a wide spectrum<br />

<strong>of</strong> single and twice chlorinated phenols to chlorobrenzcatechins. At the reduction <strong>of</strong> the<br />

above-mentioned 2,4-D, the brenzcatechin-dioxygenase is catalysing the twiceoxidation.<br />

It reacts more substrate specifically, so that the chlorobrenzcatechins temporary<br />

be accumulated [FRITSCHE 1998]. He says, it applies to the monochlorophenols,<br />

that chloro-substituted phenols are reduced in 4-position well, in 2-position moderate<br />

and in 3-position bad.<br />

There are also some specialists which partly dechlorinate pentachlorophenol (PCP).<br />

Plural the process finished at tetra-, tri- and dichlorophenols. Aerobic bacteria like rhodococcus<br />

chlorophenolicus realise a para-hydroxylation to tetrachlorohydrochinon<br />

(para-Hydroxylierung zu Tetrachlorohydrochinon). Via hydrolytic and reductive reactions<br />

this substance is dechlorinated to 1,2,4-trihydroxybenzene. Organisms like phanerochaete<br />

chrysosporium build several metabolites such as the methoxylated compound<br />

pentachloroanisole. At the aerobic reductive dehalogenation a wide spectrum <strong>of</strong> tetra,<br />

tri and dichlorophenoles emerge. Thus, possibilities to abolish these environmental<br />

chemicals microbial arise because twice chlorinated phenoles are mineralised aerobically.<br />

This way the basics for the development <strong>of</strong> specific bioremidiation methods exist<br />

[FRITSCHE 1998].<br />

Limits <strong>of</strong> Degradability - Polychlorinated Biphenyls and Dioxins<br />

Multi-chlorinated aromatic compounds build up <strong>of</strong> two aromatic rings, are hardly reduced<br />

aerobically because the chlorine substitutes impede the enzymatic attack.<br />

Thereby the number and the position <strong>of</strong> the chlorine substitutes and the structure <strong>of</strong> the<br />

molecule play an important part. If this differentiation is not be made seeming contradictory<br />

propositions about the persistence level <strong>of</strong> such compounds take place<br />

[FRITSCHE 1998].


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• Polychlorinated Biphenyls (PCB): In laboratory studies a degradation pathway for<br />

a cometabolic aerobic degradation <strong>of</strong> low chlorinated biphenyls is ascertained, starting<br />

at the non or single chlorinated ring <strong>of</strong> the molecule and follows the scheme <strong>of</strong><br />

meta-cleavage. Chlorobenzoat and a C5-acid are the end-products but their metabolism<br />

is already unexplained. Experiments with pseudomonas testosteroni showed<br />

that the process is strongly inhibited by accumulating <strong>of</strong> intermediate products. For<br />

this reason one searches for non-sensitive strains in order to get a detoxification <strong>of</strong><br />

the PCBs existing in the environment [FRITSCHE 1998]. He mentions present tests<br />

about the reductive dechlorination <strong>of</strong> PCB in anaerobic river sediments. Here it may<br />

be evidenced that at the -in the environment <strong>of</strong>ten be found - tetra till octa homologue<br />

<strong>of</strong> the archlor 1260 (a congener <strong>of</strong> the PCB) a 20-40 % de-halogenation take<br />

place so that the starting product is detoxicated. Because lower chlorinated PCB are<br />

potentially aerobic bio-degradable a combination <strong>of</strong> anaerobic-aecobic-processes is<br />

pondered.<br />

• Polychlorinated Dibenzodioxins (PCDD): The most well-known substance <strong>of</strong> this<br />

group is the high toxical known as seveso-poison 2,3,7,8-terrachlorodibenzodioxin.<br />

Dibenzodioxins are bio-degradable if they have no or only one chlorine substitute<br />

For strategies to construct specialists <strong>of</strong> bio-degradation for higher chlorinated congeners<br />

the results are interesting made with pseudomonas and brevibacterium<br />

[FRITSCHE 1998].<br />

Potential and Acute Possibility <strong>of</strong> Metabolism <strong>of</strong> Xenobiotical Substances<br />

It must be differentiated between the potential and the actual, that means in the environmental<br />

medium realised capacity <strong>of</strong> decomposition. For many for the environment<br />

critical substances, micro-organisms could be isolated having biodegradation potentials<br />

under laboratory conditions but they are unusually realised in the environment. For the<br />

development <strong>of</strong> specific methods <strong>of</strong> bioremediation the cognition about potential capacity<br />

<strong>of</strong> decomposition are important. At the same time limits <strong>of</strong> the natural achievement<br />

potential are shown which resulted in a production prohibition <strong>of</strong> especially critical substances<br />

like DDT and lindane [FRITSCHE 1998]. He continued that at the investigation<br />

<strong>of</strong> bio-degradation, it was made clear several times that the starting compounds vanished<br />

but the metabolites still stay or be further transformed. This way critical products<br />

could be formed like diazo compounds. Contrary to the degradation also bioaccumulation<br />

could happen.<br />

The degradation in the environment depends on a multiplicity <strong>of</strong> factors as shown in<br />

Figure 8-1. [FRITSCHE 1998] points out, that these factors have to be recorded for<br />

making propositions about the destiny <strong>of</strong> compounds. Beside the microbial processes<br />

also physicochemical transformations are important.


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micro-organisms<br />

pure and mixed culture<br />

N- and P-sources,<br />

H-acceptors<br />

concentrations<br />

<strong>of</strong> xenobiotical<br />

substances<br />

Substrates for<br />

co-metabolism<br />

Page 57 <strong>of</strong> 136<br />

Figure 8-1: Factors and interdependent action which are decisive for the realisation <strong>of</strong> potential<br />

microbial capacity <strong>of</strong> decomposition, modified according to [FRITSCHE 1998].


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9 LEVEL OF POLLUTION IN WATER AND SEDIMENT<br />

In the [ENVIRONMENTAL ATLAS BERLIN] it is said that there is a continual accumulation<br />

<strong>of</strong> pollutants in water bottom soils, such as heavy metals and chlorinated hydrocarbons.<br />

In the material cycle <strong>of</strong> waters sediments form a natural buffer and filter system. The<br />

waters are subject to strong variations <strong>of</strong> current, substance input, substance transport<br />

and sedimentation. In addition to the water sample analyses practised for years, sediment<br />

analyses is increasingly important in evaluating qualities <strong>of</strong> the total ecosystem <strong>of</strong><br />

a water body. In comparison to water analyses and independent <strong>of</strong> current inputs,<br />

sediment tests reflect the long term quality situation. For this reason, sediment tests are<br />

a better basis for fundamental comparisons with other flowing waters. The suspended<br />

and precipitate substances stored on the water bottom form a reservoir for many pollutants<br />

and trace substances <strong>of</strong> low solubility and low degree <strong>of</strong> degradability. According<br />

to their chemical persistence and the physical-chemical and biochemical characteristics<br />

the substances are conserved in sediments over longer periods <strong>of</strong> time. Even after<br />

sedimentation, portions <strong>of</strong> fixed substances can be remobilised and re-enter the material<br />

cycle <strong>of</strong> water. Analyses <strong>of</strong> sediment samples from different depths give a chronological<br />

record <strong>of</strong> inputs in waters and can also allow conclusions to be drawn regarding<br />

sources <strong>of</strong> contamination. Also mineral suspension and precipitation substances are<br />

able to store heavy metal ions on their outer surface and they can also be bound in<br />

water organisms. The heavy metals can be taken up by higher organisms through the<br />

food chain, or they sink to the bottom as sediment, depending on the flow velocity <strong>of</strong><br />

water. Various pesticides and PCB have the characteristic <strong>of</strong> being stored adsorptively<br />

on suspended matter or in plant organisms. After attaining into the sediment this substances<br />

and by ingestion <strong>of</strong> the organisms they reach the food chain. Eels have a high<br />

fat content and eat bottom organisms and bury themselves in sediment. That way, the<br />

intake <strong>of</strong> pesticides and PCB not only takes place through nutrients. They also ingest<br />

them through the skin and accumulate them in the body fat [ENVIRONMENTAL ATLAS<br />

BERLIN].<br />

9.1 TRANSPORT AND ACTION OF TRANSPORT IN WATER<br />

[FENT 1998] refers that several processes are responsible for the destiny <strong>of</strong> chemicals<br />

in water bodies, like disposition, dilution in the water, volatility in the atmosphere, sedimentation,<br />

abiotic chemical conversation (hydrolysis, photolysis, oxidative and reductive<br />

processes), biotic conversations(microbial reduction, metabolism) and bioaccumulation.<br />

He continues that chemicals having a high vapour pressure and a low water solubility<br />

are given to the atmosphere very fast. If substances have a low water solubility and a<br />

low vapour pressure they prefer to adhere at particles and sediment. Figure 9-1 shows<br />

the apply <strong>of</strong> contaminants to their volatility in a simplified version.


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Figure 9-1: Organic contaminants [FENT 1998]<br />

Page 59 <strong>of</strong> 136<br />

Chemicals normally spread in water more or less by solubility, adsorption at particles<br />

and the accumulation in organisms. The compounds can be deposited from the atmosphere<br />

to the water[FENT 1998]. From here they can reach the soil by disposals.<br />

These relations are shown in Figure 9-2. As adsorbents particles play an important part<br />

in waters. Through sorption to particles and sediments contaminants can be eliminated<br />

from the water body. The adsorption abilities <strong>of</strong> the particles to the ground or sediment<br />

are responsible for their rate <strong>of</strong> mobilisation and migration in and out <strong>of</strong> the ground in a<br />

significant way [FENT 1998].<br />

input<br />

Infiltration <strong>of</strong><br />

groundwater<br />

Air/Water-exchange<br />

ATMOSPHERE<br />

Deposition<br />

Transport<br />

Transformation<br />

WATER<br />

SEDIMENT<br />

Photolyse<br />

Sedimentation<br />

Sediment-Waterexchange<br />

Figure 9-2: Transport- and transformation processes <strong>of</strong> contaminants in stagnant waters,<br />

modified according to [FENT1998].<br />

dish


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Figure 9-3: Connection between<br />

the bioaccumulation <strong>of</strong> persistent<br />

contaminants in fishes and the nutrient<br />

ratio in lakes [FENT 1998]<br />

Page 60 <strong>of</strong> 136<br />

The nutrient ratios in lakes and the resulting changes in the organic parts <strong>of</strong> the lake<br />

water could be important for the accumulation <strong>of</strong> foreign substances. The bioaccumulation<br />

<strong>of</strong> persistent contaminants like PCB and DDT in fishes is connected with<br />

the lake’s productivity and the chemistry. The lake’s trophic level and the content <strong>of</strong><br />

humates have an great influence. In eutrophic lakes (high productivity) the fishes contain<br />

less PSB and DDT as in oligotrophic lakes. The reason therefore is the faster<br />

growth <strong>of</strong> the fishes and a faster turnover <strong>of</strong> the plankton. Supplementary a reduction <strong>of</strong><br />

the concentration <strong>of</strong> foreign matter referring to the weight takes place [FENT 1998].<br />

Figure 7-3 shows the connection between bio-accumulation <strong>of</strong> persistent contaminants<br />

in fishes and the nutrient balance in lakes.


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10 THE CATCHMENT AREAS<br />

Anthropogenic land use, especially agricultural and forestry, has an important influence<br />

on the quality <strong>of</strong> ground and surface water and also influences the whole water balance.<br />

Water quality can be influenced by the input <strong>of</strong> pollutants and nutrients from both<br />

diffuse and point sources. Besides this the water balance can be changed by different<br />

actions like sealing <strong>of</strong> land, water regulation and land amelioration [WINKLER 1996].<br />

[WINKLER 1996] refers to the necessity <strong>of</strong> a registration and evaluation <strong>of</strong> land use in<br />

accordance with their influence on the water balance and quality to protect the ground<br />

and surface water as well as water reservoirs, and for the restoration <strong>of</strong> alreadyimpaired<br />

water resources.<br />

In the catchments investigated diffuse and point sources are identified and their impacts<br />

are described. Point sources include local and industrial sewage, collected by<br />

sewers and transported via sewage treatment plants into the surface waters. . Precipitation<br />

water directly passed into surface water, sewage from domestic sewage plants as<br />

well as untreated sewage from individual farms and sewage water from leaky sewers<br />

are also point sources. Inputs like surface run<strong>of</strong>f, sewage and direct input <strong>of</strong> substances<br />

from the atmosphere are diffuse sources [PRASUHN et al 1996].<br />

Besides these influences a major source <strong>of</strong> endocrine disrupters is sewage treatment<br />

plants because they can not be eliminated by the common treatment methods.<br />

In the following the lakes and their catchment areas are introduced and the land use<br />

and data about pollution sources concerning the special hazard contamination <strong>of</strong> endocrine<br />

disrupters are described.<br />

The Figure 10-1 shows the pollution inputs into water caused by agriculture, transport,<br />

industry and households being the major sources <strong>of</strong> water pollution.<br />

Figure 10-1: Pollution inputs into water [BUWAL a]


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With exception <strong>of</strong> Loch Lomond, that turns out to be a “reference area”, the 3 lakes are,<br />

in terms <strong>of</strong> pollution, characterised by domestic sewage and its breakdown products.<br />

Although there is also industrial’s effect on the environment, the areas are not dominated<br />

by typical industrial pollution sources. The section hereafter gives a concise description<br />

<strong>of</strong> relevant pollutants in the catchment areas <strong>of</strong> the lakes. For some pollutants<br />

little information is currently available and (in contrast to e.g. heavy metals), and as yet<br />

no test methods and effective screening methods known. Therefore, the picture is still<br />

incomplete.<br />

10.1 CATCHMENT AREA OF LAKE CONSTANCE (BODENSEE)<br />

After Lake Geneva Lake Constance is the second largest lake on the northern edge <strong>of</strong><br />

the Alps [BROMBACH and MICHELBACH 1998]. The lake basin was formed by the<br />

erosive forces <strong>of</strong> the Rhine glacier which excavated a 500 m deep valley during its last<br />

extension, about 30.000 years before the present. At the end <strong>of</strong> this glaciation, 15.000<br />

years ago, the lake area was more than twice its present cover, including large parts <strong>of</strong><br />

the Rhine Valley and both Lake Walen and Lake Zurich. Lake Constance and its 11<br />

487 km² large catchment area belong to the flow system <strong>of</strong> River Rhine [BROMBACH<br />

and MICHELBACH 1998]. The lake is divided into two parts, the upper lake (including<br />

the Überlingersee) and the lower lake (including the Gnadensee and Zellersee). The<br />

Rhine bridge Constance can be taken as the parting line. The contact between both<br />

parts <strong>of</strong> Lake Constance is named Seerhein. The catchment area <strong>of</strong> the upper lake is<br />

10919 km² large. The catchment area <strong>of</strong> the lower lake is only 568 km² large [GURTZ<br />

et al 1997]. The surface <strong>of</strong> the lake is ca. 540 km² large. The catchment area includes<br />

parts <strong>of</strong> the German "Bundesländer" Baden-Wuerttemberg and Bavaria, Austria,<br />

Liechtenstein, Switzerland and Italy. The volume <strong>of</strong> Lake Constance amounts to 48.5<br />

billion m³ and the maximum depth is ca. 254 m. The mean discharge referring to the<br />

tide gauge Constance is ca. 372 m³/s approximating 1.000 mm discharge rate per annum<br />

or a mean dwell <strong>of</strong> 4.1 years in the lake [BROMBACH and MICHELBACH 1998].<br />

In its natural state, Lake Constance was a typical oligotrophic pre-alpine lake with low<br />

concentrations <strong>of</strong> nutrients, low densities <strong>of</strong> phytoplankton, high water transparency and<br />

high hypolimnic oxygen concentrations. Until the early 1970's, the major part <strong>of</strong> this<br />

sewage entered the lake without any treatment, resulting in a strong increase <strong>of</strong> the Pload,<br />

additionally enhanced by increasing inputs from agricultural sources and from<br />

precipitation. At present, 75 % <strong>of</strong> the sewage phosphorus is chemically precipitated in<br />

treatment plants. Further reduction <strong>of</strong> the P-load is expected after completion <strong>of</strong> the<br />

sewage purification programme in large treatment plants. Depending on the remaining<br />

P-load, new lower equilibrium concentrations will be reached in the lake. Thus, this provides<br />

an example <strong>of</strong> a successful restoration programme beyond national borders.The<br />

Lake Constance and its environs is a densely populated area with a Europe-wide relevance.<br />

The ecosystem Lake Constance has an unique flora and fauna and therefore<br />

having a high ecological value. The drinking water for more than 4 million people living<br />

in the neighbouring countries is gained from the lake. The whole drinking water draw-<strong>of</strong>f<br />

from Lake Constance amounts 0.14 km³/a being 1.2 % <strong>of</strong> the yearly intake <strong>of</strong> 11.6<br />

km³/a [BROMBACH and MICHELBACH 1998]. Table 10-1 shows the portion <strong>of</strong> area <strong>of</strong><br />

the countries in the catchment area <strong>of</strong> Lake Constance.<br />

Country Area Part <strong>of</strong> the Forest Agricul- Non- Resi-


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[ha] tural area<br />

[ha]<br />

productive<br />

[ha]<br />

Page 63 <strong>of</strong> 136<br />

dential<br />

estate<br />

[ha]<br />

Upper Lake<br />

Bavaria 58762 5.4 15351 38365 1447 3599<br />

Baden-Wuerttemberg<br />

211998 19.4 58103 130098 3333 20463<br />

Vorarlberg (A) 233539 21.4 71716 127710 25478 8636<br />

Switzerland 519886 47.6 131874 204255 166072 17685<br />

Italy 5400 0.5 75 0 5325 0<br />

Lake area 47600 4.3 0 0 47600 0<br />

Upper Lake total<br />

Lower Lake<br />

109318<br />

5<br />

100.0 283300 506317 251109 52459<br />

Baden-Wuerttemberg<br />

42012 77.0 13910 21424 851 5827<br />

Switzerland 6228 11.4 2503 2881 59 785<br />

Lake area 6300 11.6 0 0 6300 0<br />

Lower Lake total 54539 100.0 16413 24305 7209 6612<br />

Catchment area<br />

total<br />

114772<br />

4<br />

299713<br />

26.1 %<br />

530622<br />

46.2 %<br />

258318<br />

22.5 %<br />

59071<br />

5.1 %<br />

Table 10-1: portion <strong>of</strong> area <strong>of</strong> the countries in the catchment area <strong>of</strong> Lake Constance<br />

[PRASUHN, et al. 1996].<br />

Data <strong>of</strong> Land Use with Relevance to the Water Supply<br />

About 2.2 million people live in the international Lake Constance region, and almost<br />

one million work here. Beside that, this area is also a favourite vacation and recreational<br />

area. In the following the percentage <strong>of</strong> industry agriculture and forestry at the<br />

catchment area is described. (The data are taken from Table 10-1).<br />

Industry: The economic structure is dominated by the manufacturing industry. The<br />

main focus is formed by the mechanical engineering, vehicle construction, electrical<br />

engineering, precision mechanics and optics [Bodenseekreis]..<br />

Agriculture: The contamination <strong>of</strong> soil and groundwater by the high use <strong>of</strong> pesticides<br />

and nitrates in the agriculture is an environmental problem. The climate in the area <strong>of</strong><br />

Lake Constance enables intensive cultivation <strong>of</strong> fruit, wine, vegetables and hops.<br />

Therefore agriculture plays an important role concerning the contamination <strong>of</strong> soil, surface<br />

and ground water in this region. Open land and traditional orchards have given<br />

way increasingly to plantations <strong>of</strong> dwarf fruit trees that require high levels <strong>of</strong> agricultural<br />

chemicals. As a result <strong>of</strong> that, the pollution <strong>of</strong> the lake with pesticides, fertilisers and<br />

petroleum waste has grown. The agricultural area <strong>of</strong> 530622 ha is equivalent to 46.2 %<br />

<strong>of</strong> the total catchment area.


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Figure 10-2: Catchment Area <strong>of</strong> Lake Constance<br />

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Forestry: Poor forestry practices have the potential to pollute water, damage watersheds<br />

and destroy wildlife habitat. The natural ecological process that maintain a<br />

healthy forest can be interrupted by conversion to a monoculture. The run<strong>of</strong>f from disturbed<br />

areas can carry sediment, nutrients, pesticides and fertilisers. Surface and<br />

ground water can be contaminated with these pollutants. The forest area <strong>of</strong> 299713 ha<br />

is equivalent to 26.1 % <strong>of</strong> the total catchment area.<br />

Amounts <strong>of</strong> <strong>Contaminants</strong> in the Catchment Area <strong>of</strong> Lake Constance<br />

It could not be realised to get more information about pesticides via an assessment <strong>of</strong><br />

the used substances in the catchment area <strong>of</strong> Lake Constance. For each border state<br />

there only exist details about the countrywide used pesticides as well as the recommendations<br />

for their special use in the agriculture. From the recommendations <strong>of</strong> use it<br />

could not be deduced the used substances or the amounts [MÜLLER 1993].<br />

Data about Pollution Sources<br />

Beside nutrients an increasing amount <strong>of</strong> other substances are admitted into Lake<br />

Constance. The sources and possible effects are shown in the following figure.<br />

natural indus- traf- naviga- agriculture and<br />

non point<br />

point sources caused<br />

by accidents, discharges,<br />

drain systems<br />

f t t<br />

Pollutants in Lake Constance<br />

Hydrocarbons (especially petrol,<br />

solvents, pesticides, herbicides)<br />

heavy metals<br />

non point point sources<br />

accumula- acutementimpair-<br />

oxygen consump-<br />

f i l l t<br />

tion<br />

during the micobial re-<br />

sediments animals and<br />

l t burden <strong>of</strong> any member <strong>of</strong> the food chain<br />

sub-lethal impairment<br />

<strong>of</strong> the soil bio-<br />

sub-lethalimpairments Figure 10-3: Diagram <strong>of</strong> source and effects <strong>of</strong> pollutants in Lake Constance [according to<br />

UBR 1994]


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The existing threshold values are fixed on the basis <strong>of</strong> the substances toxicity to humans<br />

and not on their ecotoxicity. The threshold values refer on the open water but a<br />

plurality <strong>of</strong> foreign matter was measured partly in higher concentrations in the sediment.<br />

About the impacts <strong>of</strong> these substances is known very less the more so as between different<br />

substances interactions could happen. Aggravating is the fact, that the detection<br />

limit for some substances and groups <strong>of</strong> substances is already relative high. Chronic<br />

toxic impacts and interference <strong>of</strong> natural biological processes like reproduction and<br />

search for food can not be excluded even at very low concentrations [UBR 1994].<br />

In the UBR-study it is mentioned, that the direct discharges into the open water <strong>of</strong> Lake<br />

Constance are caused by navigation because the exhaust gases <strong>of</strong> the outboard motors<br />

are discharged directly into the lake. That way a significant amount <strong>of</strong> the emission<br />

products come into the water like polycyclic aromatic hydrocarbons (PAH) and<br />

emulsified oils. A direct connection between the amount <strong>of</strong> hydrocarbons into the water<br />

and the intensity <strong>of</strong> the shipping traffic on Lake Constance could be proved. The mixture<br />

and the quantity depend very much on the motor type and fuel. At local places high<br />

concentrations are reached. Calculations in 1980 reveal that the emissions caused by<br />

navigation lie approximately at 1120 t highly volatile hydrocarbons for the whole lake.<br />

Approximately 67 % <strong>of</strong> this emissions are caused by sport sips and 50 % by two-stroke<br />

engines. Ecotoxicological surveys have shown that the exhaust gases <strong>of</strong> two-stroke engines<br />

have high toxicological impacts to standardised biological test procedures. For<br />

the four-stroke engines the results have shown lower values.<br />

The input <strong>of</strong> polycyclic aromatic hydrocarbons result particularly from the road dust<br />

contaminated with asphalt particles. The input <strong>of</strong> these pollutants can be prevented by<br />

a purification <strong>of</strong> the surface and street effluents in special plants at the main streets<br />

near the lake [UBR 1994]. An other safety hazard is the transport <strong>of</strong> hazardous goods<br />

on the roads and rail roads near the lake. The annual transport <strong>of</strong> hazardous goods in<br />

the inflow area <strong>of</strong> Lake Constance is substantial, at approximate 3.4 million tonnes. The<br />

ratio <strong>of</strong> road to rail transport is 54:46. The most significant traffic streams are the transport<br />

<strong>of</strong> mineral oil from the Singen region to Konstanz, and further on to the area <strong>of</strong><br />

Switzerland around Lake Constance, and from around Ulm and Freiburg to the area <strong>of</strong><br />

southern Germany around the lake, and further on to Austria [KREUTLER et. al. 2000].<br />

The high concentrations <strong>of</strong> heavy hydrocarbons are found also in younger sedimentation<br />

layers consist <strong>of</strong> minimum 90 % <strong>of</strong> fossil hydrocarbons. The sources <strong>of</strong> these hydrocarbons<br />

can not be named but the emission at several sources can be estimated.<br />

Motorboats are account for approximately 42 t/a, inputs <strong>of</strong> road effluents mount up to<br />

approximately 32.5 t/a, inputs from the burning <strong>of</strong> coal as well as from exhaust fumes<br />

and oil heating. An other aspect are accidents. Between 1988 and 1990 18 000 l oil<br />

were leaked in the administrative district <strong>of</strong> Konstanz. In the period 1986 to 1990 64<br />

300 l water-endangering substances were leaked in the administrative district <strong>of</strong> Bodenseekreis<br />

[UBR 1994].<br />

The UBR-study points out, that volatile hydrocarbons belong to the substances, to be<br />

descended from industrial manufacturing processes and are found in the sediment <strong>of</strong><br />

Lake Constance in higher concentrations. They are used as solvents in great quantities.<br />

To these substances also belong phthalates (plasticizer in plastics) which were emitted<br />

by use. Different heavy metals were partly remobilized from the sediment if the oxygen


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concentration near the sediment surface deteriorates. In 1985 approximately 1.5 t zinc,<br />

755 kg lead and 208 kg copper reaches Lake Constance via road effluents. The main<br />

source <strong>of</strong> these emissions is the road traffic. The untreated surface waters reach the<br />

sewage water system but not a treatment plant and enter the lake unchanged.<br />

Along the busy road B 31 all the direct discharges in Lake Constance will stop not until<br />

the realisation <strong>of</strong> the planned by-pass. The waste water treatment <strong>of</strong> the textile industry<br />

from the region make problems because the state <strong>of</strong> the art according to the pretreatment<br />

is still a contentious issue. The industry is subject to the indirect discharger<br />

directive. In 1988 and 1989 it was ascertained that the threshold values were not be<br />

observed in pre-treatment plants in the administrative district <strong>of</strong> Konstanz [UBR 1994].<br />

Besides agricultural and forestry the source <strong>of</strong> pesticide residues are also weed control<br />

methods at the railways. Official information from the DB (German railway) state that<br />

every year 1.18 to 1.3 g herbicides (diuron tender) per square meter are sprayed. This<br />

way <strong>of</strong> weed control must be stopped at the railways near Lake Constance [UBR 1994].<br />

From 1996 to 1998 five investigations about pharmaceutical products and some byproducts<br />

take place in the catchment area <strong>of</strong> Lake Constance. The water samples from<br />

two sewage treatment plant effluents, the most important feeders <strong>of</strong> Baden-<br />

Wuerttemberg as well as from the nearshore and the open water <strong>of</strong> the "upper lake"<br />

were checked to more than 60 substances. More than one third <strong>of</strong> the substances have<br />

been proved [ROßKNECHT, HETZENAUER 2000]. The authors continue, that mainly<br />

some antibiotics, different antirheumatics and x-raying radio-opaque dye as well as the<br />

antiepileptikum carbamazine and the lipid lowerer cl<strong>of</strong>ibrin acid has been proved more<br />

<strong>of</strong>ten and in higher concentrations. With all these substances travel varying concentration<br />

levels from the sewage treatment plant effluents to the concentrations in the open<br />

water in the middle <strong>of</strong> the lake.<br />

Pesticides Load <strong>of</strong> Lake Constance and Flowing Waters<br />

In [MÜLLER 1993] the results <strong>of</strong> a two years study about the spatial and temporal distribution<br />

<strong>of</strong> pesticides are resumed for Lake Constance. The intention <strong>of</strong> this study<br />

was the result <strong>of</strong> several surveys about pesticides in the ground and surface water<br />

which have shown that different compounds occur in increased concentrations. During<br />

six sampling series in 1990 and 1991 several samples <strong>of</strong> water from the lake, feeders<br />

and outlets have been tested to 80 different pesticides and by-products <strong>of</strong> pesticides.<br />

Substances for which during the first testing period no positive results were found have<br />

not been tested in the second testing period [MÜLLER 1993]. He points out that only<br />

four substances could be found in each sampling: atrazine, desethylatrazine, simazine,<br />

and terbutylazine. Atrazine was found in the water <strong>of</strong> Lake Constance in more<br />

than 90 % <strong>of</strong> the samplings in a constant concentration <strong>of</strong> 0.03 mg/m³ and a maximum<br />

value <strong>of</strong> 0.04 mg/m³. The by-product <strong>of</strong> atrazine desethylatrazine has a detection limit<br />

<strong>of</strong> 0.03 mg/m³ and could not be found in any lake-sampling since the halfway through<br />

1991. Before this time the concentrations were laying between 0.03 and 0.06 mg/m³.<br />

In January 1990 simazine was not provable in any sampling <strong>of</strong> Lake Constance and<br />

reached in July 1990 nearly in each sampling nearly the detection limit. Since February<br />

1991 nearly the same amount <strong>of</strong> 0.02 mg/m³ was measured. Terbutylazine was only<br />

occasionally found in concentrations near the detection limit <strong>of</strong> 0.01 mg/m³ [MÜLLER


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1993]. With the exception <strong>of</strong> the feeders the same substances were found in the water<br />

<strong>of</strong> Lake Constance. The maximum values were always higher than in the lake water<br />

(atrazine 0.12 mg/m³, desethylatrazine 0.014 mg/m³, simazine 0.05 mg/m³, terbutylazine<br />

0.03 mg/m³). On the other hand these substances were multiple not be provable<br />

especially in the Dornbirnerach and sometimes in the Old Rhine. [MÜLLER 1993]<br />

stresses, that beside the four named triazines two more substances - cyanazine and<br />

diuron - and as well the by-products desethysimazine and desethylterbutylazine were<br />

found in some samples <strong>of</strong> the feeders.<br />

In accordance with other investigations like places for drinking water samplings at the<br />

lake the results prove the occurrence <strong>of</strong> low amounts <strong>of</strong> pesticides in the water <strong>of</strong> Lake<br />

Constance. The found concentrations are obviously lower than the permitted limit values<br />

in accordance to the German Drinking Water Directive (for single substances 0.1<br />

mg/m³ and for the summation 0.5 mg/m³) [MÜLLER 1993]. The survey did not produce<br />

alarming results. Nearly 90 % <strong>of</strong> the tested pesticides were not be provable. The total<br />

herbicides atrazine and simazine are contained non-seasonal in traces in the whole<br />

Lake. An effect <strong>of</strong> the substances ban for atrazine being in force since spring 1991 in<br />

Germany has not be recognised during this random sample inquiry.<br />

In the period May 1999 to May 2000 in the flowing water Seefelder Aach, Riedgraben<br />

as well as the sewage treatment plant effluents in Fricken, Biegensegel and Grasbeuren<br />

a continual load <strong>of</strong> pesticides have been detected. 37 <strong>of</strong> the 58 investigated<br />

substances have been found. Withal 84 % <strong>of</strong> all load res. 94 % <strong>of</strong> the measured sewage<br />

treatment plant effluents have shown pesticides whereas up to 8 different active<br />

substances per single probe have been detected. The most commonly measured substances<br />

were the herbicides diuron, simazin, isoproturon, 2,4-D, dichlorprop-P, MCPA<br />

as well as mecoprop-P, the fungicides pyrimethanil, fenarimol, cyprodinil, penconazol<br />

and carbendazim as well as the insecticides primicarb and tebufenozid [SCHLICHTIG<br />

et al. 2001]. From the catchment area <strong>of</strong> the Seefelder Aach al least 9.2 kg active substances<br />

have been entered Lake Constance. The part <strong>of</strong> the pesticide loads from the<br />

sewage treatment plants were 61,5 % <strong>of</strong> the measured total load at the estuary <strong>of</strong> the<br />

Seefelder Aach. Due to degradation processes several <strong>of</strong> the from the sewage treatment<br />

plants emitted substances could not be detected at the mouth <strong>of</strong> the Seefelder<br />

Aach [SCHLICHTIG et al. 2001].<br />

Investigation Programme - Feeders and Measured Parameters<br />

[HETZENAUER 1997] reports about samplings at selected places in the feeders Nonnenbach,<br />

Argen, Schussen, Rotach, Mühlbach Friedrichshafen, Manzeller Bach, Brunnisach,<br />

Lipbach, Kniebach, Dysenbach, Seefelder Aach, Nußbach, Tobelbach, Stockacher<br />

Aach, Mühlbach Randolfzell, Kasernengraben and Radolfzeller Aach has been<br />

performed.<br />

In the period between January 1993 and December 1995 the heavy metals arsenic,<br />

lead, cadmium, chrome copper and zinc and adsorbed organic halogen compounds<br />

(AOX) and volatile halogenated hydrocarbon <strong>of</strong> the group <strong>of</strong> the organic pollutants and<br />

oxygen depleting substances has been analysed. The measuring method for the heavy<br />

metals was the atom absorption spectrometry (AAS) for the AOX the "AOX Automat"


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(kind <strong>of</strong> measuring instrument) was used and the volatile halogenated hydrocarbons<br />

were measured with the headspace gas chromatography.<br />

Heavy Metals<br />

The feeders load with heavy metals is discussed now. For all feeders the 90-percentile<br />

for chrome lies in a range which is deemed to be anthropogenic uncontaminated. The<br />

result for lead is the same apart from the two small feeder Kasernengraben and Mühlbach<br />

Friedrichshafen. Because <strong>of</strong> its varied use zinc is an indicator for anthropogenic<br />

influences. High 50-percentile and peaks are found in the Kasernengraben and in the<br />

Mühlbach Friedrichshafen while the other feeders are minor affected. The 50-percentile<br />

values for cadmium lie under 0.05 µg/l in every feeder so they are classified to be only<br />

slightly burdened. With the exception <strong>of</strong> the Kasernengraben the concentrations for<br />

copper lie in the area <strong>of</strong> a low load in every feeder [HETZENAUER 1997]. The author<br />

continues, that the Institute for Lake Research measures selected heavy metals in the<br />

feeder Schussen since more than 15 years. In this period a reduction <strong>of</strong> the concentration<br />

<strong>of</strong> some metals are recognised. In the period 1984 till 1987 the medium concentration<br />

for arsenic has been reduced from more than 5 µg/l to 1 µg/l and is now constant<br />

on this level. The lead concentrations in the Schussen are also reduced. Both could be<br />

the result <strong>of</strong> a processing conversion <strong>of</strong> an polluter/ discharger. In general, the heavy<br />

metal contamination <strong>of</strong> the Lake Constance feeders in Baden-Wuerttemberg is low till<br />

moderate. An exception are the small feeders Kasernengraben and Mühlbach<br />

Friedrichshafen which <strong>of</strong>ten have higher concentrations.<br />

AOX and Volatile Halogenated Hydrocarbons<br />

The relevant 50-percentile values for the adsorbed organic halogen compounds (AOX)<br />

in 16 <strong>of</strong> the 17 tested feeders lie at 7-14 µg/l. This is a small till moderate contamination.<br />

Because <strong>of</strong> a high 50- and 90- percentile value the Kasernengraben is special.<br />

This high concentrations could be the result <strong>of</strong> sewage discharge as well as <strong>of</strong> contaminated<br />

sides from a former military use. In contrast to the other parameters, at the<br />

group <strong>of</strong> volatile halogenated hydrocarbons only five random samples are analysed in<br />

1995. The compounds bromidchlormethan, brom<strong>of</strong>orm, dibromchlormethan, tetrachlorcarbon,<br />

trichlorethyten, chlor<strong>of</strong>orm, tetrachlorethylen and trichlorethan have been<br />

tested. The four first named compounds always lain below the determination limit <strong>of</strong> ca.<br />

0.1 µg/l. The other four volatile halogenated hydrocarbons were found only in some<br />

feeders, especially in the Kasernengraben (maximum value 2.6 µg/l for trichlorethylen,<br />

1.7 µg/l for chlor<strong>of</strong>orm) and in the Mühlbach Friedrichshafen (maximum value 2.1 µg/l<br />

for tetrachlorethylen). Chlor<strong>of</strong>orm values higher than 1 µg/l are classified as an increased<br />

burden. The maximum value in the Kasernengraben is higher than this value.<br />

In the rivers Schussen, Randolfzeller Aach, Seefelder Aach, Rotach, Stockacher Aach<br />

and Nonnenbach only some volatile halogenated hydrocarbons could be measured. All<br />

the measured concentrations are lower than 0.25 µg/l [HETZENAUER 1997].<br />

Summary <strong>of</strong> the Situation at Lake Constance Concerning Endocrine Disrupters<br />

As shown, several active substances like pesticides and heavy metals have been detected<br />

in the water <strong>of</strong> the Bodensee and in investigated feeders. Due to the numerous<br />

flowing waters in the Lake Constance catchment and the high measured pesticide<br />

loads SCHLICHTIG et al 2001 emphasising the need <strong>of</strong> further controls <strong>of</strong> the small


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flowing waters to protect the aquatic communities. Because <strong>of</strong> its high volume the pesticide<br />

load from the Seefelder Aach cause no risk for the lake but the catchment <strong>of</strong> this<br />

flowing water is only a small part <strong>of</strong> 2.4 % <strong>of</strong> the whole catchment area <strong>of</strong> the Bodensee.<br />

In comparison <strong>of</strong> the 17 feeders <strong>of</strong> Lake Constance in Schussen, Mühlbach Randolfzell<br />

and Mühlbach Friedrichshafen increased concentrations are found. Even higher concentrations<br />

are found in the Kasernengraben and can be named as “heavy contaminated”.<br />

The survey <strong>of</strong> [HETZENAUER 1997] shows, that even small feeders <strong>of</strong>ten are<br />

contaminated with higher concentrations. This small feeders are not so important for<br />

the overall loads flowing into Lake Constance. But higher concentrations could be local<br />

harmful to the nearshore in the estuary. (For the limnological condition <strong>of</strong> Lake Constance<br />

this area play an important part. For this reason it is necessary to reduce also<br />

the contamination <strong>of</strong> the small feeders to a tolerable level.<br />

In the survey <strong>of</strong> SCHLICHTIG et al 2001 a total diuron load <strong>of</strong> 40 % have been detected<br />

in the Seefelder Aach. This cannot be the result <strong>of</strong> the agricultural diuron use and<br />

causes the research need in non-agricultural areas.<br />

10.2 CATCHMENT AREA OF LAKE GENEVA (LAC LÉMAN)<br />

Lake Geneva is located in the Alps and <strong>of</strong> glacial origin is bordered by Switzerland in<br />

the north and France in the south. The lake is divided in two parts, the "small lake" and<br />

the "large lake" (Figure 10-4). The "small lake" in the west part has a volume <strong>of</strong> 3 km³, a<br />

maximum depth <strong>of</strong> 76 m and a water surface <strong>of</strong> 81.2 km². The eastern "large lake" has<br />

a volume <strong>of</strong> 86 km³, a maximum depth <strong>of</strong> 309.7 m and a water surface <strong>of</strong> 498.9 km².<br />

Lake Geneva has a surface <strong>of</strong> 580.1 km² where<strong>of</strong> 234.8 km² are located in France and<br />

345.3 km² in Switzerland (cantons Waadt, Wallis and Geneva). The mean volume<br />

come to 89 km³ and the mean rate <strong>of</strong> discharge between 1935 and 1996 were 250<br />

m³/s. The theoretical retention time <strong>of</strong> the water is 11.4 years [CIPEL 200a].


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Figure 10-4: Lake Geneva [CIPEL 2000a]<br />

Page 71 <strong>of</strong> 136<br />

The catchment area with the lake mount up to 7 975 km² and without the lake to 7 393<br />

km². 890 km² <strong>of</strong> this area belong to France and 6 503 km² to Switzerland (Figure 10-5).<br />

The most important kinds <strong>of</strong> land use are forests (22 %), pastures (23 %), arable land<br />

(20.5 %) and non arable areas (34.5 %). The 1 515.5 km² arable land is distributed as<br />

follows: 63.1 % meadows, 26.7 % fallow land, 6.6 % vines, 2.6 % intensive orchards<br />

and 1 % vegetable growing. The catchment area <strong>of</strong> Lake Geneva has a population <strong>of</strong><br />

904 550 people [CIPEL 200a]. Figure 10-6 and Figure 10-7 show the situation concerning<br />

population, industry and tourism res. the land use in the catchment.<br />

Figure 10-5: Catchment Area <strong>of</strong> Lake Geneva [CIPEL 2000a]


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Land Use and Industry in the Lake Geneva Catchment<br />

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Figure 10-6 shows the proportion <strong>of</strong> population, industry and tourism in the Lake Geneva<br />

catchment. Important industries are chemical industry, mechanics, power plants,<br />

ironworks and cement works and clock industry. The locations with the highest population<br />

are in the areas <strong>of</strong> Geneva, Lausanne, Nyon, Evian and Montreux .<br />

Figure 10-6: Population, industry and tourism in the Lake Geneva Catchment Area [CIPEL<br />

2000a<br />

Regarding the land use in this area Figure 10-7 gives an overview. Near the lake shore<br />

extensive and intensive cultivation are dominating beside areas used for viniculture.<br />

Beside this, there are although forests as well as pastures and meadows.


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Figure 10-7: Land use in the Catchment Area <strong>of</strong> Lake Geneva [CIPEL 2000a]<br />

Drinking Water Extraction and Sewage Treatment<br />

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Lake Geneva is one <strong>of</strong> the greatest drinking water reservoirs in West Europe. After a<br />

simple treatment the water can be used as drinking water. At Lake Geneva there are 11<br />

<strong>of</strong> such treatment plants. Metals dissolved in the water and unnatural micro-pollutants<br />

are hardly or not removed by this treatment. Currently, in the middle <strong>of</strong> the lake the<br />

water comply with the legal requirements for drinking water concerning all measured<br />

substances like e.g. metals and pesticides but some <strong>of</strong> them could be proved in traces.<br />

Although the concentrations are low they are undesired [CIPEL 2000c]. In the catchment<br />

area <strong>of</strong> Lake Geneva 80 % <strong>of</strong> the population have a connection to a sewage<br />

treatment plant in 1991 and now in 2000 there are 90 % [CIPEL 2000d].<br />

Pollution Situation in Lake Geneva<br />

There are no systematic studies <strong>of</strong> occurrence <strong>of</strong> natural or synthetic estrogens in Switzerland.<br />

The environment can be influenced by the load <strong>of</strong> hormonal active substances.<br />

But today the degree <strong>of</strong> this influence can not be assessed because there are exist only<br />

a few investigations about and the complexity <strong>of</strong> the effect mechanisms. The inadequate<br />

knowledge about pollution in Switzerland and the possible disturbances associated<br />

with it point to a requirement for research. There is a need for research into identifying<br />

endocrine disrupters, characterisation <strong>of</strong> their effects and risk assessment<br />

[BÄTSCHER et al. 1999]. In Switzerland approximately 400 active substances are<br />

authorised in pesticides. For ground water the threshold value is 0.1 µg/l for the single<br />

substance res. 0.1 µg/l for a single pesticide [BUWAL a].<br />

At the monitoring <strong>of</strong> 12 flowing waters pesticides have been proved. The concentrations<br />

were low but in certain situations there is a risk for the water biology. Triazine contain-


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ing herbicides are still proved in the lake water. Although their concentration is low and<br />

below the threshold value for drinking water is their presence undesired [CIPEL 2000d].<br />

More than 800 industry plants are registered but the situation is not serious because all<br />

have their own treatment plant or are connected to a sewage treatment plant. It seems<br />

that concerning the micro-pollutants like e. g. pesticides and heavy metals no important<br />

problems exist. But it is more difficult to made an exactly estimation because only few<br />

measurements are made. According to the amounts <strong>of</strong> the measured parameters in the<br />

different compartments like natural habitats, sewage treatment plant effluents, industrial<br />

discharges and sewage sludge there are great differences. Because <strong>of</strong> this it is difficult<br />

to estimate the true influence <strong>of</strong> the industry to the natural habitats <strong>of</strong> the Lake Geneva<br />

catchment. The control <strong>of</strong> certain micro-pollutants having an negative effect to the biocenosis<br />

already in low concentrations are not part <strong>of</strong> the regular monitoring program yet<br />

[CIPEL 200d].<br />

The amounts <strong>of</strong> mercury, lead, cadmium, chrome, copper, manganese and iron measured<br />

in the water <strong>of</strong> Lake Geneva are very low and the requirements concerning the<br />

drinking water and the habitat for fishes are warranted. Investigations concerning pesticides<br />

and NTA and EDTA are also made. Very low amounts <strong>of</strong> herbicides, atrazine, simazine<br />

and terbutylazin are measured. These concentrations are below the standard<br />

for drinking water. The registered reduction <strong>of</strong> mercury charges in fish could be affirmed.<br />

The mercury and PCB concentrations in fish are harmless. On the basis <strong>of</strong> a<br />

standard-table to rate the content <strong>of</strong> metal in mussels (species Dreissena) the following<br />

propositions can be made:<br />

— Concerning cadmium, they are extremely burdened at the river banks near Bouveret,<br />

Thonon, Meillerie and near Dranse and Hermance, medium burdened at<br />

other locations,<br />

— There is a medium burden with chrome, copper, zinc and nickel at every location<br />

but some are near the level polluted,<br />

— Concerning lead there is a medium burden for Versoix, Promenthouse, Venoge,<br />

Lutry, Vidy and Thonon, other locations are not burdened [CIPEL 2000b].<br />

Between 1995 and 1997, 22 flowing waters have been explored. The biological water<br />

quality deteriorate top down. This impairment is caused by several anthropogenic ascendancies.<br />

Although certain impairments caused by nutrients and organic material are<br />

reduced by sewage treatment other replace them. For example pesticides, alluvial<br />

matters and degradation <strong>of</strong> shore vegetation. The water quality <strong>of</strong> only one third <strong>of</strong> the<br />

investigated Waadt's rivers is acceptable at their inflow into Lake Geneva [CIPEL<br />

2000b].<br />

A Swiss exploration about the influence <strong>of</strong> sewage treatment plant effluents (three <strong>of</strong><br />

the treatment plants are in the Lake Geneva catchment) shows that such effluents have<br />

in some cases a negative effect to the development <strong>of</strong> fishes [CIPEL 2000d].<br />

During the use <strong>of</strong> pesticides these products are proved in rivers. In certain cases these<br />

concentrations could be a threat to the biological condition <strong>of</strong> water bodies. Therefore


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regularly controls and investigations about the sources <strong>of</strong> these substances are necessary<br />

[CIPEL 2000d].<br />

Measurements and Investigation Programs Concerning Pollutants in Lake Geneva<br />

DDT and metabolites: In twelve feeders <strong>of</strong> Lake Geneva the o,p'- and p,p'-isomers <strong>of</strong><br />

DDT, DDD and DDE have not been found in 1997. The detection limits <strong>of</strong> these substances<br />

are between 0.05-0.1 µg/l. In a older study <strong>of</strong> 1979 the concentrations <strong>of</strong> DDT<br />

and its metabolites (p,p'-isomers) were measured in the sediments <strong>of</strong> Lake Geneva.<br />

The upper 2 cm <strong>of</strong> the sediment contained concentrations between 0.5 and 49 µg/kg<br />

dry weight <strong>of</strong> DDT and metabolites. This load was mainly composed by p,p'-DDD and<br />

p,p'-DDE, p,p'-DDT was only found sporadically. In 1982/1983 samples from the estuaries<br />

(Mündungsregionen) <strong>of</strong> the most important feeders and from sediments <strong>of</strong> Lake<br />

Geneva were tested. In every sediment sample <strong>of</strong> Lake Geneva p,p'-DDT was found in<br />

medium concentrations <strong>of</strong> 4.2 µg/kg dry weight and maximum values <strong>of</strong> 14.4 µg/kg. In<br />

the sediments <strong>of</strong> the estuaries concentrations up to 22 µg/kg were detected. In the water<br />

<strong>of</strong> Lake Geneva no isomers <strong>of</strong> DDT or its metabolites were measured at a detection<br />

limit <strong>of</strong> 0.05-0.1 µg/l [BÄTSCHER et al. 1999]. Between 1984 and 1993 the concentrations<br />

<strong>of</strong> p,p'-DDE in some fish species were proved and showed a decreasing tendency.<br />

The existing data are insufficient to derive a general decreasing tendency from<br />

that [BÄTSCHER et al. 1999].<br />

PCB: Surface sediments from the estuaries <strong>of</strong> important feeders are investigated between<br />

1982 and 1990 to their PCB-load. The total concentrations <strong>of</strong> most <strong>of</strong> the samples<br />

were between 25 and 200 µg/l dry weight. A consistent temporal trend <strong>of</strong> the PCBload<br />

could not be found. In 1978 the total load with PCB in the sediment <strong>of</strong> Lake Geneva<br />

has a medium concentration <strong>of</strong> 43 ± 28 µg/kg dry weight and 1983 at 47 ± 24<br />

µg/kg dry weight. In 1979 between 20 and 540 µg PCB/kg dry weight were found in 15<br />

sediment samples. From a perennial measuring program PCB-data <strong>of</strong> Lake Geneva are<br />

available permitting predications about the temporal trend (zeitlicher Verlauf) <strong>of</strong> the<br />

load.1995 Dreissena polymorpha living in the estuary <strong>of</strong> 12 investigated feeders <strong>of</strong> Lake<br />

Geneva were tested to their PCB-load. At 11 locations the total concentrations were<br />

between 100 and 500 µg PCB/ kg dry weight. The highest values were measured with<br />

approximately 2500 µg PCB/kg dry weight in mussels from the Venoge estuary<br />

[BÄTSCHER et al. 1999].<br />

Lindane, Endosulfan and Vinclozolin: Between 1992 and 1996 twelve feeders <strong>of</strong><br />

Lake Geneva have been explored but lindane (γ-HCH) was found in any flowing water<br />

at a detection limit was 50 ng/l. Samples showed that no HCH (α, β, γ, δ) were detected<br />

at detection limits <strong>of</strong> 50-100 ng/l [BÄTSCHER et al. 1999]. In 1995/1996 twelve feeders<br />

<strong>of</strong> Lake Geneva have been explored but endosulfan was not measured at a detection<br />

limit <strong>of</strong> 50 ng/l [BÄTSCHER et al. 1999]. Vinclozolin have never been detected in the<br />

water <strong>of</strong> Lake Geneva during several measuring campaigns between 1992 and 1995.<br />

The detection limit was 100 ng/l [BÄTSCHER et al. 1999].<br />

Antifouling Compounds: Antifouling paints prevent or retard the growth <strong>of</strong> algae,<br />

bacteria and shellfish on ships’ hulls. However, organotin compounds are among the


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most toxic substances for aquatic organisms [BUWAL b]. In Switzerland no authorised<br />

agricultural pesticide containing TBT but it is still used for wood treatment and has other<br />

industrial applications [BECKER-VAN SLOOTEN AND TARRADELLAS, 1994]. On the<br />

1 st <strong>of</strong> July 1988 a Swiss legalisation came into force banning the selling <strong>of</strong> antifouling<br />

paints containing trialcyl- or triaryltins. Importers and sellers were allowed two years <strong>of</strong><br />

dispose <strong>of</strong> their stock. The selling <strong>of</strong> antifouling paint containing these compounds was<br />

illegal after 1 st <strong>of</strong> July 1990. In France the use <strong>of</strong> TBT-containing antifoulings has been<br />

forbidden since 1982 for vessels less than 25 m in length. [BECKER-VAN SLOOTEN<br />

AND TARRADELLAS, 1994/1995]. Nowadays antifouling products contain besides<br />

copper a triazine compound which is effective against algae [BUWAL b]. In the marina<br />

<strong>of</strong> Lake Geneva only every fourth boat is painted annually and the boats left in the water<br />

during winter [BECKER-VAN SLOOTEN AND TARRADELLAS, 1994]. [BECKER et<br />

al 1992] showed high organotin levels in Lake Geneva in 1988 just as the ban came<br />

into force. In this work it was shown that the TBT contamination <strong>of</strong> water, sediment and<br />

bivalves was higher in Swiss marinas <strong>of</strong> Lake Geneva than in the French marinas. This<br />

study <strong>of</strong> [BECKER et al 1992] was designed to compare the organotin concentrations in<br />

marinas within two countries - Switzerland and France - having different legislation.<br />

Water, sediment and mollusc samples were collected from three Swiss and two French<br />

marinas (Figure 10-8). As a reference, a natural site was chosen away from sources <strong>of</strong><br />

organotin compounds, but presenting similar characteristics to a marina like a sheltered<br />

and shallow site. The results <strong>of</strong> the assessment <strong>of</strong> butyl- and phenyltin compounds in<br />

Lake Geneva are reported in Each value i a mean <strong>of</strong> 6 samples (3 stations each with<br />

one surface and one bottom sample) except for the reference point (2 stations). The<br />

range is indicated below in parantheses. TPT has not been detected. (nd = not detected,<br />

CH = Switzerland, F = France)<br />

Table 10-2, Table 10-3 and Table 10-4. the TBT concentrations ranged from not detected<br />

to 1.08 µg/l in water and from 0.03 to 4.76 µg/g dry weight in sediment. The<br />

Swiss marinas were up to 20 times more contaminated than the French ones. This difference<br />

was more pronounced for the water than for the sediment. Partly it can be explained<br />

by the fact that the use <strong>of</strong> antifouling paints is regulated in France since 1982.<br />

Furthermore, the values might reflect the degree <strong>of</strong> flushing as Geneva and Lausanne<br />

are the most enclosed marinas with the poorest water exchange. Generally the aqueous<br />

concentrations <strong>of</strong> DBT and TBT measured in June were higher than in September.<br />

This can result from the typical spring activities like hosing operations and launching <strong>of</strong><br />

the yachts .


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Figure 10-8: Sampling Locations in Lake Geneva [BECKER et al 1992]<br />

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All water and sediment samples contained more TBT than DBT suggesting that degradation<br />

takes place assuming that the primary input <strong>of</strong> butyltin to these areas is from<br />

TBT-based antifouling paint. The organotin levels in water were lower than in sediment,<br />

which confirms that they appear to concentrate there. The natural site showed concentrations<br />

below those observed in the marinas, but nevertheless organotin compounds<br />

could be detected. This indicates that the contamination extends outside the marinas<br />

onto the banks <strong>of</strong> Lake Geneva. The possibility that other important TBT sources exist<br />

seems improbable. TPT has been detected in sediments <strong>of</strong> each location but it was always<br />

present at lower concentrations than TBT [BECKER et al 1992].<br />

The measurements showed that the molluscs contained high levels <strong>of</strong> organotins, especially<br />

those collected in Swiss ports (Table 10-4). At Port d’Ouchy / Lake Geneva<br />

TBT was found in mussels in mean annual values (Jahresmittelwerte) <strong>of</strong> about 24 – 35<br />

mg/kg dry weight. During the measuring period between 1990 – 1993 no reduction <strong>of</strong><br />

the TBT concentrations at Lake Geneva could be recognised The study <strong>of</strong> [BECKER et<br />

al 1992] indicates an important organotin contamination <strong>of</strong> Lake Geneva marinas,<br />

which has reached a critical level for the most sensitive species.<br />

A study <strong>of</strong> [BECKER-VAN SLOOTEN AND TARRADELLAS, 1994] was designed to assess<br />

the effects <strong>of</strong> the new Swiss law. The tributyltin concentrations have been measured<br />

in the water <strong>of</strong> one station <strong>of</strong> Lake Geneva marina between May 1990 and October<br />

1993. The maximum values with more than 700 ng/l have been measured in spring<br />

although - according a survey - 82 % <strong>of</strong> the boats staying in the water the whole year.<br />

Because <strong>of</strong> that it can be conjecturable that metabolism, sorption to particles and sedimentation<br />

having an influence to the reduction <strong>of</strong> the concentrations during the winter<br />

time. In general, concentrations rise in summer when the pleasure boat activities are<br />

most important and decrease in autumn. The organotin concentrations <strong>of</strong> Lake Geneva<br />

marina sediment did not decrease between 1990 and 1993. The sediment concentra-


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tions (2 cm depth) in the measured harbour at Lake Geneva are for TBT in the range <strong>of</strong><br />

660 to more than 5000 µg/kg dry weight and for TPT between 118 and approximately<br />

1800 µg/kg. In comparison to other Lakes in the same study, the marina <strong>of</strong> Lake Geneva<br />

showed the highest contamination. The TPT concentrations were always lower<br />

than TBT concentrations. In 1993 TPT was not measured and the highest level reached<br />

by TPT was 0.9 µg/g dw in Lake Geneva marina in September 1990. The butyltin concentrations<br />

in zebra mussel tissue <strong>of</strong> Lake Geneva marina over the 4-year period<br />

showed no decrease <strong>of</strong> the contamination. The annual concentrations actually increased.<br />

Furthermore, the TBT concentrations were quite stable throughout the year<br />

and no clear summer-winter pr<strong>of</strong>ile was detectable. Irgarol 1051 is the trade name <strong>of</strong> a<br />

triazine herbicide (2-methylthio-4tert-butylamino-6-cyclopropylamino-s-triazine). After<br />

the ban <strong>of</strong> organotin compounds in antifouling paints in Switzerland in 1990 they were<br />

replaced by Irgarol 1051 and copper based products [TÓTH et al 1996]. In the study <strong>of</strong><br />

[TÓTH et al 1996] two marinas and one reference site were chosen in Lake Geneva.<br />

The samples were collected between August 1994 and April 1995. The present Irgarol<br />

1051 concentrations in water <strong>of</strong> Lake Geneva marinas do not reach the acute toxic levels<br />

for algae but an ecotoxic long-term effect on phytoplankton, algae and macrophytes<br />

cannot be excluded.<br />

Location Butyltin concentratíon (µg/L)<br />

June 1988 September 1988<br />

DBT TBT DBT TBT<br />

Geneva (CH) 0.014<br />

0.299<br />

0.005<br />

0.049<br />

(nd - 0.083) (nd - 1.079) (nd - 0.022) (nd - 0.087)<br />

Lausanne (CH) 0.072<br />

0.271<br />

0.037<br />

0.123<br />

(nd - 0.0103) (0.077 - 0.377) (nd - 0.065) (0.079 - 0.170)<br />

Montreux (CH) 0.061<br />

0.353<br />

0.005<br />

0.041<br />

(nd - 0.243) (nd - 0.695) (nd - 0.011) (nd - 0.106)<br />

Thonon (F) nd 0.015<br />

0.003<br />

0.026<br />

(nd - 0.063) (nd - 0.008) (nd - 0.045)<br />

Yvoire (F) nd 0.047<br />

0.007<br />

0.045<br />

Reference (CH) nd<br />

(nd - 0.064)<br />

0.013<br />

(nd - 0.053)<br />

(nd - 0.010)<br />

0.002<br />

(nd - 0.008)<br />

(nd - 0.015)<br />

0.004<br />

(nd - 0.015)<br />

Each value i a mean <strong>of</strong> 6 samples (3 stations each with one surface and one bottom sample)<br />

except for the reference point (2 stations). The range is indicated below in parantheses.<br />

TPT has not been detected. (nd = not detected, CH = Switzerland, F = France)<br />

Table 10-2:Concentrations <strong>of</strong> butyltins in water <strong>of</strong> Lake Geneva marinas and one natural<br />

site (reference) [BECKER et al 1992]


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Location Organotin concentration (µg/g dry weight)<br />

DBT* DBT TBT* TBT TPT* TPT<br />

(mean) (mean) (mean)<br />

Geneva (CH) 1 0.175<br />

1.495<br />

0.213<br />

2 0.158 0.191 0.686 0.983 0.062 0.137<br />

3 0.239<br />

0.767<br />

0.137<br />

Lausanne (CH) 1 0.285<br />

1.086<br />

0.211<br />

2 0.465 0.865 1.814 2.555 0.148 0.424<br />

3 1.846<br />

4.764<br />

0.912<br />

Montreux (CH) 1 0.448<br />

1.517<br />

0.171<br />

2 0.056 0.202 0.176 0.643 0.028 0.081<br />

3 0.103<br />

0.236<br />

0.043<br />

Thonon (F) 1 0.047<br />

0.244<br />

0.065<br />

2 0.103 0.129 0.470 0.426 0.032 0.037<br />

3 0.237<br />

0.564<br />

0.014<br />

Yvoire (F) 1 0.026<br />

0.137<br />

0.017<br />

2 0.101 0.061 0.248 0.204 0.010 0.042<br />

3 0.056<br />

0.227<br />

0.100<br />

Reference (CH) 1 nd 0.007 0.027<br />

0.020 0.011<br />

2 0.014<br />

0.040 0.034 0.002<br />

* Each value is a mean <strong>of</strong> two analyses <strong>of</strong> the same sample (top 2 cm)<br />

Table 10-3: Concentration <strong>of</strong> organotins in sediment <strong>of</strong> Lake Geneva marinas and one<br />

natural site (reference) [BECKER et al 1992]<br />

Location Organotin concentration (µg/g wet weight)<br />

June 1988 September 1988<br />

DBT* TBT TPT DBT TBT TPT<br />

Geneva (CH) Dp 1.390 9.337 2.796 4.161 8.376 3.337<br />

Ac x x x 0.101 1.596 nd<br />

Lausanne (CH) Dp 0.416 5.632 nd 1.784 7.936 2.290<br />

Ac x x x 0.209 1.222 nd<br />

Montreux (CH) Dp 0.178 2.378 0.615 2.182 6.014 1.025<br />

Ac 0.187 1.678 0.072 0.081 0.701 nd<br />

Thonon (F) Dp 0.297 3.964 nd 0.606 4.039 nd<br />

Ac 0.059 0.279 nd 0.107 0.608 nd<br />

Yvoire (F) Dp x x x 0.716 3.238 nd<br />

Ac<br />

Reference (CH) Dp<br />

Ac<br />

0.145<br />

0.119<br />

0.044<br />

0.875<br />

1.466<br />

0.332<br />

nd<br />

nd<br />

0.079<br />

0.155<br />

0.336<br />

0.049<br />

1.066<br />

2.147<br />

0.244<br />

Each value represents one composite sample.<br />

Dp = Dreissena polymorpha, Ac = Anodonia cygnaea, nd = not detected, x = no data available<br />

Table 10-4: Concentrations <strong>of</strong> organotins in bivalves <strong>of</strong> Lake Geneva marinas and one<br />

natural site (reference) [BECKER et al 1992].<br />

nd<br />

nd<br />

nd


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10.3 THE CATCHMENT AREA OF BOURGET LAKE (LAC DU BOURGET)<br />

Lac du Bourget located in the Alps is the largest natural French lake. It has a length <strong>of</strong><br />

18 km with a maximum width <strong>of</strong> 3.2 km. The surface area is 44.6 km² and the maximum<br />

depth is 145 m. Bourget Lake has an estimated volume <strong>of</strong> 3.6 x 10 9 m 3 and the average<br />

discharge rate is 16 m³/s. The main inflow to Bourget Lake is the River Leysse. It has a<br />

number <strong>of</strong> significant tributaries, rising in the Bauges and Chartreuse massifs. The main<br />

river flows for a distance <strong>of</strong> about 30 km, passing through city <strong>of</strong> Chambéry, before<br />

discharging into the southern end <strong>of</strong> the lake. The estimated hydraulic load to the lake<br />

is about 5 x 10 5 m 3 and the theoretical water retention time has been calculated to be<br />

about 7 years.<br />

The catchment <strong>of</strong> Bourget Lake is approximately 560 km 2 in area, 12.5 times greater<br />

than the area <strong>of</strong> the lake. With the main part in the south and east part <strong>of</strong> the lake.<br />

The Bourget watershed (Savoie department) is composed <strong>of</strong> sixty communes (territorial<br />

divisions), and main <strong>of</strong> them are still rural (agricultural location). The catchment area<br />

can be divided into six sub-catchments. Five <strong>of</strong> these sub-catchments are based on the<br />

main inflows to the lake. These are the Leysse, Belle Eau, Sierroz, Tillet, and<br />

Chautagne rivers. The other sub-catchment, the Montagne du Chat, is not a major<br />

inflow.<br />

Figure 10-9:Location <strong>of</strong> Bourget Lake in France (Source: SOGREAH)<br />

The largest sub-catchment is that <strong>of</strong> the River Leysse (ca. 320 km 2 ) which is grouped<br />

with the adjacent, but much smaller, Belle-Eau sub-catchment (12 km 2 ). The River


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Chautagne sub-catchment lies to the north <strong>of</strong> the lake and the Montagne du Chat subcatchment<br />

is located to the west <strong>of</strong> the lake.<br />

The Bourget Lake catchment is also characterised by groundwater flow. Aquifers are<br />

found in an area <strong>of</strong> about 25 km 2 within the Chambéry valley. The aquifer is drained by<br />

pumped wells to supply drinking water to Chambéry and also via the Belle Eau inflow.<br />

Bourget Lake is a very popular recreational site for a large range <strong>of</strong> activities both on<br />

the water and around the shore. But it is also an important source <strong>of</strong> drinking water for<br />

local municipalities<br />

Bourget Lake is an important resource both for supplying drinking water. It is also an<br />

attractive area <strong>of</strong> the Savoie department and <strong>of</strong> the Rhône-Alpes region. For example,<br />

the lake’s beaches attract more than 450,000 bathers every year. The lake is also used<br />

as a site for various water sports e.g. rowing, sailing, windsurfing, water skiing and<br />

yachting. Other visitor activities associated with the lake and catchment are walking,<br />

cycling, climbing, angling, etc. In addition, commercial activities such as pr<strong>of</strong>essional<br />

fishing are also important with 80 tonnes <strong>of</strong> fish being caught every year at an<br />

estimated value <strong>of</strong> 2 million francs (300,000 euros).


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Figure 10-10: Catchment Area <strong>of</strong> Bourget Lake (Source: SOGREAH)<br />

Red line shows the Leysse watershed<br />

Page 82 <strong>of</strong> 136


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The Chambéry and Aix les Bains area is a very urban area with specific orchards on La<br />

Motte Servolex. Chambéry, expect the city, are some agricultural area near the city. La<br />

Motte Servolex with orchards and in the south vine. On the west side and east <strong>of</strong> the<br />

lake between Aix les Bain and Chautagne there are many forests. In the north part <strong>of</strong><br />

the catchment in the Chautagne area are agriculture and forests and in the Albanais<br />

area are cattle and pigs.<br />

The upland areas <strong>of</strong> the Leysse catchment, i.e. the catchments <strong>of</strong> the upper Leysse<br />

and the Hyère-Albanne tributaries, are mainly rural. Agriculture and cattle farming predominate,<br />

although this is limited by the steep gradients, the climate and the inaccessibility<br />

<strong>of</strong> the area. Forests cover approximately 50 % <strong>of</strong> land in this part <strong>of</strong> the catchment.<br />

In contrast, the lowland areas <strong>of</strong> the Leysse catchment are much more heavily<br />

populated (> 650 per km 2 ), urbanised and industrialised, particularly in the environs <strong>of</strong><br />

the city <strong>of</strong> Chambéry. Outside the urban areas, fruit, wine and cereal production is well<br />

developed. There is an average population density <strong>of</strong> 321 people per km 2 in the whole<br />

catchment.<br />

Pollution Sources and Antropogenic impacts<br />

In the Bourget Lake catchment area are 15 sewage treatment plants with a total<br />

capacity <strong>of</strong> 387 450. Details are listed in Table 10-5.<br />

Name Capacity <strong>of</strong> sewage treatment plant<br />

Aix les Bains 70000<br />

Albens 3000<br />

La Boille 1500<br />

Le Bourget du Lac 4500<br />

Chambéry 290000<br />

Chindrieux 1000<br />

Conjux 300<br />

Les Deserts 150<br />

La Féclaz 2500<br />

Ruffieux 600<br />

Saint Félix 10700<br />

St Thibaud de Couz 200<br />

Serrières 600<br />

Technolac 2000<br />

Le Montcel 400<br />

Table 10-5: Sewage treatment plants in the Bourget Lake catchment<br />

Despite Bourget Lake’s attractive appearance, it is vulnerable to anthropogenic impacts<br />

that affect its fragile biological balance. The main threats to its ecological status are<br />

thought to be from the impacts <strong>of</strong> diffuse agricultural pollution (e.g. pesticides and<br />

nutrient enrichment), transport related pollution (e.g. run-<strong>of</strong>f from roads and accidental<br />

spillage) and domestic and industrial effluents (particulary from Chambéry and Aix-les-<br />

Bains). Most <strong>of</strong> the domestic and industrial effluents are re-routed after treatment


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directly to the Rhône river, downstream the Bourget Lake. Since effluents re-routing.<br />

phosphorus concentration in the lake is significantly decreasing. However, nitrate<br />

concentration in the lake is just a little decreasing<br />

Pesticides such as herbicides, insecticides and fungicides are used in agriculture like<br />

vine culture, cereal growing and orchards (cp. with the description <strong>of</strong> land use described<br />

before). Several products are used like e. g. diuron, simazine, alachlor, therbutylazine<br />

and lindane. Beside the agricultural usage there is also a non agricultural use <strong>of</strong><br />

pesticides. An application takes place on rail roads, roads, highways in cities, on<br />

airports on golf courses and in forests (e. g. diuron, oxadiazon, gyphosate etc.). In the<br />

departement <strong>of</strong> Savoie 6-7 t herbicides are used for non agricultural application and 65<br />

t for agricultural use [Chaton N., 1997]. Pesticide quantity used by year on the lake<br />

catchment area was estimated at 16 t in 1997 [Chaton N., 1998].<br />

Monitoring Programme<br />

Unfortunately there are no data about surveys available so nothing can be said with<br />

certainty about the concentrations <strong>of</strong> the used pesticides in the water and sediment <strong>of</strong><br />

Bourget Lake or some important feeders.<br />

10.4 CATCHMENT AREA OF LOCH LOMOND<br />

In terms <strong>of</strong> surface area (70.6 km²), Loch Lomond is the largest body <strong>of</strong> fresh water in<br />

Scotland and the second largest in volume (around 2.6 x 10 9 m 3 ). It is situated 32 km to<br />

the north-west <strong>of</strong> Glasgow [SEPA 2000c].<br />

The Loch Lomond basin is <strong>of</strong> glacial origin with deposited eroded material forming a<br />

dam at the southern end <strong>of</strong> the lake. The Lake is complex and varied in shape consisting<br />

<strong>of</strong> two main basins although there are a number <strong>of</strong> smaller subsidiary ones. The<br />

lake basin pr<strong>of</strong>ile reflects the differences in the topography <strong>of</strong> the surrounding land. The<br />

top north part <strong>of</strong> the loch is long (around 20 km), narrow (maximum width <strong>of</strong> 1.5 km)<br />

and very deep (depths to 189.9 m) compared to the large wide (maximum width <strong>of</strong> 8.8<br />

km) and shallow area (typically between 5 and 20 m depth at southern end) <strong>of</strong> the<br />

south end [SEPA 2000c]. The mean rate <strong>of</strong> discharge is 8.3 m³/s and the theoretical<br />

water retention time are 2 years.<br />

The Loch Lomond catchment area is 769 km² in size. This total area is made up <strong>of</strong> a<br />

lake surface <strong>of</strong> 71 km², a natural catchment area <strong>of</strong> 696 km² plus three areas <strong>of</strong> catchment<br />

capture around Loch Sloy and one area above the Endrick Water. At the Endrick<br />

river a number <strong>of</strong> streams are intercepted to supplement the flow to the loch. The natural<br />

catchment <strong>of</strong> Loch Lomond can be divided into two northern and two southern subcatchments<br />

based on their contrasting bedrock geology and topography [MAITLAND<br />

1981]. This dichotomy has a major influence on the soil and the land use in both areas.


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Figure 10-11: Catchment Area <strong>of</strong> Loch Lomond [SEPA, changed]<br />

Page 85 <strong>of</strong> 136<br />

Loch Lomond's catchment is characterised by a relatively low mean altitude and gentle<br />

slopes with a high percentage <strong>of</strong> arable ground and base-rich rocks. For the River<br />

Clyde catchment as a whole are far more roads than in any <strong>of</strong> the Scottish catchments<br />

and relatively high population. More than half <strong>of</strong> Scotland's population, approximately<br />

2.6 million, live within on hours drive <strong>of</strong> the lake [HAMILTON 1988], although most <strong>of</strong><br />

these are outwith the catchment.<br />

In comparison to the other catchment areas <strong>of</strong> Lake Constance, Lake Geneva and<br />

Bourget Lake it has the lowest population. The extent <strong>of</strong> arable ground and base-rich


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rocks gives a good indication <strong>of</strong> the potential natural richness <strong>of</strong> the lake waters draining<br />

from them.<br />

Loch Lomond is an important source <strong>of</strong> portable water for two supply schemes, with a<br />

total ultimate yield <strong>of</strong> 454 megalitres per day. Because <strong>of</strong> its good water quality - the<br />

European Community classification <strong>of</strong> water intended for humans consumption grades<br />

Loch Lomond the highest quality - Loch Lomond is also important as a reservoir for<br />

public water supply and hydro-electricity generation at Loch Sloy hydroelectric power<br />

station [SEPA 2000c].<br />

Data <strong>of</strong> Land Use with Relevance to the Water Supply<br />

In the two northern sub-catchments, the Falloch (area 113 km²) and the Inveruglas<br />

(area 158 km²), lie entirely to the north and west <strong>of</strong> the Highland Boundary Fault, an<br />

important geological festure which crosses the southern part <strong>of</strong> the lake. The land is<br />

used for upland sheep-grazing (87 % <strong>of</strong> the catchment area, although forestry is also<br />

important (8 % <strong>of</strong> the catchment area). The northern sub-catchments are relatively underpopulated<br />

with little urban development. The two southern sub-catchments, the<br />

Fruin (area <strong>of</strong> 161 km²) and the Endrick (area <strong>of</strong> 264 km²), lie to the south and east <strong>of</strong><br />

the Highland Boundary Fault. Here is more arable farming (26 %) although large areas<br />

are still used fore rough grazing (56 %) and forestry (13 %).<br />

The 'Loch Lomond Catchment Management Report' published by the Scottish Environment<br />

Protection Agency (SEPA) states that Loch Lomond and its catchment are an<br />

important water supply, essential for the social and economic well-being <strong>of</strong> Central<br />

Scotland. However, these resources are coming under increasing pressure from potentially<br />

conflicting uses and activities, including recreation and tourism, forestry, agriculture,<br />

power generation and water abstraction. Approximately 9 % <strong>of</strong> the catchment is<br />

covered by water, compared to 35 % for agricultural land and 13 % for forestry. Urban<br />

and industrial areas in comparison account for less than 2 % <strong>of</strong> the land cover [SEPA].<br />

Agriculture has played an important role in shaping the landscape and defining the<br />

character <strong>of</strong> the Loch Lomond catchment. The report says forestry plays an integral role<br />

in the landscape and history <strong>of</strong> the Loch Lomond catchment. In the past, forestry practices<br />

have caused a number <strong>of</strong> environmental problems within the catchment. However,<br />

recent years have seen attempts, including the introduction <strong>of</strong> the Forest and Water<br />

Guidelines, to counteract many <strong>of</strong> these negative impacts. The restructuring <strong>of</strong> commercial<br />

woodlands and an increase in the development <strong>of</strong> native and riparian woodlands<br />

have also been beneficial [SEPA].<br />

Pollution Sources in the Catchment Area <strong>of</strong> Loch Lomond<br />

Due to the size <strong>of</strong> lochs and the diluted nature <strong>of</strong> any pollutants, water quality problems<br />

<strong>of</strong>ten take a long time to become apparent.Forestry, in particular coniferous forestry,<br />

exacerbates the problem by scavenging atmospheric pollutants [SEPA 2000c].<br />

Along the shore <strong>of</strong> the lake there are numerous single dwellings, camping and caravan<br />

parks, youth hostels, hotels and small villages which discharges effluents directly or indirectly<br />

into Loch Lomond. Discharges are also received from the surrounding forest


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and farm lands. Some <strong>of</strong> the local sewage treatment plants discharge excellent quality<br />

effluents but others suffer from inadequate maintenance or erratic loading. Luss village<br />

and Luss campsite are now served by a sewage treatment plant, having previously<br />

used individual septic tanks. At other recreational sites septic tanks are provided which<br />

should have sufficient capacity to receive the sewage from a full campsite or caravan<br />

park. On the loch itself there are many cruising boats fitted with chemical toilets [SEPA<br />

200c].<br />

A number <strong>of</strong> potential damaging activities within the Loch Lomond catchment have<br />

been identified by SEPA as threatening the lake's good water quality status. These activities<br />

are as follows:<br />

— Sewage effluents leading to increased nutrient and organic loading,<br />

— Farming resulting in increased use <strong>of</strong> fertilisers, pesticides, herbicides and problems<br />

associated with leakage from silage and slurry tanks,<br />

— Afforestation causing increases in suspended soils and turbidity, and the use <strong>of</strong><br />

fertilisers and pesticides.<br />

Sewage, urban and agricultural run-<strong>of</strong>f and direct contamination through livestock watering<br />

can compromise water quality. The main potential sources <strong>of</strong> organic and toxic<br />

pollution within the Loch Lomond catchment include agriculture (sheep dip, silage,<br />

slurry, pesticides and organic fertilisers), forestry (organic fertilisers, herbicides and fuel<br />

spillage), recreation (disposal <strong>of</strong> chemical toilet contents, hydrocarbon pollution from<br />

boat exhausts and fuel spillage) and waste disposal. Because there is very little industry<br />

within the catchment pollution by industrial chemicals is less <strong>of</strong> a problem [SEPA].<br />

Sheep farming is widely spread in the catchment area <strong>of</strong> Loch Lomond. As mentioned<br />

above chemical products are used to control a range <strong>of</strong> ectoparasites, such as scab<br />

and blowfly. The application takes place by dipping the sheep in a lotion including these<br />

chemicals. All sheep dips are toxic to aquatic life and even tiny amounts <strong>of</strong> dip can affect<br />

the environment. A cup <strong>of</strong> cypermethrin, the most commonly used pyrethroid dip<br />

has the potential to kill fish and insects over several kilometres in a sizeable watercourse<br />

[SEPA 1997]. In [SEPA 2000b] it is mentioned that sheep dip continues to pose<br />

a serious chronic pollution in some upland areas throughout Scotland, particularly<br />

through the use <strong>of</strong> synthetic phyrethroid dips which are highly toxic to aquatic life. Residues<br />

<strong>of</strong> sheep dip chemicals may also be discharged to rivers via sewage treatment<br />

plants after processing <strong>of</strong> fleeces and skins by the textile industry [SEPA 1999c], although<br />

no such processing occurs within the Loch Lomond catchment.<br />

In a press release <strong>of</strong> June 2000 [SEPA 2000a] SEPA stresses that sub-standard dipping<br />

facilities and poor disposal practices pose a significant environmental risk and a<br />

number <strong>of</strong> pollution incidents over the past few months have highlighted these dangers<br />

with the watercourses affected sometimes taking a long time to fully recover. The article<br />

continues that under the Groundwater Regulations 1998, it is illegal to intentionally dispose<br />

<strong>of</strong> waste sheep dip from static or mobile dippers, shower or jetters to land without<br />

an Authorisation from SEPA.


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Water-based activities are <strong>of</strong> particular importance in Loch Lomond. Boating can increase<br />

erosion at un<strong>of</strong>ficial launching sites and sheer overcrowding may be a problem<br />

in some popular areas. fuel spillages from powered craft may cause water pollution and<br />

disposal <strong>of</strong>chemical toilets' contents may be a problem for larger motor-cruisers<br />

[SEPA]. A maximum <strong>of</strong> 1.275 boats were counted using the lake on one day during<br />

1999, the highest figure since monitoring began in 1989. This increase in powered boat<br />

traffic has led to concerns over a number <strong>of</strong> possible detrimental effects ranging from<br />

boat engine hydrocarbon emissions impacting on water quality, to boat wakes causing<br />

damage to aquatic plants in shallow waters and exacerbating problems <strong>of</strong> shore erosion.<br />

More detailed information is not available at the moment but in general the situation at<br />

Loch Lomond is not as serious as at the other three Lakes because here the interference<br />

by humans is not so important.<br />

The Situation in Scotland Concerning Endocrine Disrupters<br />

Natural hormones in drinking water are <strong>of</strong> little concern in Scotland because there is<br />

only one location where a sewage outfall enters a water course above the point where<br />

water is taken for a public water supply. Effluents from some large sewage treatment<br />

plants also discharge into rivers and estuaries and natural hormones, excreted by<br />

women, may have feminising effects on male fish as has been found in rivers in England.<br />

In addition, Scotland has a large amount <strong>of</strong> wool, textiles and electronics industry<br />

and the waste waters from these, which may contain alkyl phenol ethoxylates (APEs),<br />

enter the river and tidal waters where they may have an adverse effect on fish and<br />

other aquatic life. A survey by the Scottish Environment Protection Agency (SEPA) in<br />

1996 showed that EDCs were present in some areas but at concentrations below the<br />

'no effect' level. The results also showed that at 13 sites this level may be exceeded at<br />

certain times. SEPA points out that there have been no reports <strong>of</strong> any adverse effects<br />

on the fish in the rivers receiving these effluents, but there has been no systematic investigation<br />

yet carried out to confirm this [SEPA 1999b].<br />

The great majority <strong>of</strong> freshwater lochs in Scotland are <strong>of</strong> high water quality. Of those<br />

which have some degree <strong>of</strong> pollution, diffuse causes <strong>of</strong> pollution such as acidification,<br />

diffuse agricultural pollution and forestry were responsible for 80 % <strong>of</strong> polluted lochs,<br />

says SEPA in its report "Improving Scotland's Water Environment. SEPA (1999a) continues<br />

that only three lochs are currently listened in the poor or seriously polluted categories<br />

and only one <strong>of</strong> these has a reasonable prospect <strong>of</strong> being improved to fair water<br />

quality by the end <strong>of</strong> 2005. Sewage effluent and freshwater fish farming are the only<br />

significant point source discharges to Scottish lochs. Diffuse agricultural pollution and<br />

urban drainage are also among the top four sources <strong>of</strong> river pollution in all regions. The<br />

diffuse agricultural pollution results from the run-<strong>of</strong>f <strong>of</strong> pesticides, organic waste, soil<br />

and nutrients from agricultural land. SEPA said, that drainage from roads, yards and<br />

ro<strong>of</strong>s in urban areas is typically contaminated by metals and oils. Concerning the industrial<br />

effluent SEPA says that in rivers industrial effluent affects only about 2 % <strong>of</strong> the<br />

polluted river length and is ranked as seventh in the list <strong>of</strong> sources <strong>of</strong> polluted river waters.<br />

The largest single identifiable sector causing pollution to rivers is the textile industry.


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Concerning the measurements <strong>of</strong> water quality SEPA (1999a) points out that the quality<br />

<strong>of</strong> Scotland's waters was initially measured by chemical analysis which measured the<br />

levels <strong>of</strong> oxygen demand and suspended solids to be used to assess the impact <strong>of</strong><br />

sewage discharges and some forms <strong>of</strong> industrial pollution. Since the 1950s, the range<br />

<strong>of</strong> chemical measurements routinely carried out has increased considerably and now<br />

includes the measurement <strong>of</strong> nutrients, metals, oil and man-made organic substances<br />

such as pesticides and polychlorinated biphenyls. SEPA (1999a) stresses that the interpretation<br />

<strong>of</strong> chemical analyses also requires a good understanding <strong>of</strong> the concentrations<br />

above which a chemical causes damage to the environment, together with how it<br />

interacts with any other pollutants which may be present.<br />

10.5 SUMMARY OF THE SITUATION AT THE LAKES<br />

In the previous chapters the situation at the Lakes has been described. The evaluation<br />

<strong>of</strong> the available data shows that several substances have been detected during the different<br />

surveys. Very <strong>of</strong>ten the substances have been measured near the detection limit<br />

or in ranges being in a tolerable amount concerning the drinking water or bathing water<br />

directive. Only SCHLICHTIG et al (2001) describe in a study the situation at the<br />

Seefelder Aach in the Lake Constance catchment where three substances have been<br />

detected in higher concentrations than the set target <strong>of</strong> the LAWA. The substances diuron,<br />

isoproturon and pirimicarb have exceeded quality targets up to 200 fold. The<br />

authors blame the sewage treatment plants, the improper handling <strong>of</strong> pesticides and<br />

their use in orchard horticulture. With respect to the sewage treatment plants the study<br />

shows that the 3 investigated plants, <strong>of</strong> 10 in the whole catchment, deliver an important<br />

part <strong>of</strong> the total pesticide load <strong>of</strong> the Seefelder Aach. They also critisise the fact that<br />

there are no set targets for many substances, and some results could not be analysed.<br />

Generally, the data concerning the impact <strong>of</strong> contaminants at the four EUROLAKES<br />

can not exclude to evaluate the possibility <strong>of</strong> potential for harm to the environment.<br />

There exists much less information about the coaction <strong>of</strong> different substances.


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11 ELIMINATION OF CONTAMINANTS<br />

The new water policy re-organises Community water legislation to prevent further deterioration<br />

and to protect and enhance water quality and quantity <strong>of</strong> aquatic ecosystems<br />

and groundwater. This proposal establishes a Community Framework with a common<br />

approach, objectives, basic measures and common definitions. This water policy focuses<br />

on water as it flows naturally through river basins and lakes towards the sea,<br />

taking into account natural interaction <strong>of</strong> surface water and groundwater in quantity and<br />

quality covering the whole <strong>of</strong> a river basin district including estuaries, other transitional<br />

waters and coastal waters. A combined approach to pollution control is required with<br />

control at source combined with the setting <strong>of</strong> environmental quality standards to ensure<br />

good status <strong>of</strong> waters by 2010. Programmes <strong>of</strong> measures must take into account<br />

all sources <strong>of</strong> impact on the aquatic ecosystems including impact from agriculture, energy<br />

production, transport, and spatial planning. Systematic monitoring <strong>of</strong> achievements<br />

is required. Moreover, the proposal introduces a requirement for water pricing policies<br />

that act as an incentive for the rational use <strong>of</strong> water as a step towards the full recovery<br />

<strong>of</strong> costs for water services, including financial, environmental and resource costs. The<br />

proposed Directive furthermore implements international obligations under the United<br />

Nations Economic Commission for Europe Convention on Transboundary Water<br />

Courses and International Lakes <strong>of</strong> 1992 and the UN Convention on the nonnavigational<br />

use <strong>of</strong> waters <strong>of</strong> 1996.<br />

The occurrence <strong>of</strong> natural and anthropogenic endocrine disrupters in the environment<br />

can cause disturbances in the hormonal system <strong>of</strong> aquatic organisms. Sewage treatment<br />

plant run<strong>of</strong>fs are a major source <strong>of</strong> EDC's released into the environment since<br />

they are only incompletely eliminated in sewage treatment plants. Natural estrogens in<br />

the effluent can still reach levels which exert estrogenic effects on wildlife. Therefore<br />

the survey into the elimination <strong>of</strong> endocrine disrupters in sewage treatment plants is<br />

necessary [SCHWIER et al. 2001].<br />

The research results <strong>of</strong> several investigations have shown that small amounts <strong>of</strong> natural<br />

and synthetic steroids (in the ng/l range) are found in the run<strong>of</strong>fs <strong>of</strong> sewage treatment<br />

plants. However these concentrations are seldom detected in portable water supplies or<br />

in river water. Xenoestrogens have been detected at higher concentrations (in the µg/ml<br />

range) not only in sewage treatment plant run<strong>of</strong>f, but also in surface water receiving<br />

wastewater run<strong>of</strong>f [HELMREICH 2001].<br />

The estrogenic nonylphenol is a degradation product <strong>of</strong> frequently occurring tensides<br />

and accumulates in large quantities in the sewage sludge due to its hydrophobic behaviour.<br />

Therefore, for an input/output balance <strong>of</strong> hormonally active substances in sewage<br />

treatment plants the process <strong>of</strong> sludge treatment has to be included [SCHWIER et<br />

al. 2001].


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11.1 PROCESSES TO ELIMINATE CONTAMINANTS FROM WASTEWATER<br />

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General Description <strong>of</strong> Processes Currently Applied<br />

It basically has to be distinguished between municipal and industrial wastewater treatment<br />

which apply more or less the same basic processes but under different preconditions<br />

and frequently with different aims.<br />

Industrial Wastewater Treatment<br />

Since industrial wastewater is characterised by high concentrations <strong>of</strong> specific contents<br />

(depending on the industry sector) intensified processes suitable for elimination <strong>of</strong><br />

these specific contaminants are applied. As far as possible physical chemical processes<br />

are used and only if wastewater composition (ratio <strong>of</strong> nutrients and bio degradable<br />

carbonic compounds) allows, biological processes are applied.<br />

As the processes applied are based on the same principles as thosefor municipal<br />

wastewater treatment a more detailed process description shall be covered by the following<br />

section. It has to be noted that frequently industrial wastewater are subjected<br />

only a pre-treatment which allows a further full treatment together with municipal<br />

wastewater. The common treatment <strong>of</strong> industrial and municipal wastewater can have<br />

many advantages since municipal wastewater is frequently lacking carbonic compounds<br />

for full reduction <strong>of</strong> nutrients, whereas industrial wastewater are frequently<br />

characterised by high concentrations <strong>of</strong> carbonic compounds and a lack <strong>of</strong> nutrients.<br />

Municipal Wastewater Treatment<br />

Wastewater composition<br />

The average waste produced by a person in Europe can be characterised by the following<br />

table according to [IMMHOFF, 1990] and [ATV A131, 1991]<br />

Total<br />

g/person/<br />

day<br />

BOD5 in<br />

g/person/<br />

day<br />

Organic compounds<br />

in g/person/day<br />

There<strong>of</strong><br />

pounds<br />

dissolved com- 125 30 50 75<br />

There<strong>of</strong> settable 50 20 30 20<br />

There<strong>of</strong> not settable 15 10 10 5<br />

Total waste load 190 60 90 100<br />

COD 120<br />

Ptotal<br />

2,5<br />

11<br />

N total<br />

Table 11-1 Wastewater composition<br />

Mineral compounds<br />

in g/person/day<br />

A typical municipal wastewater treatment plant corresponding to Council Directive<br />

941/271/EEC <strong>of</strong> 21 May 1991 concerning urban wastewater treatment applies the following<br />

processes:


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Mechanical treatment<br />

1. Screening or straining: Typically a coarse screen and fine screens with a min.<br />

slots spacing down to 3mm is applied<br />

2. Sedimentation for removing <strong>of</strong> sand and grit<br />

3. Flotation for removing <strong>of</strong> oil and grease<br />

4. Pre (or primary)- sedimentation prior to biological treatment for removing <strong>of</strong> undissolved<br />

settable organic and inorganic compounds.<br />

With these mechanical treatment processes a reduction in the total waste-load <strong>of</strong> up to<br />

30 % can be achieved. Pre - sedimentation is not always applied since it is not always<br />

wished to fully reduce carbonaceous pollution load in order to keep up a the required<br />

ratio C : N : P for the following biological treatment process.<br />

Screenings are usually washed and deposed or used in other biological solid waste<br />

processes (like composting), the removed grit is washed and deposed or reused for<br />

different purposes.<br />

The settled sludge from the pre (or primary sedimentation) is referred to as primary<br />

sludge and usually submitted to further anaerobic treatment.<br />

Biological treatment<br />

Activated sludge process (processes with suspended micro -organisms growth)<br />

The principle <strong>of</strong> biological wastewater treatment is based on the ability <strong>of</strong> microorganisms<br />

to deteriorate certain organic substances contained in natural waters. This<br />

natural self purification capability <strong>of</strong> surface waters is technically applied and intensified<br />

in the activated sludge process which is mostly applied in plants designed to keep the<br />

effluent standards <strong>of</strong> western European countries.<br />

The activated sludge process essentially involves a phase in which the water to be purified<br />

is brought into contact with a bacterial floc in the presence <strong>of</strong> oxygen (aeration<br />

phase) followed by a phase <strong>of</strong> separation <strong>of</strong> the purified wastewater from this floc (clarification).<br />

In fact these processes amount to an intensification <strong>of</strong> the phenomena that<br />

occur in the natural environment. The difference lies in the greater concentration <strong>of</strong> micro<br />

organisms which result in a greater oxygen volume demand. Moreover, in order to<br />

maintain the bacterial mass in suspension, it must be artificially mixed.<br />

An activated sludge facility always includes<br />

a so called aeration tank, in which water to be purified comes into contact with the purifying<br />

bacterial mass,<br />

• a clarifier, in which the purified water is separated from the bacterial growth


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• a re-circulation device for the return <strong>of</strong> the biological sludge from the clarifier to<br />

the aeration tank. This arrangement enables the aerated tank to support the<br />

quantity <strong>of</strong> or concentration <strong>of</strong> micro-organisms required to maintain the desired<br />

level <strong>of</strong> purification<br />

• a device for the extraction and disposal <strong>of</strong> excess sludge, or surplus sludge, or<br />

surplus bacterial growth, which is permanently synthesised from the substrate,<br />

• a device supplying oxygen to the bacterial mass in the aeration tank,<br />

These plants are usually fed continuously with wastewater, and the processes are applied<br />

in separate reactors. However it is also possible to apply these processes (aeration,<br />

clarification, excess sludge removal...etc) in the same reactor with discontinuous<br />

feeding <strong>of</strong> the wastewater to different reactors. This mode <strong>of</strong> operation requires different<br />

plant design and process layout and is referred to as SBR (sequencing batch reactor)<br />

process.<br />

The compounds contained in the wastewater are aerobically degraded by excellular enzymes,<br />

by metabolising, by aerobic fermentation processes, by transformation <strong>of</strong> the<br />

compounds to gases (like CO2 and N2 ),by building up additional bio mass or by adsorption<br />

to the activated sludge floc. So the compounds contained in the wastewater<br />

leave the plant either in the form <strong>of</strong> gas (CO2) in the form <strong>of</strong> bio mass (approx. ratio 50<br />

: 50 in aerobic processes) or the not biodegradable compounds in the residual effluent.<br />

The capability <strong>of</strong> the plant is depending on the prevailing bacteria strains. Since different<br />

bacteria strains have different growth rates the “sludge age” (the retention time <strong>of</strong><br />

the bacteria in the system) is the key point in the design <strong>of</strong> biological treatment plants.<br />

The more specialised the bacteria have to be, the lower is the growth rate and consequently<br />

the longer the provided retention time has to be.<br />

For plants designed only for the removal <strong>of</strong> carbonaceous compounds a sludge age <strong>of</strong><br />

3 days is sufficient, for plants designed for nitrogen removal the sludge age must be<br />

minimum 10-12 days depending on the temperature.<br />

According to the Council Directive 941/271/EEC <strong>of</strong> 21 May 1991 concerning urban<br />

wastewater treatment most treatment plants have to be designed for enhanced nutrient<br />

removal up to the year 2005, what means that the aerobic sludge age will have to be<br />

minimum 10-12 days. This means an increase in the sludge age <strong>of</strong> up to 300 % compared<br />

to existing plants only designed for reduction <strong>of</strong> carbonaceous compounds. As<br />

will be described below this will have a great influence on the reduction <strong>of</strong> endocrine<br />

substances since the high sludge age is a precondition for the presence <strong>of</strong> bacteria<br />

which allow the degradation <strong>of</strong> compounds which are present in the wastewater in only<br />

very low concentrations.


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The growth rate <strong>of</strong> bacteria is following the function <strong>of</strong> MONOD.<br />

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Figure 11-1 Monod function<br />

Page 94 <strong>of</strong> 136<br />

That means low substrate concentrations (effluent concentrations) can only be<br />

achieved with low growth rates. Further the bacteria growth rate is approximately the inverse<br />

<strong>of</strong> the sludge age and the sludge age again is a function <strong>of</strong> the sludge load, say<br />

the pollution load per sludge (bacteria) unit. That means if a plant is operated with a low<br />

sludge load (say high activated bacteria / sludge masse for the incoming waste load)<br />

the sludge age is high and bacteria with low growth rates, specialised for the metabolisation<br />

<strong>of</strong> compounds which are difficult to reduce, can accumulate in the system. According<br />

to MONOD the effluent concentration is then not a function <strong>of</strong> the incoming inflow<br />

concentration but a function <strong>of</strong> the growth rate, say sludge age. In plants designed<br />

to meet the requirements <strong>of</strong> Council Directive 941/271/EEC the sludge load is low<br />

enough to allow the growth <strong>of</strong> bacteria which are able to metabolise compounds which<br />

are in very low concentrations and which are difficult to reduce. [KREUZINGER, 1998]<br />

Processes with attached growth<br />

Most micro-organisms are able to grow on the surface <strong>of</strong> solid when organic compound,<br />

mineral salts and oxygen are available. They are anchored by means <strong>of</strong> an exopolymerbased<br />

gelatinous material produced by the bacteria, inside, which the bacteria can, to<br />

some extent, move about. The colonisation <strong>of</strong> the solid matters begins in selected areas,<br />

whence the bio-film develops continuously until the entire surface <strong>of</strong> the support is<br />

covered with a monocellular layer. From this moment on , growth is carried on by the<br />

production <strong>of</strong> new cells covering the first layer.


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The oxygen and nutrients carried in the water to be treated diffuse throughout the bi<strong>of</strong>ilm<br />

until the deepest cellular accumulations are no longer affected by the oxygen and<br />

nutrients. After some time, stratification occurs with an aerobic layer, where the oxygen<br />

is diffused, on top <strong>of</strong> a deeper anaerobic layer in which there is no oxygen. This shall<br />

generally be avoided by hydraulically designing the system so that the when the bio-film<br />

exceeds a certain thickness the bacteria are washed away. The use <strong>of</strong> bio-film methods<br />

for treating water shows that the bacteria attached to a support usually display higher<br />

specific activity than those observed in suspended growth.<br />

This principle has long been applied in the 60ies and 70ies in the so called trickling filters<br />

which were designed for removal <strong>of</strong> carbonaceous compounds and in some cases<br />

even for nitrification and simultaneous sludge stabilisation. However in order to fulfil the<br />

requirement <strong>of</strong> nutrient removal most if these trickling filters have been replaced by activated<br />

sludge process plants in Germany and Austria the last 20 years.<br />

Trickling filters allow the water to be treated to trickle onto a mass <strong>of</strong> material with a<br />

high specific surface area, supporting a film <strong>of</strong> purifying micro-organisms. These filters<br />

are aerated by natural draught, occasionally by forced countercurrent ventilation. When<br />

the bio-film is charged with only a low waste load also bacteria with low growth rates are<br />

able to grow on the supporting material. The advantage that the bacteria are fixed to a<br />

support and need not pass the clarifier, is being used in processes with submerged<br />

contact structures, which are situated in a tank <strong>of</strong> activated sludge, allowing bacteria<br />

with very low growth rates to grow in the system. Thus with that arrangement it is possible<br />

to improve the performance <strong>of</strong> an activated biological sludge stage without enlarging<br />

the clarifier which may be limited by the solids loading applied.<br />

Processes with submerged contact structure are more and more applied since they allow<br />

very specialised bacteria, which can also reduce substances present in very low<br />

concentrations in the water, to settle on the supports.<br />

Treatment <strong>of</strong> surplus sludge - primary sludge and excess biological sludge<br />

Primary sludge<br />

Primary sludge is usually pre thickened in a pre thickener, (frequently together with the<br />

excess biological sludge) or is directly sent to the anaerobic digester. The supernatant<br />

liquid <strong>of</strong> the pre thickener is usually added to the influent. Frequently primary sludge<br />

and excess biological sludge are thickened together.<br />

Excess biological sludge<br />

The excess biological sludge needs further reduction <strong>of</strong> organic material. This is done<br />

either by aerobic stabilisation or by anaerobic digestion. The ratio organic/inorganic<br />

material in excess sludge typically is 2 /3 to 1 /3, thus stabilisation <strong>of</strong> excess sludge allows<br />

a reduction <strong>of</strong> the sludge dry weight by 2 /3.


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Anaerobic digestion<br />

In an anaerobic digester the organic material is metabolised into approx. 2 /3 CH4, 1 /3<br />

CO2 and biomass. The process is performed in a stirred reactor at a temperature between<br />

30-37 °C. The gas can be used for heating or energy generation. After anaerobic<br />

digestion the stabilised sludge is thickened to the extent required for the final disposal.<br />

Aerobic stabilisation<br />

Excess sludge can also be stabilised aerobically by increasing the aerobic sludge age<br />

to an extent where organic material is aerobically degraded and mineralised. This is<br />

practically done simultaneously in the aeration tank in small plants (up to 10.000 P.E),<br />

or in a separate aerated stabilisation basin. The aerobic stabilisation process is much<br />

more energy consuming than anaerobic fermentation. Also the de-watering <strong>of</strong> the aerobically<br />

stabilised sludge is more difficult and energy consuming. For this reason aerobic<br />

stabilisation is only applied in small treatment plants. (up to 10.000 – 25.000 PE).<br />

Supernatant liquids and process water<br />

The supernatant liquids from all processes for thickening (static thickeners, mechanical<br />

de-watering) are usually charged with high loads <strong>of</strong> nutrients and also COD. For that<br />

reason different strategies for adding the waters to the plant or even for separate treatment<br />

are applied.<br />

A general flow sheet showing the mass streams in a typical wastewater treatment plant<br />

designed according to the state <strong>of</strong> the art is shown in Figure 11-2<br />

Figure 11-2 Mass streams in a typical wastewater treatment plant, according to<br />

[KREUZINGER, 1998]


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Final disposal <strong>of</strong> excess sludge<br />

The following disposal routes for excess sludge are mainly used in the EC:<br />

1. Use in agriculture (sludge spreading)<br />

2. Use on other land (recultivation)<br />

3. Disposal on landfills<br />

4. Disposal (on landfills) after incineration<br />

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Partly sludge is further treated by composting together with other organic waste prior to<br />

beneficial use in agriculture or on other land.<br />

Which pathways are used in which country and the tendency on European level for the<br />

future is depending on a variety <strong>of</strong> factors like ecology, economy, social aspects, the<br />

current knowledge about the benefits and potential harmful effects <strong>of</strong> the utilisation <strong>of</strong><br />

sewage sludge, and the trends in European legislation [WITTE, 2000].<br />

The existing and extrapolated future pathways for Germany and the EC according to<br />

WITTE (2000) and MARMO (1999) are given in the following Figure.<br />

Figure 11-3 Pathways <strong>of</strong> sewage sludge disposal<br />

According to MARMO (1999) for the year 2000 53 % <strong>of</strong> the sludge are used for agriculture<br />

and recultivation <strong>of</strong> soils, 23% <strong>of</strong> the sludge is disposed in landfills, 22% <strong>of</strong> the<br />

sludge is incinerated and 2% is disposed by other ways.


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The Council Directive 86/278/EEC <strong>of</strong> 12 th June 1986 on the protection <strong>of</strong> environment<br />

and in particular <strong>of</strong> soil, when sludge is used in agriculture; and most <strong>of</strong> all Council Directive<br />

1999/31/EC <strong>of</strong> 26 th April 1999 on the landfill <strong>of</strong> waste, which makes disposal <strong>of</strong><br />

surplus sludge on landfills practically only possible after sludge drying (which is very<br />

energy consuming) will favour the incineration and agricultural use <strong>of</strong> sewage sludge,<br />

and reduce disposal on landfills for the future.<br />

Other processes applied<br />

Besides these basic processes applied for treatment <strong>of</strong> sewage the following processes<br />

are applied for improving the effluent quality, in particular in order to meet the requirements<br />

for phosphorus removal according to Council Directive 91/271/EEC on urban<br />

waste water treatment.<br />

• Phosphorus removal: According to this directive urban wastewater discharged into<br />

sensitive areas must be subjected to further treatment in order to reduce phosphorus<br />

and nitrogen concentrations. In fact the most common way to reduce phosphorus<br />

is precipitation with metal salts which is added mostly the aeration tank and the<br />

precipitant being disposed with the surplus sludge. It is also possible to reach phosphorus<br />

concentrations in the effluent below 2mg/l by enhanced nutrient removal, say<br />

by biological phosphorus removal.The principle <strong>of</strong> biological phosphorus removal is<br />

based on providing the treatment plant with a supply <strong>of</strong> micro-organisms (or rather<br />

groups <strong>of</strong> micro-organisms) that are capable <strong>of</strong> enhanced phosphorus incorporation<br />

into their cells as a polyphosphate. These must Therefore be given a selection advantage<br />

over the other groups <strong>of</strong> micro-organisms. This can be done by setting the<br />

biocoenosis <strong>of</strong> the treatment plant, at least for a short period, under strong anaerobic<br />

conditions by connecting an anaerobic tank into the sludge cycle<br />

• Wastewater disinfection: Direct discharge into bathing waters requires the disinfection<br />

<strong>of</strong> wastewater. Whereas in the past chlorine has been used now UV radiation<br />

is mostly applied.<br />

The effect <strong>of</strong> these processes on Endocrine Substances<br />

Current knowledge about endocrine substances in wastewater and their elimination<br />

/ breakdown in wastewater treatment plants in general<br />

Only a very few research works have been done on this matter, consequently only very<br />

little information is available. It must be noted that in wastewater technology an analytic<br />

accuracy <strong>of</strong> only 1/10 mg/l is usually applied, and that wastewater is characterised by<br />

sum parameters like BOD5 or COD. So it simply has never been possible to take care<br />

<strong>of</strong> these substances by operating entities <strong>of</strong> wastewater treatment plants.<br />

The few publications on this matter shall be summarised in the following. It must be<br />

outlined that the existing publications hardly contain any information about processes<br />

applied or process parameters which would be necessary to gain information about the<br />

effect <strong>of</strong> processes and operation modes on the substances considered. Obviously the<br />

involved scientists were not wastewater process engineers.


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Another problem is that the standard <strong>of</strong> wastewater treatment has changed considerably<br />

the last 20 years what makes extrapolation or interpretation <strong>of</strong> data gained in the<br />

80ies impossible.<br />

A research programme in these questions has started on June 2000 in Austria under<br />

the Title “Austrian Research Co-operation on Endocrine Modulators (ARCEM). The<br />

programme is scheduled up to mid 2003 and is initiated by Austrian Scientists from<br />

different universities together with the Austrian Federal Environment Agency and the<br />

Federal Ministry for Agriculture, Forestry, Environment and water management.<br />

One module under this programme will deal with the aspect <strong>of</strong> the reduction <strong>of</strong> endocrine<br />

modulators from the point <strong>of</strong> wastewater /drinking water process engineering.<br />

However results may not be expected before mid 2001.<br />

Currently the following can be stated regarding the effect <strong>of</strong> wastewater treatment processes<br />

on endocrine substances:<br />

• The elimination rate <strong>of</strong> the substances by mechanical treatment, particularly in the<br />

primary sedimentation is depending on the hydraulic retention time <strong>of</strong> the wastewater<br />

in the primary sedimentation tank. Since the substance in this treatment stage<br />

are sourced out with the primary sludge the physical chemical properties <strong>of</strong> these<br />

substances in relation to the primary sludge play an important role. Considering<br />

classical wastewater parameters as BOD5, max. 30 % <strong>of</strong> the waste load can be<br />

eliminated in this stage. Since many endocrine substances are lipophil the rate <strong>of</strong><br />

reduction in this treatment process can even be higher if high amounts <strong>of</strong> fat are<br />

contained in the wastewater. [KREUZINGER, 1998]<br />

• However from the point <strong>of</strong> view <strong>of</strong> wastewater process engineering it has to be<br />

stated that a high reduction <strong>of</strong> waste by primary sedimentation is not always desired.<br />

There is even a recent trend to reduce the efficiency <strong>of</strong> primary sedimentation since<br />

too much reduction <strong>of</strong> carbonaceous compounds in the primary sedimentation can<br />

cause difficulties in Nitrogen reduction in the activated sludge process. (change <strong>of</strong><br />

ratio C:N). And since more and more treatment plants are legally obliged to reduce<br />

nitrogen the efficiency <strong>of</strong> primary sedimentation is being reduced.<br />

• Difficult biodegradable substances are being adsorbed to activated sludge flocks<br />

due to their higher molecular weight (most <strong>of</strong> all steroid hormones are made up <strong>of</strong><br />

large molecules), and are being soured out with the excess biological sludge for<br />

further treatment. [KREUZINGER, 1998]<br />

• During aerobic excess sludge stabilisation, in which course the sludge is aerated for<br />

days, even weeks, a further reduction <strong>of</strong> endocrine substances is assumed. Anaerobic<br />

stabilisation can also induce anaerobic degradation mechanisms which can<br />

complete aerobic processes, like it is the case with NPnEOs [KREUZINGER, 1998]).<br />

• If the final excess sludge is disposed in agriculture or if it is composted (what exposes<br />

the sludge to further intensive aerobic biological processes) also the ad-


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sorbed difficult to degrade substances are assumed to be reduced. An additional<br />

reduction <strong>of</strong> these substances is expected from UV radiation to which sludge spread<br />

on (mostly agricultural) land is exposed. If sludge is incinerated the adsorbed substances<br />

are assumed to be destroyed [KREUZINGER, 1998]).<br />

Reduction <strong>of</strong> endocrine substances in wastewater treatment plants– results <strong>of</strong><br />

monitoring studies in Austria<br />

In 1998 a monitoring campaign was done in Austria, initiated by the Federal Environment<br />

Agency –Austria, in which course the influent and effluent <strong>of</strong> 17 WWTP (3 out <strong>of</strong><br />

them are industrial plants) was analysed with regards to Xenohormones and Steroidhormones.<br />

In particular the following 7 substances were considered under this campaign:<br />

1. Polychlorinated Biphenyls (PCB)<br />

2. Phthalates<br />

3. Organotin compounds<br />

4. Alkylphenoles<br />

5. Nonylphenolmono and diethoxylates<br />

6. Bisphenol A (BPA)<br />

7. Buthylhydroxyanisol (BHA)<br />

The results are published by the Federal Environment Agency – Austria; BE-154 (1999)<br />

and are summarised hereafter:<br />

Results <strong>of</strong> the filtered wastewater samples:<br />

Polychlorinated Biphenyles (PCB):<br />

• In the influent to the WWTPs some PCB –congeneres (PCB 28, 52, 77, 138, 153,<br />

180) could be detected (concentration above 0,002 µg/l).<br />

• In the effluent PCB were not detectable.<br />

Phthalates<br />

• The highest concentrations <strong>of</strong> Phthalates in the influent to the WWTPs were measured<br />

with max. 26 µg/l Diethylphthalate, max. 17 µg/l Dimethylphthalate and max.<br />

7,5 µg/l Di(2-ethyhexyl)phthalate.<br />

• In the effluent only Dimethylphthalate with a median (n=17) <strong>of</strong> 1 µg/l was regularly<br />

detectable.<br />

• Dibutylphthalate and Butylbenzylphthalate, which are suspected to have estrogenic<br />

effects could not or only sporadically be detected above the detection concentration<br />

<strong>of</strong> 0,5 µg/l and 0,4 µg/l in the effluent <strong>of</strong> the monitored plants.<br />

Organo-tin-compounds<br />

• The highest detected concentration <strong>of</strong> Tributyltin in the influent to the plants was<br />

0,02µg/l.


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• In 8 out <strong>of</strong> 17 influent samples Tributyltin was detected above the detection concentration<br />

<strong>of</strong> 0,01 µg/l.<br />

• The highly toxic Tributyltin was found in the effluent samples <strong>of</strong> 4 plants above the<br />

detection concentration <strong>of</strong> 0,01 µg/l, with a max. concentration <strong>of</strong> 0,014 µg/l.<br />

• The most frequently detected organo-tin compound in the effluent was monobutyltin<br />

with 5 out <strong>of</strong> 17 samples above the detection concentration <strong>of</strong> 0,01 µg/l. The maximum<br />

concentration lay at 0,019 µg/l.<br />

• Dibutyltin was detected only in one effluent sample above the detection concentration<br />

(0,01 µg/l), although it could be analysed in many influent samples.<br />

• In 9 out <strong>of</strong> 17 influent samples the concentration <strong>of</strong> Dibutyltin was above 0,01 µg/l,<br />

with the maximum detected concentration at 0,023 µg/l.<br />

• All other Organo-tin compounds were not detectable above the detection concentration<br />

<strong>of</strong> 0,005 µg/l.<br />

Alkylphenoles<br />

• The dominating alkylphenole in influent and effluent <strong>of</strong> the WWTPs was 4-NPtec.(mixture<br />

<strong>of</strong> 4-NP and 2-NP in ratio 9:1).The maximum concentration in the influent<br />

samples was 9,4 µg/l; in the effluent 1,9 µg/l.<br />

• Further frequently detected alkylphenoles in influent and effluent were 4-tert –<br />

Buthylphenole and 4-tert-Octylphenole. The 4-tert–Buthylphenole concentrations in<br />

the effluent samples ranged from 0,06 to 0,45 µg/l, for 4-tert-Octylphenole between<br />

0,06 and 0,24 µg/l.<br />

Nonylphenolethoxylates (NP1EO, NP2EO)<br />

• In the influents <strong>of</strong> the monitored treatment plants surprisingly high maximum concentrations<br />

<strong>of</strong> 11,4 µg/l NP1EO and 27,5 µg/l NP2EO were found.<br />

• In the effluent <strong>of</strong> these plants the concentrations were significantly lower (NP1EO<br />

Min0,142 µg/l, Max. 0,86 µg/l; NP2EO Min. 0,169 µg/l, Max. 2,164 µg/l;)<br />

Buthylhydroxyanisol (BHA)<br />

• The antioxidans (E 320) could be found in the influent as well as in the effluent <strong>of</strong> 9<br />

out <strong>of</strong> 17 treatment plants above the detection concentration <strong>of</strong> 0,05 µg/l (Min. effluent:<br />

0,044 µg/l; Max. effluent 0,137 µg/l).<br />

Bisphenol A (BPA)<br />

• The max concentration detected in the influent was 8,43 µg/l.<br />

• The concentrations in the effluent were significantly lower with a median (n=17) <strong>of</strong><br />

0,243µg/l, and a maximum concentration <strong>of</strong> 0,884 µg/l.


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Phthalates<br />

• In 50-60% <strong>of</strong> the samples Di(2-ethyhexyl)phthalate- and Dibutylphthalate concentrations<br />

were detected.<br />

• Dimethylphthalate and Diethylphthalate could be detected only scarcely, Butylbenzylphthalate<br />

could not be detected in any <strong>of</strong> the samples.<br />

Organo-tin-compounds<br />

• In the solid matters <strong>of</strong> 40 % <strong>of</strong> the analysed samples Tributyltin could be detected<br />

above the detection concentration.<br />

• Only in 20 % <strong>of</strong> the samples Dibutyltin could be detected, and Monobutyltin could<br />

only be detected in one single sample.<br />

Nonylphenolethoxylates (NP1EO, NP2EO)<br />

• In the solid matters <strong>of</strong> 75 % <strong>of</strong> the analysed samples Nonylphenole could be analysed<br />

• NP1EO and NP2EO was found in 50% and 40% <strong>of</strong> all analysed samples. Mostly the<br />

concentration <strong>of</strong> NP1EO was found above the concentration <strong>of</strong> NP2EO.<br />

The effect <strong>of</strong> wastewater treatment on steroid hormones and Alkylphenolpolyethoxylates<br />

in particular<br />

The only publication regarding more detailed reduction pathways <strong>of</strong> endocrine substances<br />

in sewage treatment plants is from [KREUZINGER, 1998]. He summarises<br />

publications on steroid hormones and Alkylphenolethoxylates and comes to the following<br />

results:<br />

Effect <strong>of</strong> wastewater treatment processes on Steroid Hormones<br />

Estrogens are collected in the sewer system and reach the wastewater treatment plants<br />

most probably in their biologically less effective conjugated form<br />

[UMWELTBUNDESAMT BERLIN, 1995]<br />

Considering the decomposition properties <strong>of</strong> other complex compounds during treatment<br />

<strong>of</strong> wastewater [GIGER, AHEL, KOCH, 1986;MARCOMINI, 1989; AHEL], it may be<br />

assumed that the further degradation <strong>of</strong> estrogens in wastewater treatment plants is<br />

strongly depending on the processes and mode <strong>of</strong> operation applied in the sewage<br />

works.<br />

[FÜRHACKER, 1998] and [SCHWEINFURTH, 1997] summarise the decomposition <strong>of</strong><br />

EE2 in wastewater and environment as follows:<br />

After incubation <strong>of</strong> EE2 – and also mestranol – with activated sludge under aerobic<br />

conditions over a duration <strong>of</strong> 5 days Norpoth et.al. (1973) noticed a reduction in the<br />

concentration <strong>of</strong> theses substances.


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[TABAK and BUNCH ,1970] noticed a reduction <strong>of</strong> 95 % <strong>of</strong> EE2 (20mg/l) at continuous<br />

incubation with activated sludge after a period <strong>of</strong> 4 weeks, whereas with adapted microorganisms<br />

within 3 weeks a reduction <strong>of</strong> 97 % and after 4 weeks a full primary reduction<br />

was noticed. It seemed that the substances were in an initial stage adsorbed to<br />

the activated sludge flocks. As has been expected EE2 showed to be more stabile under<br />

these conditions than the endogene estrogenes estradiole, estron and estriol.<br />

[TABAK et al., 1981] further conducted a field study in several wastewater treatment<br />

plants (n=12-14) in the United States, investigating the degradation <strong>of</strong> different<br />

Stereoidhormones. They reported a reduction <strong>of</strong> 20-40 % in the course <strong>of</strong> the wastewater<br />

treatment. Considering the analytical procedures applied under this study, it is<br />

assumed that the measured concentrations also include conjugated metabolites <strong>of</strong> EE2,<br />

so that the percentage <strong>of</strong> actually eliminated free compounds is even higher.<br />

Adsorption to activated sludge particles might mainly contribute to the reduction <strong>of</strong> concentrations.<br />

Considering the structure <strong>of</strong> EE2 it is assumed that hydrolysis and photolysis<br />

processes are <strong>of</strong> minor contribution to the elimination <strong>of</strong> EE2.<br />

As can be seen, important information on process parameters like age <strong>of</strong> the incubated<br />

sludge, waste load, origin (from which process) <strong>of</strong> the sludge is very scarce and does<br />

not allow any statements on the performance <strong>of</strong> existing treatment plants designed according<br />

to the current state <strong>of</strong> the art. Another problem is that the state <strong>of</strong> the applied<br />

technology in wastewater engineering has changed considerably since the 80ies.<br />

Effect <strong>of</strong> wastewater treatment processes on Alkylphenolpolyethoxylates<br />

(NPnEOs)<br />

There exists a number <strong>of</strong> detailed research works on the behaviour <strong>of</strong> NPnEOs in the<br />

biological wastewater treatment process which have been conducted by the EAWAG in<br />

Switzerland. [AHEL.et.al 1994, BRUNNER et.al 1984, GIGER et al 1984, MARCOMINI<br />

at.al 1988, SIEGRIST et.al.1989].<br />

The following paragraphs summarise the results and findings <strong>of</strong> these Swiss research<br />

works and are based on the recently published pathways for the decomposition <strong>of</strong><br />

NPnEOs [published by CORCIA et.al 1998].<br />

Transformation <strong>of</strong> NPnEOs in sewer system and mechanical wastewater treatment<br />

According to [GIGER,1986], and AHEL (1994) the distribution <strong>of</strong> NPnEOs in the analysed<br />

raw water influents to sewage treatment plants did not significantly differ from the<br />

distribution <strong>of</strong> the primary sedimentation tanks effluent. (Refer to Figure 11-2)<br />

However the concentrations in short chain NPnEOs is changed considerably. This<br />

could be explained by the fact that short chain NPnEOs are more hydrophobe and are<br />

Therefore easier adsorbed to non dissolved wastewater particles which settle in the<br />

primary sedimentation tank and are sourced out with the primary sludge.


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Due to the fact that the distribution function <strong>of</strong> technical products (which is following a<br />

Poisson distribution) is differing from the bimodal distribution <strong>of</strong> the NPnEOs in the influent<br />

to the plant, and since only etoxylated NPs can be found in the influent, it is assumed<br />

that initial transformation processes are taking place already in the sewer system.<br />

Figure 11-4 Distribution <strong>of</strong> NPnEO oligomeres<br />

Transformation <strong>of</strong> NPnEOs in aerobic biological wastewater treatment processes<br />

In the aerobic biological treatment stages in which the oxidation <strong>of</strong> organic wastewater<br />

substances takes place the Ethoxyl and Alkyl-Side Chains are reduced to NP2EO and<br />

NP1EO and carboxylation <strong>of</strong> Ethoxyl and Alkyl-Side Chains takes place.<br />

In the effluent <strong>of</strong> the treatment plants with biological treatment mainly NP2EO and<br />

NP1EO (also a few traces <strong>of</strong> NP3EO – NP10 EO) can be found, long chain oligomeres<br />

are missing.<br />

The publication <strong>of</strong> [GIGER (1986] compares the distribution <strong>of</strong> NPnEO groups in the effluent<br />

<strong>of</strong> two treatment plants (WWTP Opfikon and WWTP Bassersdorf) which are designed<br />

and operated at different levels (one with high sludge age and nitrification, the


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other with low sludge age). The results clearly demonstrate that there is a relation between<br />

reduction <strong>of</strong> NPnEOs and the process parameters like sludge age, sludge load,<br />

nitrification and reduction <strong>of</strong> organic wastewater contents as outlined above.<br />

Transformation <strong>of</strong> NPnEOs in anaerobic sludge stabilisation<br />

The further degradation <strong>of</strong> NPnEOs (NP2EO and NP1EO) which are adsorbed to the<br />

excess biological sludge, takes place during anaerobic stabilisation in the sludge digester,<br />

by elimination <strong>of</strong> the Ethoxy groups down to NP. Tschui et al (18) could verify<br />

this reduction in a batch test. After a retention time <strong>of</strong> 20 days some 60% <strong>of</strong> the NP2EO<br />

and NP1EO were decomposed and the amount <strong>of</strong> NP was doubled.<br />

They could even notice a surplus <strong>of</strong> NP which did not result from the degradation <strong>of</strong><br />

NP2EO and NP1EO.<br />

This could be explained by the fact that probably remaining NP3EO – NP10 EO chains<br />

and CAPEs as well as CAPECs (which were not measured) are reduced to NP under<br />

anaerobic conditions.<br />

11.2 SUMMARY AND OUTLOOK<br />

Obviously endocrine substances can be reduced in wastewater treatment plants but not<br />

fully. With the Council Directive 91/271/EEC on urban waste water treatment, May 21 th ,<br />

1991, most European WWTPs are obliged to apply aerobic biological treatment processes<br />

with high sludge age what favours the growth <strong>of</strong> bacteria capably <strong>of</strong> metabolising<br />

substance which are contained in low concentrations in the wastewater.<br />

Further advantageous are aerobic conditions for the deposed excess sludge as provided<br />

in agricultural use or composting <strong>of</strong> the sludge. According to studies regarding<br />

future trends in the European Union it may be expected that an increase <strong>of</strong> the sludge<br />

used for agriculture will take place.<br />

However, still the information required to prepare strategies in design and operation <strong>of</strong><br />

WWTPs is insufficient, and most probably it will not be able to completely eliminate the<br />

substances in the course <strong>of</strong> the treatment.<br />

Theoretically the effluent could be further treated by membrane processes or activated<br />

carbon processes which can completely eliminate nearly all substances targeted. In<br />

other words “technically everything is possible”, but these processes are extremely<br />

costly and it is not considered a sound approach to invest in end <strong>of</strong> pipe technology.<br />

Avoiding <strong>of</strong> these substances by production restrictions and strict regulations would be<br />

a much more economic and reasonable approach for reducing the emission <strong>of</strong> endocrine<br />

modulators into the environment.<br />

11.3 PROCESSES TO ELIMINATE CONTAMINANTS FROM SOURCES FOR<br />

DRINKING WATER SUPPLY<br />

General considerations


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The aim <strong>of</strong> any water treatment is defined in Mutschmann et Stimmelmayer (1999) as:<br />

1. To change natural parameters <strong>of</strong> the water so that water is hygienically harmless for<br />

human consumption and suitable for technical use. This includes s<strong>of</strong>tening <strong>of</strong> water,<br />

iron and manganese removal, modifying <strong>of</strong> carbonate balance, aeration <strong>of</strong> water,<br />

etc..<br />

2. To remove anthropogeneous substances. Originally this mainly meant removal <strong>of</strong><br />

bacteria and viruses by disinfection. However since intensivation <strong>of</strong> agriculture and<br />

industrialisation it means removal <strong>of</strong> nitrates, pesticides, heavy metals, organic chlorine<br />

compounds, and others<br />

For the removal <strong>of</strong> anthropogeneous substances extremely cost intensive treatment<br />

processes exist, like reverse osmosis, ultra filtration, ion exchange, biological treatment,<br />

etc...which would also be suitable for the removal <strong>of</strong> endocrine substances.<br />

That means technically each substance can be removed. With membrane processes<br />

for example (ultra filtration, nano-filtration, reverse osmosis, electro dialysis) it is possible<br />

to remove any molecules desired, but this would undoubtedly double or triple present<br />

water tariffs what is economically and also politically very difficult.<br />

On the other hand the effect <strong>of</strong> conventionally applied processes on endocrine substances<br />

is not known at all, and there are no publication available on this matter. So the<br />

effect <strong>of</strong> these processes on endocrine substances must be investigated prior to deciding<br />

to go for high tech processes, supposed this approach is considered reasonable<br />

at all.<br />

Protection <strong>of</strong> the natural water sources by avoiding the contamination with anthropogeneous<br />

substances must be given priority to investing into end <strong>of</strong> pipe technology.<br />

Commonly applied processes for treating <strong>of</strong> drinking water<br />

Since water quality is individual for each source <strong>of</strong> drinking water each source required<br />

individual treatment to render it into drinkable water complying with national and European<br />

directives.<br />

Water treatment engineering and chemistry is a science for itself, and the following<br />

shall only give a rough overview about commonly applied processes.<br />

Figure 11-5 illustrates the main treatment lines commonly found, which may be supplemented<br />

by additional special treatment lines made necessary by the presence <strong>of</strong><br />

specific undesirable substances in the raw water (e.g. fluorine, nitrates, calcium)<br />

Line 1 is designed to treat clean, unpolluted raw water requiring only disinfection to<br />

achieve the required microbiological quality. Line 2 is designed to treat water with no<br />

pollutants, except SS, and requiring simple filtration prior to disinfection. Where the<br />

water contains a small quantity <strong>of</strong> colloids, or has a more pronounced colour, in-line coagulation<br />

will solve the problem (Line 3). If the quantity <strong>of</strong> coagulant required to remove<br />

the colloids or reduce the colour is too high, the floc formed will be large and will rapidly


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clog the filter creating the need for frequent washing. It is therefore essential to provide<br />

a floc separation stage that uses settling or flotation techniques prior to filtration (Line<br />

4).<br />

The floc formed after addition <strong>of</strong> coagulant clarifies the water. This floc also has adsorbent<br />

qualities allowing a number <strong>of</strong> pollutants to be adsorbed on its surface. However,<br />

if the concentration <strong>of</strong> pollutant organic matter is too high, it may be necessary to<br />

include additional treatments, such as oxidation (Line 6) or adsorption (Line 5), which<br />

are used together with one or other <strong>of</strong> the clarification processes.<br />

Some <strong>of</strong> the above treatment stages have a biological effect (Line 7). Whenever a<br />

treatment process involves a solid liquid interface, the latter encourages the development<br />

<strong>of</strong> micro-organisms, which may have a positive effect on the treated water. This is<br />

true <strong>of</strong> filter stages (sand or GAC) and, to a lesser extent, the sludge bed employed in<br />

settling tanks.<br />

Figure 11-5 Basic processes in Drinking Water Treatment according to [DEGREMONT, Water<br />

Treatment Handbook, 1991]<br />

The traditionally applied processes in rendering surface waters suitable for drinking are:<br />

1. Mechanical treatment (screening, straining, sand removal, etc.)<br />

2. Aeration<br />

3. Sedimentation <strong>of</strong> suspended solids, mostly in combination with coagulation and<br />

flocculation


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4. Filtration (mostly rapid filtration, formerly slow sand filtration)<br />

5. Polishing processes (ozonisation, activated carbon adsorption <strong>of</strong> odours and<br />

taste)<br />

6. Disinfection<br />

These processes are combined according to requirement and have to be completed<br />

according to other substances contained in the raw water.<br />

In developing countries the processes described above are still being applied as the<br />

only treatment for raw water. In Europe modern sea and river water plants are more<br />

and more applying ozone and activated carbon as completing and substituting treatment<br />

stages to the traditional ones.<br />

Ozone<br />

• can support coagulation and flocculation by converting large monopolar molecules<br />

into smaller polar compounds<br />

• can crack organic molecules like phenoles<br />

• can oxidise soluble gases as sulphides and mercaptanes, in order to reduce odour<br />

and taste<br />

• can de-colourise by destroying colloids and colours <strong>of</strong> humic acids<br />

• can rise the BOD/COD ratio what increases the biodegradability <strong>of</strong> organic substances<br />

Ozone is usually used as pre-ozonisation prior to flocculation and filtration and as main<br />

ozonisation after flocculation and filtration in order to reduce odour colour and taste and<br />

for disinfection. Ozonisation is mostly applied in combination with activated carbon in<br />

order to reduce residual ozone in the treated water. [LEITZKE, 1999, a presentation <strong>of</strong><br />

applied ozone processing from the company Philaqua, Germany]<br />

Activated carbon<br />

Activated carbon has a broad spectrum <strong>of</strong> adsorptive activity, as most organic molecules<br />

are retained on its surface. The hardest to retain are the molecules which are the<br />

most polar and the linear ones with a very low molecular weight.. Molecules which are<br />

slightly polar, generating taste and smell, and molecules with a relatively high molecular<br />

weight are for various reasons well adsorbed on carbon.<br />

Beyond these adsorbent properties activated carbon is also a bacteria support that is<br />

capable <strong>of</strong> breaking down a fraction <strong>of</strong> adsorbed phase. Thus, a part <strong>of</strong> the support is<br />

continuously being regenerated and capable <strong>of</strong> freeing sites, allowing new molecules to<br />

be retained. (DEGREMONT, Water Treatment Handbook, 1991)<br />

The fact that activated carbon is also a bacteria support lead to the development <strong>of</strong><br />

biological activated carbon, which operates similar to trickling filters, allowing the growth<br />

<strong>of</strong> bacteria which can specialise in metabolising difficult biodegradable substances.<br />

Activated carbon is applied in two forms:<br />

Powdered activated carbon (PAC) and granular activated carbon.(GAC). PAC takes the<br />

form <strong>of</strong> grains between 10 and 50µm and its use is generally combined with clarification


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treatment. It is added continuously to the water together with flocculation reagents, it<br />

enters the floc and is then extracted from the water by sedimentation.<br />

The advantage <strong>of</strong> PAC is that adsorption is rapid since large surface area <strong>of</strong> powder is<br />

directly accessible, that it is constantly exchanged by new one and that quantities can<br />

be dosed according to requirement. For that reason it can also eliminate difficult to adsorb<br />

substances like pesticides. The big disadvantage <strong>of</strong> PAC is that it can not be regenerated<br />

and that it is difficult to remove final traces <strong>of</strong> impurities without adding excessive<br />

amounts <strong>of</strong> activated carbon. It is therefore used when intermittent or small<br />

quantities are required.<br />

Granular activated carbon (GAC) is used as filter bed through which the water to be<br />

treated passes, leaving behind the impurities which are thus extracted methodically.<br />

The water, as it progressively loses its pollutants, encounters zones <strong>of</strong> activated carbon<br />

which are less and less saturated and therefore more and more active.<br />

Some examples <strong>of</strong> applied surface water treatment processes in European cities are<br />

shown in Figure 11-6.


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Figure 11-6 Applied processes for treatment <strong>of</strong> surface waters in European Cities<br />

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Processes which might have an effect on the degradation <strong>of</strong> endocrine substances<br />

State <strong>of</strong> research<br />

Currently there are no publications available on the effect <strong>of</strong> drinking water processes<br />

on endocrine substances.<br />

A research programme in this has started on June 2000 in Austria under the Title “Austrian<br />

Research Co-operation on Endocrine Modulators (ARCEM). The program is<br />

scheduled up to mid 2003 and is initiated by Austrian Scientists from different universities<br />

together with the Austrian Federal Environment Agency and the Federal Ministry for<br />

Agriculture, Forestry, Environment and Water Management. One module under this<br />

programme will deal with the aspects <strong>of</strong> drinking water treatment.<br />

Under this programme the following treatment processes will be considered with regards<br />

to its effect on endocrine substances.<br />

1. Adsorption<br />

2. Metabolism <strong>of</strong> the substances under influence <strong>of</strong> oxidants like ozone, ozone in<br />

combination with UV radiation, persulfate, caroate.<br />

3. Metabolism <strong>of</strong> the substances under influence <strong>of</strong> chlorine compounds like chlordioxid,<br />

hypochlorit and hypochlorit in combination with UV radiation<br />

4. General effect <strong>of</strong> UV radiation on the substances<br />

5. Biological reduction <strong>of</strong> these substances by biological active activated carbon<br />

6. Biological reduction <strong>of</strong> these substances by slow sand filtration<br />

7. Biological reduction <strong>of</strong> these substances by biological Iron and manganese filters<br />

8. Influence <strong>of</strong> precipitation, flocculation and sedimentation on these substances.<br />

However results are not expected before mid 2001<br />

Based on the current knowledge <strong>of</strong> the effects <strong>of</strong> wastewater treatment processes on<br />

endocrine substances the following processes could in the opinion <strong>of</strong> the author be<br />

suitable to reduce or eliminate endocrine substances. However it is only the hypothetical<br />

opinion <strong>of</strong> the author.<br />

Membrane processes<br />

Endocrine substances can theoretically be fully removed from water (drinking water and<br />

also waste water) by membrane processes.<br />

Membrane bioreactors are a particularly promising alternative to conventional activated<br />

sludge treatment with respect to effluent quality, not just regarding the removal <strong>of</strong> endocrine<br />

disrupting substances [SCHWIER et al. 2001].<br />

These processes are classified according to the size <strong>of</strong> the pores <strong>of</strong> the membrane and<br />

thus by the size <strong>of</strong> water contents retained.(Figure 11-7).


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Figure 11-7 classification <strong>of</strong> membrane processes according to [DEGREMONT Water<br />

Treatment Handbook, 1991]<br />

Reverse osmosis:<br />

The raw water is pumped at 5 to 100 bar against a semi-permeable membrane which<br />

allows water to pass through while solutes are retained except for certain organic molecules<br />

similar to water (with a low molecular weight and strong polarity). In order to prevent<br />

fouling and scaling on the membrane, pre-treatment <strong>of</strong> the water with processes<br />

like ion exchanging, flocculation, micro filtration, treatment with polyphosphates, etc. is<br />

necessary. The treated water needs further treatment for pH adjusting and increasing <strong>of</strong><br />

salt concentration. 20 % <strong>of</strong> the treated raw water remains as wastewater which disposal<br />

is very costly. With that process nearly pure water can be produce, but technical needs<br />

and costs are tremendous.<br />

Ultra filtration:<br />

These membranes allow to retain compounds <strong>of</strong> a defined size in the raw water. Ultrafiltration<br />

allows only the coarsest solutes (macromolecules) to be rejected. The process<br />

is mainly applied to retain bacteria and viruses. Also turbidity can be reduced down to<br />

0,1 FNU. Ultrafiltration is frequently used for recycling <strong>of</strong> backwashwater from filtration.<br />

Micro filtration<br />

These membranes do not change the composition <strong>of</strong> the solution in any way, only suspended<br />

solids, colloids, bacteria etc. are rejected. It is assumed that micro filtration is<br />

suitable to retain endocrine substances only to a very little extent.<br />

Electrodialysis:<br />

If a liquid that is rich in ions, is subjected to an electrical field by means <strong>of</strong> two electrodes<br />

with a continuous potential difference applied between them, the cat-ions will be<br />

attracted to the negative electrode and the an-ions will be attracted to the positive electrode.<br />

If nothing impedes their movement, they will each lose their charge on the opposite<br />

sign electrodes and thus electrolysis takes place. However if a series <strong>of</strong> selective<br />

dialysis membranes is placed between the electrodes cation membranes, permeable<br />

only to the cations, and anion membranes, permeable only to the anions the migration


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<strong>of</strong> ions is restricted as the anions cannot pass through the negative membranes an the<br />

cation cannot pass through the positive membranes. (supposed they are arranged alternately).<br />

Compared to reverse osmosis the percentage <strong>of</strong> wastewater produce is only<br />

10%. A disadvantage is that all dissolved salts are retained what requires additional<br />

treatment <strong>of</strong> the produced water to make it suitable for drinking. With special membranes<br />

it is possible to retain only defined ions, like Nitrates, therefore it is used to remove<br />

nitrates from groundwater [DEGREMONT Water Treatment Handbook, 1991].<br />

With this process it is possible to demineralise water. However, the non ionised molecules<br />

in particular organic compounds remain behind in the treated water. Therefore<br />

electrodialysis can never remove all endocrine substances.<br />

Adsorption to activated carbon<br />

Another promising process to eliminate endocrine substances is adsorption to activated<br />

carbon as it is used to eliminate pesticides. The main features <strong>of</strong> the process are described<br />

above.<br />

The problem with regards to endocrine substance is the fact that these substances are<br />

found in raw water in very low concentrations. That means the adsorbent is likely to be<br />

saturated with other pollutants. Another problem is that more easily absorbable substances<br />

can re-mobilise already adsorbed substances. In any case the water treated<br />

with activated carbon must be properly pre treated with other processes prior to go for<br />

particular substances which are contained in the water in very low concentrations. A<br />

promising approach would be a two step process with PAC followed by a GAC process.<br />

Activated carbon and membrane processes are also applied for “tertiary treatment” <strong>of</strong><br />

wastewater treatment plants effluent. Both processes can retain dissolved organic<br />

compounds which have resisted upstream biological treatment. So also endocrine substances<br />

contained in wastewater can theoretically be retained from the effluent. In other<br />

words also for wastewater “technically everything is possible”, its just a question <strong>of</strong><br />

costs.<br />

Biological processes<br />

According to what is known about Alkylphenolpolyethoxylates and steroid hormones,<br />

aerobe biological processes seem to contribute to a shortening <strong>of</strong> NPnEO chains and to<br />

a degradation <strong>of</strong> steroid hormones. So one can assume that also aerobe biological processes<br />

as used in drinking water treatment will have an effect on these substances.<br />

However the role <strong>of</strong> biological processes in drinking water treatment is not comparable<br />

to wastewater treatment. Raw water <strong>of</strong> drinking water contains only very little nutrients<br />

which mostly have to be added to the process.<br />

Nevertheless, bio-films can be found on slow sand filters which are nowadays only used<br />

in small water works. According to Degrémont the biological action <strong>of</strong> slow sand filters<br />

is not effective when it comes to removing all micropollutants (phenoles, detergents,<br />

pesticides). For instance, they can only remove about 50 % <strong>of</strong> organo chlorinated pesticides.


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Attached growth <strong>of</strong> bacteria can also be found on activated carbon and on biological<br />

Iron and manganese filters.<br />

Oxidation<br />

Oxidation with ozone, a combination with ozone and UV radiation, or H2O2 + UV is a<br />

common process in drinking water treatment to eliminate or change organic compounds.<br />

In combination with an adsorption to activated carbon this is also a very promising<br />

process to eliminate endocrine substances.<br />

11.4 SUMMARY AND OUTLOOK<br />

It is assumed by the author that also the currently applied combination <strong>of</strong> processes for<br />

treating <strong>of</strong> surface waters (flocculation, sedimentation, filtration) are contributing a great<br />

deal to the reduction <strong>of</strong> these endocrine substances. A completion <strong>of</strong> these processes<br />

by ozonisation, followed by an activated carbon adsorption process (as frequently already<br />

now applied for polishing treatment) should be sufficient for the reduction <strong>of</strong> endocrine<br />

substances beyond the detection concentration.<br />

However, it can never be a reasonable solution to contaminate water and apply extremely<br />

expensive “end <strong>of</strong> pipe technology” to remove these contaminants. Avoiding <strong>of</strong><br />

contamination is for sure the more economic approach.<br />

Further research is necessary in order to evaluate the degradation behaviour <strong>of</strong> endocrine<br />

disrupters with respect to different wastewater technologies. In addition, the possibility<br />

<strong>of</strong> ground water contamination as a result <strong>of</strong> sludge deposition should be investigated<br />

[HELMREICH, 2001]


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12 OUTLOOK AND RECOMMENDATIONS WITH RESPECT TO HAZARDOUS<br />

SUBSTANCES<br />

The overall objective <strong>of</strong> the WFD is to achieve ‘good status’ for all waters. It is therefore<br />

<strong>of</strong> paramount importance to define the term ‘good status’ precisely and consistently and<br />

to apply identical criteria to all waters throughout the Community and accession countries.<br />

Many technical and political steps lie ahead which have to be mastered in order to<br />

safeguard comparable status assessments, thus creating a ‘level playing field’ for water<br />

protection in the EU.<br />

Key issues to be addressed:<br />

Member States will have to co-operate closely and from the very beginning in elaborating<br />

the criteria that define ‘good status’ and the administrative mechanisms necessary<br />

to achieve it for all Community waters. The development <strong>of</strong> such criteria should not be<br />

compromised by the political and/or economic implications <strong>of</strong> their application at Member<br />

State level. Member States should only use derogations from restoration where the<br />

costs are genuinely disproportionate to the long-term benefits. Good status should be<br />

ambitious and it should be meaningful. Clear provision must be made for a review <strong>of</strong> all<br />

Ecological Status criteria at regular intervals, with the aim <strong>of</strong> ensuring that these continue<br />

to optimise both the protection <strong>of</strong> existing quality and the incentive for ecological<br />

improvement according to new available scientific knowledge. Public involvement<br />

should be actively encouraged for all relevant decisions.<br />

All actors involved in decision-making – Member States, the Commission, the European<br />

Parliament as well as industry associations – have to apply the provisions <strong>of</strong> the WFD<br />

concerning priority hazardous substances. The objective <strong>of</strong> preventing inputs <strong>of</strong> a<br />

handful <strong>of</strong> particularly problematical chemicals within 20 years is not too ambitious, but<br />

a necessary prerequisite for efficiently protecting waters, including the marine environment.<br />

The Commission, Council and Parliament have to work together in devising progressive<br />

and ambitious groundwater legislation. Notably, a new balance needs to be found between<br />

agricultural interests and the protection <strong>of</strong> groundwater, which is after all the<br />

source <strong>of</strong> no less than two thirds <strong>of</strong> EU drinking water.<br />

The Commission will have to control that the river basin authorities have the competence,<br />

legal power and resources to realise the objectives <strong>of</strong> the WFD. The principles <strong>of</strong><br />

the WFD with respect to the status objectives, sustainable use <strong>of</strong> water and full-cost<br />

pricing are reflected in all sectoral Community policies and decisions. This applies more<br />

specifically to the Common Agricultural Policy, Structural and Cohesion Funds, and<br />

possible future policies on the organisation <strong>of</strong> the water industry. Member States should<br />

fully integrate water management into all sectors, including land-use activities. In order<br />

to make management more transparent, public consultation has to be introduced at<br />

every level and stage <strong>of</strong> the drawing-up <strong>of</strong> river basin management plans. Public participation<br />

will not only increase the effectiveness <strong>of</strong> the measures adopted to achieve


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the WFD’s objectives, but also the legitimacy and general acceptance <strong>of</strong> EU water policies.<br />

The Commission and Member States have to develop guidelines together for the economic<br />

analysis <strong>of</strong> water uses in a river basin district, which allow the sufficient assessment<br />

<strong>of</strong> all costs including environmental costs by 2004. But water is not just a commercial<br />

good and market forces are not easily applicable; the economically based calculation<br />

<strong>of</strong> environmental costs is therefore complicated. Simple and straightforward<br />

action - like identifying and reducing subsidies, charges or levies for water abstraction<br />

and use and earmarking them etc. – should be given priority.<br />

From a formal point <strong>of</strong> view and from the detailed analysis <strong>of</strong> the major provisions <strong>of</strong> the<br />

WFD, it is clear that it will be crucial that all the directives to be repealed in 2013 and<br />

especially the Groundwater and Dangerous Substances Directives have to be implemented<br />

and enforced as soon as possible. The WFD <strong>of</strong>fers a useful supporting frame<br />

to implement these directives and the full implementation <strong>of</strong> existing directives is a prerequisite<br />

for meeting the WFD objectives.


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13 ABBREVIATIONS<br />

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ADME Absorption, distribution, metabolism and excretion<br />

AG Ano-genital distance<br />

Ah Arylhydrocarbon<br />

AMH Anti-Mullerian hormone<br />

AR Androgen receptor<br />

BOD5<br />

Biological Oxygen Demand during 5 days<br />

BPH Benign prostatic hyperplasia<br />

CEFIC European Chemical Industry Council<br />

COD Chemical Oxygen Demand<br />

COMMPS (combined monitoring-based and modelling-based priority setting):<br />

COMMPS has been elaborated in collaboration with a consultant<br />

(Fraunh<strong>of</strong>er Institute for Environmental Chemistry and Ecotoxicology,<br />

Germany). The basic idea is to rank substances for which sufficient<br />

data are available according to their relative risk to the aquatic environment<br />

in an automated manner and to apply expert judgement for<br />

the final selection <strong>of</strong> priority substances.<br />

DBCP 1,2-dibromo-3-chloropropane<br />

DDE p,p-DDE: 1,1-bis(4-chlorophenyl)-2,2-dichloroethene<br />

DEPA Danish Environmental Protection Agency<br />

DES Diethylstilboestrol<br />

DHT Dihydrotestosterone<br />

EC European Community<br />

ECETOC European Centre for Ecotoxicology and Toxicology <strong>of</strong> Chemicals<br />

EDS Endocrine disrupting substance<br />

EEA European Environment Agency<br />

EEF Oestrogen equivalent factor<br />

ELV Emission Limit Values<br />

EQS Environmental Quality Standard<br />

ER Oestrogen receptor<br />

ESF European Science Foundation<br />

FSH Follicle stimulating hormone<br />

GAC Granular Activated Carbon<br />

GFEA German Federal Environment Agency<br />

GnRH Gonadotrophin-releasing hormone<br />

hAR Human androgen receptor<br />

hER Human oestrogen receptor<br />

IEH Institute for Environment and Health<br />

ISE International School <strong>of</strong> Ethology<br />

IUCLID International Uniform Chemical Information Database<br />

LH Luteinising hormone<br />

MRC Medical Research Council<br />

OECD Organisation for Economic Co-operation and Development<br />

ORD [United States <strong>of</strong> America] Office <strong>of</strong> Research and Development<br />

OSPAR The Convention for the Protection <strong>of</strong> the Marine Environment <strong>of</strong> the


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North-East Atlantic ("OSPAR Convention") was opened for signature<br />

at the Ministerial Meeting <strong>of</strong> the Oslo and Paris Commissions in<br />

Paris on 22 September 1992. The Convention has been signed and<br />

ratified by all <strong>of</strong> the Contracting Parties to the Oslo or Paris Conventions<br />

(Belgium, Denmark, the Commission <strong>of</strong> the European Communities,<br />

Finland, France, Germany, Iceland, Ireland, the Netherlands,<br />

Norway, Portugal, Spain, Sweden and the United Kingdom <strong>of</strong> Great<br />

Britain and Northern Ireland) and by Luxembourg and Switzerland.<br />

The OSPAR Convention entered into force on 25 March 1998. It replaces<br />

the Oslo and Paris Conventions, but Decisions, Recommendations<br />

and all other agreements adopted under those Conventions<br />

will continue to be applicable, unaltered in their legal nature, unless<br />

they are terminated by new measures adopted under the 1992<br />

OSPAR Convention.<br />

PAC Powdered Activated Carbon<br />

PCB Polychlorinated biphenyls<br />

PCO Polycystic ovaries<br />

PE Population Equivalent (usually 60g BOD5)<br />

POP Persistant organic pollutant<br />

PR Progesterone receptor<br />

QSAR Quantitative structure-activity relationship<br />

RBMP River Basin Management Plan (Article 13, WFD)<br />

SAR Structure-activity relationship<br />

SHBG Sex hormone binding globulin<br />

SS Suspended Solids<br />

Sts Sulphotransferase enzymes<br />

T3 Tri-iodothyronine<br />

TBT Tributyltin<br />

TCDD 2,3,7,8-tetrachlorodibenzo-p-dioxin<br />

TEF Toxic equivalent factor<br />

TR Thyroid hormone receptor<br />

UDP Uridine diphosphate<br />

UGT UDP-glucuronyl transferase<br />

USEPA United States Environmental Protection Agency<br />

WFD Water Framework Directive (full title: European Parliament and<br />

Council Directive establishing a framework for Community action in<br />

the field <strong>of</strong> water policy)<br />

WHO World Health Organisation<br />

WWTP Wastewater Treatment Plant


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LIST OF REFERENCES<br />

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2000/60/EC (23. October 2000): Directive <strong>of</strong> the European Parliament and <strong>of</strong> the Council<br />

establishing a framework for Community action in the field <strong>of</strong> water policy.<br />

1997/0067(COD), C5-0347/2000, LEX 224. Edited by the European Union.<br />

AHEL, M., GIGER W. and Ch. SCHAFFNER (1994): Behaviour <strong>of</strong> alkylphenol polythoxylate<br />

surfactants in the aquatic environment - I. Occurrence and transformation in<br />

sewage treatment, Wat. Res. 28<br />

AHEL, M., GIGER W. and M. KOCH (1994): Behaviour <strong>of</strong> alkylphenol polythoxylate<br />

surfactants in the aquatic environment - I. Occurrence and transformation in sewage<br />

treatment, Wat. Res. 28<br />

ANKLEY, G., Mihaich, E., Stahl, R., Tillitt, D., Colborn, T., McMaster, S., MilLer, R.,<br />

Bantle, J., Campbell P., Denslow, N., Dickerson R., Folmar, L., Fry, M., Giesy, J., Gray,<br />

LE., Guiney, P., Hutchinson, T., Ringer, R., Thomas, P., Touart, L., Van der Kraak, G.,<br />

Zacharewski, T. (1998): Overview <strong>of</strong> a workshop on screening methods for detecting<br />

potential (anti-) estrogenic/androgenic chemicals in wildlife. Environ toxicol chem.<br />

17 :68-87<br />

ATV, Abwassertechnische Vereinigung e.V. (1991): Bemessung von einstufigen Belebungsanlagen<br />

ab 5000 Einwohnerwerten<br />

BÄTSCHER, R., STUDER, C., FENT, K. (1999): St<strong>of</strong>fe mit endokriner Wirkung in der<br />

Umwelt, Schriftenreihe Umwelt Nr. 308, Hrsg. Eidgenössische Anstalt für Wasserversorgung,<br />

Abwasserreinigung und Gewässerschutz (EAWAG) und Bundesamt für Umwelt,<br />

Wald und Landschaft (BUWAL), Bern.<br />

BECKER – VAN SLOOTEN, K. (1994) Origine, contamination et comportement des organoétains<br />

dans les écosystèmes lacustres.École Polytechnique Fédérale de<br />

Lausanne. Dissertation<br />

BECKER E.C., BRINGEZU S. (1992) Belastung von Binnengewässern durch biozide<br />

Organozinnverbindungen – Immissionen, Wirkungen, Qualitätsziele, Anwendungsverbote.<br />

Z. Wasser – Abwasser – Forsch. 25: 40-46<br />

BECKER R., WINTER, D (1998): Umweltgifte: Antibiotika im Wasser, Beobachter<br />

16/98. Online in the internet:<br />

URL:"htpp://www1.beobachter.ch/reusable/detail.cfm?ObjectID=9BFF37B0-6EZ5-<br />

11D4BCD200104B673532&navid=0" (release order in November 2000).<br />

BECKER, K., MERLINI, L., DE BERTRAND, N. DE ALENCASTRO, L. F.,<br />

TARRADELLAS, J. (1992) : Elevated levels <strong>of</strong> organotins in Lake Geneva: Bivalves as<br />

sentinel organism. Bulletin <strong>of</strong> Environmental Contamination and Toxicology (1992)<br />

48:37-44.<br />

BECKER-VAN SLOOTEN, K., TARRADELLAS, J. (1994): Organisms in Swiss Lakes<br />

after their Ban: Assessment <strong>of</strong> water, sediment and Dreissena polymorpha Contamination<br />

over a four-year period. Archives <strong>of</strong> Environmental Contamination and Toxicology<br />

29, 384-392 (1995)


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

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Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 121 <strong>of</strong> 136<br />

BODENSEEKREIS: Wirtschaft im Wandel. Online in the Internet: URL:<br />

"http://www.bodenseekreis.de/include/baim.asp?/bodenseekreis/bodenseekreis/bodens<br />

eekreis-home.htm" (release order in January 2001).<br />

BROMBACH, H., MICHELBACH, S. (1998): Abschätzung des einwohnerbezogenen<br />

Nährst<strong>of</strong>faustrages aus Regenentlastungen im Einzugsgebiet des Bodensees. Bericht<br />

Nr. 49 der internationalen Gewässerschutzkommission für den Bodensee (International<br />

Water Protection Commission for Lake Constance (IGKB).<br />

BRO-RASSMUSSEN F., Calow, P., Canton, JH., Chambers, PH., Silva Fernandes, A.,<br />

H<strong>of</strong>fmann, L., Jouany JM., Klein, W., Persoone, G., Scoullos, M., Tarazona, JV., Vighi,<br />

M. (1994): EEC water quality objectives for chemicals dangerous to the environment<br />

(List I) . Rev. Environ. Contam. Toxicol. 137: 83-110<br />

BURGERMEISTER, P. G., ASWALD, K., MACHADO, L., MOWRER, J., and<br />

TARRANDELLAS, J. (1983). Concentrations en PCB et DDT des sédiments superficiels<br />

de la rive suisse du Lake Geneva. Schweiz. Z. Hydrol 45, 233-245<br />

BUWAL (1997): Gewässerschutz und Fischerei, Vom Leitgedanken zur Strategie. Online<br />

in the internet URL: “http://www.buwal.ch/wasser/d/leitgedanken.htm” (release order<br />

October 2000).<br />

BUWAL a: Chapter 11 "water" <strong>of</strong> the environmental report. Online in the internet<br />

URL:"http://www.buwal.ch/d/themen/umwelt/wasser/ek11u00pdf" (release order in February<br />

2001)<br />

BUWAL b: Chapter 18 "substances and organisms" <strong>of</strong> the environmental report. Online<br />

in the internet URL:"http://www.buwal.ch/d/themen/umwelt/st<strong>of</strong>fe/ek18u00pdf" (release<br />

order in February 2001)<br />

CHATON, N. (1997) Pollution des eaux par les produits phytosanitaires en Savoie.<br />

Rapport de stage - DDAF Savoie - Université d’Orlénas - Ecole supérieure de l’énergie<br />

et des matériaux, 123 p.<br />

CHATON, N. (1998) Pollution des eaux du bassin du lac du Bourget par les produits<br />

phytosanitaires en Savoie. Chambéry, 32 p.<br />

CIPEL (2000a): Geographie. Online in the internet URL: "http://www.cipel.org/deutsch<br />

/Geographie/geographie_bassin.htm" (release order in December 2000).<br />

CIPEL (2000b): Allgemeine Situation. Online in the internet URL:<br />

"http://www.cipel.org/deutsch /AllgSituation/etatgeneral_sante.htm" (release order in<br />

December 2000)<br />

CIPEL (2000c): Der Genfersee: Trinkwasser im Überfluss, Publikationen - Rund um<br />

den Genfersee n°21, Juni 2000. Online in the internet URL:<br />

"http://www.cipel.org/deutsch/publikationen/ RuG/publications_lettre_21.htm" (release<br />

order in December 2000)<br />

CIPEL (2000d): Zwischenbilanz der Aktionspläne 1991-2000 und Zustandsbericht (See<br />

und Fliessgewässer), Zusammenfassung. Published by CIPElL - Internationale Kommission<br />

zum Schutz des Genfersees. Online in the Internet URL: "http://www.cipel.org."<br />

(release order in December 2000)


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

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Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 122 <strong>of</strong> 136<br />

COM (1999) 706 final (17.12.1999): Communication from the Commission to the Council<br />

and the European Parliament, Community strategy for endocrine disrupters - a range<br />

<strong>of</strong> substances suspected <strong>of</strong> interfering with the hormone systems <strong>of</strong> humans and wildlife.<br />

Edited by the Commission <strong>of</strong> the European Communities<br />

COM (2000) 47 final, 2000/0035 (COD) (07. 02. 2000): Proposal for a European Parliament<br />

and Council Decision establishing the list <strong>of</strong> priority substances in the field <strong>of</strong><br />

water policy. Edited by the Commission <strong>of</strong> the European Communities<br />

COMFORT, S. D., ROETH, F. D (1996): Questions and Answers about Atrazine. University<br />

<strong>of</strong> Nebraska, Institute <strong>of</strong> Agriculture and Natural Resources. Online in the internet<br />

URL:"http://www.ianr.unl.edu/pubs/pesticides/g1158.htm" (release order in July<br />

2000).<br />

CORVI, C., and KHIM-HEANG, S. (1995). Polychlorobiphényles et mercure dans les<br />

ombles Chevaliers. Rapp. Comm. Int. Prot. Eauy Léman contre pollut. Campagne<br />

1994, 79-85<br />

CORVI, C., and KHIM-HEANG, S. (1996). Métaux et micropolluants organiques dans<br />

l´eau du Léman. Rapp. Comm. Int. Prot. Eauy Léman contre pollut. Campagne 1995,<br />

187-197<br />

COUNCIL DIRECTIVE 76/160 EEC <strong>of</strong> 8. December 1975 concerning the quality <strong>of</strong><br />

bathing water<br />

CROSSLAND, NO. (1992): Hazard assessment in freshwater ecosystems. Toxicol.<br />

Letter 64/65: 511-117<br />

DEVITT, T. (editor) (1997): What are endocrine disrupters?, How does the endocrine<br />

system work?, What’s being done? The Why Files, a magazine, focussing on the science<br />

behind today’s stories. Online in the internet:<br />

URL:”http://whyfiles.org/045env_hormone/index.html” (release Order in October 2000)<br />

DIEFENBACH, A., Schwermetalle, online in the internet: URL:"http://staff-www.unimarburg.de/<br />

~ gvw./texte.mix/chemie_metalle.html. (release order in June 2000)<br />

DREWS, J. E., BORNHARDT Ch. and M. JEKEL (1996): Untersuchung der Adsorptionseigenschaften<br />

von kommunalen Abwasserinhaltsst<strong>of</strong>fen während der Abwasserbehandlung<br />

und anschließender Bodenpassage; Vom Wasser, 86<br />

EC (1996): European commission; Technical guidance documents in support <strong>of</strong> Commission<br />

Directive 93/67/EEC on risk assessment for new notified substances and<br />

Commission Regulation EC 1488/94 on risk assessment for existing substances.<br />

ECETOC (1993): Environmental hazard assessment <strong>of</strong> substances. Technical Report<br />

No 51 January 1993, Brussels<br />

ecomed Verlagsgesellschaft AG & Co. KG, Landsberg<br />

ENVIRONMENTAL ATLAS BERLIN: 02.01 Quality <strong>of</strong> surface waters, section 7 <strong>of</strong> 10:<br />

Pollutant impacts in sediment and eels. Edited by the Senatsverwaltung für Stadtentwicklung,<br />

Berlin. Online in the internet: URL:<br />

"http://www.sensut.berlin.de/UISonline/dua96/html/ed201_07.htm" (release order in November<br />

2000)


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

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Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 123 <strong>of</strong> 136<br />

EPPENBERGER, D. (1997): Landwirtschaft muss das Antibiotika-Problem ausbaden.<br />

Online in the internet: URL: "http://www.eppenberger.ch//artikel/artikel8.htm" (release<br />

order in September 2000)<br />

EXTOXNET (1996) - Extension Toxicology Network, Pesticide Information Pr<strong>of</strong>iles. Online<br />

in the internet URL: "http://www.ace.orst.edu/info/extoxnet/pips/atrazine.htm" (release<br />

order in February 2001).<br />

FEDERAL ENVIRONMENT AGENCY LDT, AUSTRIA: Online in the internet<br />

URL:"http://www.ubavie.gv.at/umweltregister/sachinfo/atrazin/atrazin1.htm" (release order<br />

in July 2000).<br />

FENT, K. (1996) Ecotoxicology <strong>of</strong> organotin compounds. Crit. Rev. Toxicol. 26: 1-117<br />

FENT, K. (1998): Ökotoxikologie - Umweltchemie·Toxikologie·Ökologie. Georg<br />

Thieme Verlag Stuttgart.<br />

Fent, K., and Müller, M.D. (1991) Occurrence <strong>of</strong> organotins in municipal wastewater<br />

and sewage sludge and behaviour in a treatment plant. Environ. Sci. Technol. 25, 489-<br />

493.<br />

FRAUNHOFER INSTITUTE (98/788/3040/DEB/E1) (1999): Revised proposal for a list<br />

<strong>of</strong> priority Substances in the context <strong>of</strong> the Water Framework Directive (COMMPS Procedure)<br />

(98/788/3040/DEB/E1). Published in the Study on the Priorisation <strong>of</strong> substances<br />

dangerous to the aquatic Environment. Edited by the European Commission<br />

FRITSCHE, W (1998): Mikrobiologie, Grundlagen und Anwendungen. Gustav Fischer<br />

Verlag Jena.<br />

FÜRHACKER, M. (1998): Hormonell wirksame Substanzen i Klärschlamm – ein Problem?;<br />

Wiener Mitteilungen 153<br />

GIGER W., AHEL M., KOCH M., LAUBSCHER H.U., SCHAFFNER C., SCHNEIDER J.<br />

(1987) Behaviour <strong>of</strong> alkylphentol polyethoxylate surfactants and <strong>of</strong> nitrilotriacetate in<br />

sewage treatment. Wat. Sci. Tech., 19: 449-460<br />

GIGER W., BRUNNER, P. H., AHEL, M., MCEVOY, J., MARCOMINI, SCHAFFNER, C.<br />

(1987) Organische Waschmittelinhaltsst<strong>of</strong>fe und deren Abbauprodukte in Abwasser<br />

und Klärschlamm. Gas – Wasser – Abwasser 67: 111-122<br />

GIGER, W., AHEL M. and M. KOCH (1986): Das Verhalten von Alkylphenolethoxylat-<br />

Tensiden in der mechanisch-biologischen Abwasserreinigung, Vom Wasser, 67<br />

GONZALES, OJ. (1996): Formulating an ecosystem approach to the environmental<br />

protection. Environ. Managem. 20: 597-605<br />

GREENPEACE AUSTRIA (1999): Umweltwissen Chemie, hormonell wirksame Cemikalien,<br />

Effekte beim Menschen; bzw. Umweltwissen Chemie, Dauergifte (POPs). Online<br />

in the internet: URL: “HTTP://WWW.<br />

GREENPEACE.AT/umweltwissen/chemie/HormonellwirksameChemikalien.htm” resp.<br />

“HTTP://WWW. GREENPEACE.AT/umweltwissen/chemie/dauergifte/dutzend.htm”<br />

(release order date 2000-03-24)


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

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Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 124 <strong>of</strong> 136<br />

GURTZ, J., LANG, H., LUFT, G., STROBEL, F. WAGNER, G., (1997): Untersuchung<br />

der Wasserbilanz des Bodensees. Berichte und Skripten Nr. 61, Geografisches Institut<br />

ETH Zürich.<br />

HAMILTON, J. D. (1988): Recent human influences on the ecology <strong>of</strong> Loch Lomond,<br />

Scotland. Verhandlungen der Internationalen Vereinigung für theoretische und angewandte<br />

Limnologie, 23, 403-413.<br />

HETZENAUER, H. (1997): Zur st<strong>of</strong>flichen Belastung baden-württembergischer Bodenseezuflüsse.<br />

Landesanstalt für Umweltschutz Baden-Württemberg, Institut für Seenforschung,<br />

1. Auflage Langenargen 1997.<br />

http://www.sepa.org.uk/publicatio...quality/report/text/watertext.htm" (release order in<br />

February 2001)<br />

IMHOFF, K. (1990): Taschenbuch der Stadtentwässerung, 27. verb. Aufl. – München;<br />

Wien: Oldenbourg<br />

JARGER, D. (1994) 1 : Script for the lecture hydrobiology (in German) am Fachbereich<br />

BPV der Fachhochschule Hamburg.<br />

KA – WASSERWIRTSCHAFT, ABWASSER, ABFALL (2000): Zukunft der landwirtschaftlichen<br />

KEPPLER, R. Arzneimittel im Grundwasser, Risiken aus dem Wasserhahn. Online in<br />

the Internet: URL: "http://www.s-line.de/homepage/keppler/arznei.htm". (release order<br />

in November 2000)<br />

Klärschlammverwertung unter Einberufung der europäischen Entwicklung<br />

KLINKE; R., SILBERNAGEL, S. (editors) (1994), Lehrbuch der Physiologie, Georg<br />

Thieme Verlag Stuttgart,<br />

KÖCK, G. (1996): Schwermetalltoxizität bei Fischen, in Steinberg, Behrendt, Klapper,<br />

Handbuch angewandte Limnologie, V-3.1.1<br />

KOLLER, U. (1993): Qualitätsnormen und Grenz-bzw. Richtwerte für Schadst<strong>of</strong>fe im<br />

Trinkwasser. Online in the internet URL:<br />

"http://www.bayern.de/STMLU/umweltberat./ubaqua.htm" (release order in May 2000)<br />

KREUTLER, E., ITEL, W, KATTE, R., MATHIS, C. STÄMPFLI, A, UHLRICH, T,<br />

WIDMER, U. (2000): Transport wassergefährdender St<strong>of</strong>fe im Ufer- und im Zuflussbereich<br />

des Bodensees. Bericht Nr. 52 der internationalen Gewässerschutzkommission<br />

für den Bodensee (International Water Protection Commission for Lake Constance<br />

(IGKB).<br />

KREUZINGER; N., TU-Wien (1998): Zum Verhalten einiger hormonell wirksamer Substanzen<br />

in der Abwasserreinigung<br />

LANZ K., SCHEUER S.(2001): EEB Handbook on EU Water Policy under the Water<br />

Framework Directive (January 2001)<br />

1 This Script was spread in winter semester 1994/1995


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

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Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 125 <strong>of</strong> 136<br />

LEISEWITZ, A. (1996): Greenpeace Studie: Angriff auf das Hormonsystem - Umweltchemikalien<br />

verursachen Fortpflanzungsschäden und gefährden die Gesundheit.<br />

Edited by Greenpeace e. V. Hamburg. Online in the internet:<br />

URL:”http://www.greenpeace.de/GP_DOK_3P/CHLOR/SEITEN/C03HI12.HTM#krank”<br />

(release order in March 2000)<br />

LEITZKE, O. (1996): Methods for cleaning heavily polluted water with ozon combined<br />

with biological processes and ultra-violet radiation, proceedings <strong>of</strong> the first Australasian<br />

confernce <strong>of</strong> IOA, 1996, Vol. 2, pp 110-120<br />

LIVINGLAKES: Lake Constance (Bodensee): Austria, Germany and Switzerland. Online<br />

in the internet: URL: "http://www.livinglakes.org/bodensee/index.htm" (release order<br />

in January 2001).<br />

LÖW von, E. (1998): organische Schadst<strong>of</strong>fe, Überprüfung der Töxizität des Trinkwassers.<br />

Online in the internet URL: "http://www.med.unimarburg.de/umwelthy/kapb322.htm"<br />

and "http://www.med.unimarburg.de/umwelthykapb6.htm"<br />

(release order in May 2000).<br />

MAITLAND, P. S. (1981):introduction and catchment analysis. The ecology <strong>of</strong> Scotland's<br />

largest lochs: Lomond, Awe, Ness, Morar and Shiel, P. S. Maitland (ed), 1-27,<br />

Dr. W. Junk Publishers, The Hague.<br />

MARCOMINI, A., CARPEL P. D. (1989): Lichtensteiger Th., Brunner P. H., Giger W.;<br />

Behavior <strong>of</strong> Aromatic Surfactants and PCBs in Sludge-Treated Soil and Landfills; Environ.<br />

Qual., 18<br />

MARMO, L. (1999): Vortrag EREAU, Kontaktgespräch mit der EU-Kommission am 25.<br />

Februar 1999<br />

Merz, W., Metzger, J. W., Kemper, C., and Jenkins, E. (1998). Untersuchungen zum<br />

Eintrag, Verhalten und Verbleib von Sexualhormonen im Abwasser und Klärschlamm –<br />

Abschlussbericht für das Forschungsvorhaben (Stuttgart: Institut für Siedlungswasserbau,<br />

Wassergüte- und Abfallwirtschaft der Universität Stuttgart, Abt. Hydrochemie).<br />

MRASEK, V., KÜMMER, K. (2000): Antibiotika in Schiffsanstrichen - fragwürdige Taktik<br />

bei Jachtbesitzern. Deutschland Radio Berlin, Manuskript vom 28.3. 2000. Online in the<br />

internet: URL:"http://www.dradio.de/cgi-bin/user/fm1004/es/neu-forschak/22542.htm"<br />

(release order in September 2000).<br />

MÜLLER, H. (1993) Limnologischer Zustand des Bodensees Nr.19, Jahresbericht<br />

Januar 1991 bis März 1992 - Freiwasser, Pestizide -. Internationale Gewässerschutzkommission<br />

für den Bodensee (International Water Protection Commission for Lake<br />

Constance (IGKB).<br />

MUTSCHMANN, J., STIMMELMAYR F. (1999): Taschenbuch der Wasserversorgung,<br />

12. überarb. Aufl./bearb. Von Gerhard Bredel, Braunschweig; Wiesbaden: Vieweg,<br />

1999<br />

NORPOTH, K. (1973): Investigations on the problem <strong>of</strong> solubility and stability <strong>of</strong> steriod<br />

ovulation inhibitors in water, waste water and activated sludge. Zbl. Bakt. Hyg. I. Abt.<br />

Orig. B156


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

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Version: 4.0<br />

Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 126 <strong>of</strong> 136<br />

OECD (1989): Report <strong>of</strong> the OECD workshop on ecological effects assessment, OECD<br />

Environm. Monographs No 26<br />

PFEIFFER C., EMMERLING, CH., SCHRÖDER, D., NIEMEYER, J. (1998): Antibiotika<br />

(Ivermecin, Monensin) und endokrine Umweltchemikalien (Nonylphenol, Ethinylestradiol)<br />

im Boden.<br />

PICHLER, R. (1996): Antibiotika im Fleisch. Vegetarismus, Heft 3/96. Online in the<br />

internet: URL: "http://www.vegetarismus.ch./heft 96-3/antibio.htm" (release order in<br />

September 2000)<br />

PINDER, L. C. V., Pottinger, T. G., Billinghurst, Z., Depledge, M., H. (1999): Endocrine<br />

function in Aquatic Invertebrates and Evidence for Disruption by Environmental Pollutants.<br />

R&D Technical Report E67, EMSG; the institute <strong>of</strong> Freshwater Ecology; Pymouth<br />

environmental Research Centre.<br />

PRASUHN, V., SPIESS, E. und BRAUN, M. (1996): Methoden zur Abschätzung der<br />

Phosphor- und Stickst<strong>of</strong>feinträge aus diffusen Quellen in den Bodensee. Bericht Nr. 45<br />

der internationalen Gewässerschutzkommission für den Bodensee (International Water<br />

Protection Commission for Lake Constance (IGKB).<br />

ROßKNECHT, HETZENAUER (2000): Zum Vorkommen von Arzneimittel-Rückständen<br />

im Bodensee-Obersee und in einigen baden-württembergischen Bodensee-Zuflüssen.<br />

Landesanstalt für Umweltschuttz Baden-Württemberg Institut für Seenforschung, 2. Auflage<br />

Karlsruhe 2000.<br />

ROTH, E. (2001): Water Pricing in the EU, A Review; European Environmental Bureau;<br />

Publ. No. 2001/002<br />

SATTELBERGER, R. (1999): Arzneimittelrückstände in der Umwelt, Bestandsaufnahme<br />

und Problemstellung. Report R-162. Umweltbundesamt GmbH, Wien.<br />

SCHARF, S. SATTELBERGER R. and G. LORBEER (1999): Hormonell wirksame Substanzen<br />

im Zu- und Ablauf von Kläranlagen, Umweltbundesamt Wien 1999<br />

SCHLICHTIG, B., SCHÜLE, E., ROTT, U.: Eintrag von Pflanzenschutzmitteln in die<br />

Seefelder Aach. Published in Wasser und Abfall 3/2001, Vieweg Verlag.<br />

SCHRENK-BERGT, CH., STEINBERG, CH. (1998):Endokrine Substanzen in der Umwelt<br />

in Steinberg, Bernhardt, Klapper - Handbuch angewandte Limnologie, V-3.8<br />

SCHWEINFURTH H., LÄNGE R., MIKLAUTZ H. and G. SAHAUER (1997): Umweltverhalten<br />

und aquatische Toxizidät von Ethinylestradiol, Bayrisches Landesamt für<br />

Wasserwirtschaft: St<strong>of</strong>fe mit endokriner Wirkung im Wasser, Oldenbourg Verlag,<br />

München 1997<br />

SEPA (1997): SEPA Warns <strong>of</strong> Environmental Dangers <strong>of</strong> Sheep Dip. Online in the<br />

internet URL: "http://www.sepa.org.uk/pressrel/1997/sheepdip.htm" (release order in<br />

January 2001).<br />

SEPA (1999a) Improving Scotland's Water Environment. Online in the internet URL:"<br />

SEPA (1999b): Endocrine Disrupters. Published by the Scottish Environment Protection<br />

Agency


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SEPA (1999c): Strategy for Reducing Sheep Dip Chemical Pollution from the Textile<br />

Industry Launched. Online in the internet URL:<br />

"http://www.sepa.org.ukpressrel/1999/sepapr1599.htm" (release order in January<br />

2001).<br />

SEPA (2000a): SEPA Stresses Need For Care With Sheep Dips. Online in the internet<br />

URL: "http://www.sepa.org.uk/pressrel/2000/sepapr3300.html" (release order in January<br />

2001).<br />

SEPA (2000b): Scottish Agricultural Pollution Group Publish 13 th Annual Review. Online<br />

in the internet URL."http://www.sepa.org.uk/pressrel/2000/sepapr4200.htm" (release<br />

order in January 2001).<br />

SEPA (2000c): West region water quality review. Section 4 Loch Lomond and Section 8<br />

Lochs.<br />

SEPA: Loch Lomond Catchment Management Plan. Online in the internet: URL:<br />

"http://www.sepa.org.uk/publications/technical/LochLomondCatchmentPlan.pdf" (release<br />

order in January 2001).<br />

SETAC (1994): Aquatic dialogue group: Pesticide risc assessment and mitigation<br />

SETAC Pensacola<br />

Shore, L. S., Gurewitz, M., and Shemesh, M., (1993) Estrogen as an environmental<br />

pollutant. Bull. Environ. Contam. Toxicol. 51, 361-366.<br />

SOTO A. M., SONNENSCHEIN C., CHUNG K.L., FERNANDEZ M.F., OLEA N., OLEA<br />

SERRANO F. (1995) The e-screem assay as a tool to identify estrogens: an update on<br />

estrogenic environmental pollutants. Environm. Hlth. Perspect. 103: 7, 113-122<br />

STEINBERG, CH., BRÜGGEMANN, R., HARTMANN, A., HELLER, W., KIRCHNER,<br />

M., LIENERT, D., MÜLLER, K., PESTLIN, G., SCHEUNERT, I., SEILER, K.-P.,<br />

ERNST., D., SPIESER, O., KLEIN, J. (1996): Wirkungstests, in Steinberg, Bernhardt,<br />

Klapper - Handbuch angewandte Limnologie, V.-3.1<br />

STUMPF M., TERNES T.A., HABERER K., BAUMANN W. (1996) Nachweis von natürlichen<br />

und synthetischen Östrogenen in Kläranlagen und Fließgewässern. Vom Wasser<br />

87: 251-261<br />

Stumpf, M., Ternes, T. A., Haberer, K., and Baumann, W. (1996). Nachweis von natürlichen<br />

und synthetischen Östrogenen in Kläranlagen und Fliessgewässern. Vom<br />

Wasser 87, 251-261<br />

TABAK, H. H. (1981): Steroid Hormons as water pollutants. II. Studies on the persistence<br />

and treated wastewater: Developments i Industrial Microbiology (22) Proc. 37,<br />

General Meeting <strong>of</strong> Soc. Industr. Microbiol. August 1980, Flagstaff<br />

TABAK, H. H., Bunch R. L. (1979): Steroid Hormons as water pollutants. I. Metabolism<br />

<strong>of</strong> natural and synthetic ovulation inhibiting hormons by microorganisms <strong>of</strong> activated<br />

sludge and primary sttled sewage. Developments in Industrial Microbiology (11) Proc.<br />

26, General Meeting <strong>of</strong> Soc. Industr. Microbiol. Aug. 1969 Burlington, Garamond/Pridemark<br />

press Baltimore 367-376, 1970


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TÓTH, S., BECKER-VAN SLOOTEN, K., SPACK, L., DE ALENCASTRO, L.F.,<br />

TARRADALLAS, J (1996): Irgarol 1051, an antifouling compound in freshwater, sediment<br />

abd biota <strong>of</strong> Lake Geneva. Bulletin <strong>of</strong> Environmental Contamination and Toxicology,<br />

57:426-433.<br />

TSCHUI, M. BRUNNER H.P. and W. GIGER (1984): Accumulation <strong>of</strong> Refrctionary 4-<br />

Nonylphenol during mesophilic anaerobic sludge stabilisation. New Developments in<br />

Processing <strong>of</strong> Sludge and Slurries processings, Elevier Applied Science Publishers,<br />

London, Brüssel and Luxenburg, 79-81, 1984<br />

UBR (1994): Umweltprogramm Bodenseeraum, I Zusammenfassung und Wertung.<br />

Umweltministerium Baden-Württemberg Projektgruppe UBR Planungsgruppe Landschaftsarchitktur<br />

und Ökologie.<br />

UMWELTBNDESAMT BERLIN (1995): Fachgespräch – Umweltchemikalien mit endokriner<br />

Wirkung, Texte 65/95<br />

VAN STRAALEN, NM., DENNEMANN, CAJ. (1989): Ecotoxicological evaluation <strong>of</strong> soil<br />

quality criteria. Ecotox. Environ. Saf. 18: 241-251<br />

Wacker , Sriptum zur Pharmatox-Vorlesung für UWT-Studenten, Toxikologischer Teil,<br />

Fachhochschule Hamburg Bergedorf, WS 1994/95<br />

WATER TREATMENT HANDBOOK (1991): Sixth edition, Volume 1, Degremont –<br />

Water and the Environment<br />

WINKLER, G (1996): Zusammenfassung des Reports Flächennutzungs- und Flächenbezogene<br />

Daten der österrreichischen amtlichen Statistiken mit wasserwirtschaftlicher<br />

Relevanz. Online in the Internet: URL:<br />

"http://www.ubavie.gv.at/publikationen/reports/r1292.htm" (release order in January<br />

2001).<br />

WITTE, W. (1998): Antibiotika werden noch immer in der Tiermast verwendet. Ärztezeitung<br />

online, 3. 6. 1998. Online in the internet: URL:<br />

"http://www.aerztezeitung.de/does/1998/06/03/ 101a.asp?cat=/medizin/antibiotika" (release<br />

order in September 2000)<br />

WWF CANADA (July 1999): WWF Canada’s Web Guide to Endocrine Disrupting<br />

Chemicals. Online in the Internet: URL: ”http://www.wwfcanada.org/hormonedisruptors/index.html”<br />

(release order in March 2000)<br />

WWF CANADA, online in the internet: URL: "http://wwf.ca/pops/index.html", and several<br />

links (release order in November 2000).<br />

WWF US, online in the internet: URL:<br />

"http//www.worldwildlife.org/toxics/progareas/pop/index. htm and several links (release<br />

order in November 2000).


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LIST OF FIGURES<br />

Figure 5-1: Grasshopper effect with consequences to Canada [WWF Canada] .......... 23<br />

Figure 6-1: Approaches to identify endocrine disrupting substances (EDS). Dotted<br />

arrows represent entries to the sequence <strong>of</strong> testing that require further research<br />

before they can be endorsed or eliminated [WEYBRIDGE REPORT, 1996] ......... 31<br />

Figure 6-2: hazardous evaluation <strong>of</strong> substances [FENT 1998]..................................... 39<br />

Figure 6-3: Concept <strong>of</strong> the environmental or ecotoxicological risk assessment <strong>of</strong><br />

chemical substances [FENT 1998]......................................................................... 41<br />

Figure 7-1: Cross-linked effects to different biological-ecological levels, according to<br />

[FENT 1998]........................................................................................................... 43<br />

Figure 8-1: Factors and interdependent action which are decisive for the realisation <strong>of</strong><br />

potential microbial capacity <strong>of</strong> decomposition, modified according to [FRITSCHE<br />

1998]. ..................................................................................................................... 57<br />

Figure 9-1: Organic contaminants [FENT 1998] ........................................................... 59<br />

Figure 9-2: Transport- and transformation processes <strong>of</strong> contaminants in stagnant<br />

waters, modified according to [FENT1998]. ........................................................... 59<br />

Figure 10-1: Pollution inputs into water [BUWAL a]...................................................... 61<br />

Figure 10-2: Catchment Area <strong>of</strong> Lake Constance......................................................... 64<br />

Figure 10-3: Diagram <strong>of</strong> source and effects <strong>of</strong> pollutants in Lake Constance [according<br />

to UBR 1994].......................................................................................................... 65<br />

Figure 10-4: Lake Geneva [CIPEL 2000a].................................................................... 71<br />

Figure 10-5: Catchment Area <strong>of</strong> Lake Geneva [CIPEL 2000a]..................................... 71<br />

Figure 10-6: Population, industry and tourism in the Lake Geneva Catchment Area<br />

[CIPEL 2000a]........................................................................................................ 72<br />

Figure 10-7: Land use in the Catchment Area <strong>of</strong> Lake Geneva [CIPEL 2000a] ........... 73<br />

Figure 10-8: Sampling Locations in Lake Geneva [BECKER et al 1992]...................... 77<br />

Figure 10-9:Location <strong>of</strong> Bourget Lake in France (Source: SOGREAH)........................ 80<br />

Figure 10-10: Catchment Area <strong>of</strong> Bourget Lake (Source: SOGREAH)......................... 82<br />

Figure 10-11: Catchment Area <strong>of</strong> Loch Lomond [SEPA, changed] .............................. 85<br />

Figure 11-1 Monod function.......................................................................................... 94<br />

Figure 11-2 Mass streams in a typical wastewater treatment plant, according to<br />

[KREUZINGER, 1998]............................................................................................ 96<br />

Figure 11-3 Pathways <strong>of</strong> sewage sludge disposal........................................................ 97<br />

Figure 11-4 Distribution <strong>of</strong> NPnEO oligomeres........................................................... 104<br />

Figure 11-5 Basic processes in Drinking Water Treatment according to [DEGREMONT,<br />

Water Treatment Handbook, 1991]...................................................................... 107<br />

Figure 11-6 Applied processes for treatment <strong>of</strong> surface waters in European Cities ... 111<br />

Figure 11-7 classification <strong>of</strong> membrane processes according to [DEGREMONT Water<br />

Treatment Handbook, 1991] ................................................................................ 113


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LIST OF TABLES<br />

Table 3-1: List <strong>of</strong> priority substances in the field <strong>of</strong> water policy [COM (2000) 47 final] 19<br />

Table 7-2: Atrazine-Effects at Concentrations till 50 µg/l [FENT 1998]......................... 50<br />

Table 7-3: Toxic effects <strong>of</strong> environmental chemicals to aquatic organisms in the<br />

different biological levels [FENT 1998]................................................................... 52<br />

Table 8-1: Processes responsible for the destiny <strong>of</strong> environmental chemicals [FENT<br />

1998] ...................................................................................................................... 53<br />

Table 10-1: portion <strong>of</strong> area <strong>of</strong> the countries in the catchment area <strong>of</strong> Lake Constance<br />

[PRASUHN, et al. 1996]......................................................................................... 63<br />

Table 10-2:Concentrations <strong>of</strong> butyltins in water <strong>of</strong> Lake Geneva marinas and one<br />

natural site (reference) [BECKER et al 1992]......................................................... 78<br />

Table 10-3: Concentration <strong>of</strong> organotins in sediment <strong>of</strong> Lake Geneva marinas and one<br />

natural site (reference) [BECKER et al 1992]......................................................... 79<br />

Table 10-4: Concentrations <strong>of</strong> organotins in bivalves <strong>of</strong> Lake Geneva marinas and one<br />

natural site (reference) [BECKER et al 1992]......................................................... 79<br />

Table 10-5: Sewage treatment plants in the Bourget Lake catchment ......................... 83


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Schemata with the mode <strong>of</strong> action <strong>of</strong> endocrine disrupters<br />

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Cells have receptors where hormones are able to tie<br />

down. The hormone-receptor-complex is activating the<br />

cell. Natural hormones dock at receptors and activates<br />

it in the appropriate level [WWF CANADA, DEVITT<br />

1997].<br />

Endocrine disrupters are able to dock at the receptor,<br />

too. They are blocking normal signals because the<br />

body hormones can not fit into the receptor. Hormone<br />

blockers interferes with the signal from the body hormones<br />

[WWF CANADA, DEVITT 1997].<br />

The messages send by the endocrine disrupters are<br />

wrong. Either they give a signal stronger than the<br />

body's hormone (and at the wrong time), or...<br />

endocrine disrupter gives a signal weaker than natural<br />

hormones and at the wrong time [WWF CANADA,<br />

DEVITT 1997].


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EDC List<br />

Chemicals in the environment reported to have reproductive and endocrine disrupting<br />

effects.<br />

The list and references are based on: Colborn T (1998) Endocrine disruption from environmental<br />

toxicants. In: Rom WN (ed.) Environmental and Occupational Medicine,<br />

Third Edition. Lippincott-Raven Publishers, Philadelphia, 803-812. (in press) [WWF<br />

CANADA].<br />

Table <strong>of</strong> environmental pollutants with a putative endocrine effect [WWF<br />

CANADA]<br />

Herbicides<br />

- 2,4-D - ethiozin - picloram<br />

- 2,4,5-T - glufosinate-ammonium - pendimethalin<br />

- acetochlor - ioxynil - prodiamine<br />

- alachlor - linuron - pronamide<br />

- amitrole - metribuzin - simazine<br />

- atrazine - molinate - terbutryn<br />

- bromacil - nitr<strong>of</strong>en - thiazopyr<br />

- bromoxynil - oryzalin - triclorobenzene<br />

- cyanazine - oxyacetamide (FOE - trifluralin<br />

- DCPA<br />

Fungicides<br />

5043)<br />

- paraquat<br />

- benomyl - nabam<br />

- etridiazole - pentachloronitrobenzene<br />

- fenarimol - triadimefon<br />

- fenbuconazole - tributyltin<br />

- hexachlorobenzene - vinclozolin<br />

- mancozeb - zineb<br />

- maneb<br />

- metiram<br />

Insecticides<br />

- ziram<br />

- aldrin - dinitrophenol - mirex<br />

- bifenthrin - endosulfan (a and ß) - oxychlordane<br />

- carbaryl - eth<strong>of</strong>enprox - parathion<br />

- carb<strong>of</strong>uran - fenitrothion (methylparathion)<br />

- chlordane - fenvalerate - photomirex<br />

- chlordecone - fipronil - pyrethrins<br />

- chlorfentezine - ß-HCH - synthetic pyrethroids


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- l-cyhalothrin - heptachlor and H- - ronnel (fenchlorfos)<br />

- DDT and metabolites<br />

epoxide<br />

- endrin - toxaphene<br />

(DDE, DDD) - lindane (ß-HCH) - transnonachlor<br />

- deltamethrin - malathion - aldicarb<br />

- dic<strong>of</strong>ol - methomyl - DBCP<br />

- dieldrin<br />

- dimethoate<br />

Other Types <strong>of</strong> Pesticides<br />

- methoxychlor - n-2-fluorenylacetamide<br />

- ethylene thiourea (ETU) - pentachlorophenol (PCP)<br />

- pentachlorobenzene - piperonyl butoxide<br />

Industrial Chemicals & <strong>Contaminants</strong><br />

- 4-OH-alkylphenol - 4-OH 2',3',4',5' tetrachlorobiphenyl<br />

- aluminum* - 2,2',3,3',6,6' hexachlorobiphenyl<br />

- benzopyrene - pentabromodiphenyl ether<br />

- bisphenol-A - penta- to nonylphenols<br />

- 4-OH-biphenyl - phthalates<br />

- t-butylhydroxyanisole (BHA) - benzylbutylphthalate<br />

- cadmium* - di2ethylhexylphthalate (DEHP)<br />

- carbon disulfide - diisobutylphthalate<br />

- dioxin (2,3,7,8-TCDD) - dinhexylphthalate (DnHP)<br />

- furans - di-n-octylphthalate (DnOP)<br />

- hydroxy (hydro)-quinones - diOHbenzoicacids (DHBA)<br />

- lead* - phenol<br />

- mercury* - polychlorinated diphenyl ether<br />

- methylcolanthrene (MCA) - radioactive iodine<br />

- polybrominated biphenyls (PBBs) - resorcinol<br />

- polychlorinated biphenyls (PCBs) - styrenes<br />

- 2 to 4-OH 2',5' dichlorobiphenyl - tetrachloro-benzyltoluenes<br />

- 2,3,4 trichlorobiphenyl - thiocyanate<br />

- 4-OH trichlorobiphenyls (2,2',5;2',4',6') - vinyl acetate<br />

- 3-OH 2',3',4',5' tetrachlorobiphenyl *metals


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ANNEX 2<br />

Examples <strong>of</strong> environmental effects<br />

The great lakes in North America include a whole cocktail <strong>of</strong> POPs. A detailed investigation<br />

<strong>of</strong> the animals living at these place, has been carried out over many years<br />

[LEISEWITZ 19969]. Besides unknown symptoms at several living free animals even<br />

the disappearance <strong>of</strong> whole species is described. In the case <strong>of</strong> 16 investigated fish,<br />

bird, reptile and mammal species which drops have been died or which are not able to<br />

reproduce themselves in a normal way, are top predators standing at the top <strong>of</strong> the food<br />

chain. They are eating fish or fish-eating animals. The symptoms lead to a reduction <strong>of</strong><br />

population, reach from a kind <strong>of</strong> "wasting" over damages <strong>of</strong> the immune system and organs,<br />

interference <strong>of</strong> the thyroid gland, deformities, tumours and cancer as well as behavioural<br />

abnormalities until reproductive damages [GREENPEACE AUSTRIA 1999].<br />

Related interference are found as well at humans which ate fish from the Great Lakes.<br />

Tumours and cancer, behavioural abnormalities and learning deficits at children which<br />

mothers ate a lot <strong>of</strong> fish during the pregnancy, impairment <strong>of</strong> the immune system and<br />

interference <strong>of</strong> the sexual system, poor fertility, diabetes and many more is ascertained<br />

[LEISEWITZ 1996]. DDT and it's decomposition products, PCB, dioxins and several<br />

pesticides belong to the dedicated substances having the origin in the neighbouring<br />

industry and agriculture [GREENPEACE AUSTRIA 1999].<br />

Behavioural and perception interference<br />

EDCs have the potential to disrupt the normal neurological development which lead to<br />

behavioural and cognitive abnormalities [WWF CANADA].<br />

Seagulls burdened with DDT res. it's decomposition product DDE show changes in the<br />

sexual ratio. As a result <strong>of</strong> this, female nested with female. In Florida it was noticed, that<br />

adult birds did not mate or take interest in breeding colonies [WWF CANADA,<br />

GREENPEACE AUSTRIA] .<br />

Hormonal malfunction and feminisation<br />

A 1980 dic<strong>of</strong>ol spill (a pesticide similar in structure to DDT) into Lake Apopka, Florida<br />

caused serious hormonal dysfunction and feminisation in the lake's alligator population<br />

[WWF CANADA]. The <strong>of</strong>fspring were hermaphrodites or have a quite belittled phallus<br />

so that they were unable to mat themselves ]LEISEWITZ 1996]. Ratios <strong>of</strong> estrogen to<br />

testosterone in eggs were twice as high as normal. Adult female alligators produced<br />

about twice the normal estrogen levels for a typical female, while male alligators<br />

emerging from eggs produced almost no testosterone [WWF CANADA].<br />

Male fishes exposed to nonyl phenols, a substance used in detergents and various industrial<br />

processes, produce vitellogenin. Vitellogenin is an estrogen stimulated egg-yolk<br />

protein produced by female during egg production. Vitellogenin concentrations in male<br />

trout living in river outfalls <strong>of</strong> sewage treatment plants were up to 100,00 times higher<br />

as in normal male fishes. More than half <strong>of</strong> their blood protein was yolk [WWF<br />

CANADA].<br />

Decreased immune defence system


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Dioxin, even at levels 25 % below the amount found in general human populations, reduces<br />

white blood cells and the organism is more susceptible to viral infections [WWF<br />

CANADA].<br />

Levels <strong>of</strong> PCB were two-to-three times higher in seals and dolphins died in the North<br />

Sea, the Baltic Sea, along the Eastern Seaboard <strong>of</strong> the United States and the Mediterranean<br />

Sea than in healthy animals. Synthetic chemicals and heavy metals have been<br />

reduced the animals' immune system function and they died at infectious diseases.<br />

Seals fed with PCB- and dioxin-contaminated Baltic Sea fish had significantly lower killer<br />

cell activity and antibody response than seals fed a less contaminated source from<br />

the Atlantic [WWF CANADA].<br />

Thyroid effects<br />

Certain PCBs and dioxins are known to impair normal thyroid function. Thyroid hormones<br />

are essential for the whole brain development during the embryonic period and<br />

the time after. Interference with thyroid function at this time can lead to a loss <strong>of</strong> intelligence<br />

and behaviour abnormalities. Studies are finding links between in utero exposure<br />

and behavioural responses in children. Most notably is hyperactivity. A hyperactivity is<br />

also be initiated if the level <strong>of</strong> thyroid hormones is reduced during the pregnancy [WWF<br />

CANADA].<br />

Researches at the Great Lakes report <strong>of</strong> a 100 % prevalence <strong>of</strong> thyroid enlargement in<br />

2-4 year old salmons. Some salmons have been found with thyroids over a million<br />

times their normal size. In Lake Erie the problem is so severe that they are beginning to<br />

rupture. Almost all the salmons observed had hermaphroditic reproductive system[WWF<br />

CANADA].<br />

Carcinogenic effects<br />

An excess exposure to estrogen is a primary risk factor for getting breast cancer, endometrial<br />

cancer and for endometriosis (a painful disease characterised by cells which<br />

are normally found inside the uterus growing outside the uterine wall). The increase <strong>of</strong><br />

endometriosis was found at female monkeys exposed to low levels <strong>of</strong> dioxin were subsequently<br />

found to develop endometriosis [WWF CANADA].<br />

DDT, PCBs, keptone and atrazine increase the production <strong>of</strong> a more potent form <strong>of</strong><br />

estrogen in the body which increase the chance <strong>of</strong> cancer [WWF CANADA].<br />

Testicular cancer has increased dramatically in industrial countries. Precancerous cells<br />

develop during embryonic periode and lie dormant until some hormonal surge during<br />

puberty triggers their proliferation. Prostate cancer is the most common cancer in<br />

American men and has increased 126 % from 1973 to 1991. Animal studies have found<br />

that long-term exposure to estrogen can induce prostate cancer [WWF CANADA].<br />

Decrease <strong>of</strong> sperm count<br />

Sperm counts have dropped by approximately 50 % over the past 50 years. In several<br />

studies men from different regions <strong>of</strong> North and South America, Europe and Asia were<br />

studied. The indicated average sperm count decreased 45 % between 1938 and 1990.<br />

The rate <strong>of</strong> decline was greater in younger males, suggesting that the damage was<br />

done in the womb. Surveys <strong>of</strong> men born in the UK between 1955 and1974 have found<br />

that younger men have significantly poorer sperm quality. Thereto belong a decrease in<br />

concentration and motility [WWF CANADA].


Integrated Water Resource Management for Important Deep European Lakes and their Catchment Areas<br />

EUROLAKES<br />

<strong>D10</strong>: <strong>Impact</strong> <strong>of</strong> <strong>Contaminants</strong><br />

FP5_Contract No.: EVK1-CT1999-00004<br />

Version: 4.0<br />

Date: 25/07/01<br />

File: <strong>D10</strong>-vers.4.0.doc<br />

Page 136 <strong>of</strong> 136<br />

One hypothesis is that the production <strong>of</strong> sertoli cells responsible for sperm production,<br />

is being reduced by exposure to estrogenic and/or anti-androgenic chemicals during the<br />

embryonic development. Since each sertoli cell produces only a fixed number <strong>of</strong> sperm,<br />

their number are limit the number <strong>of</strong> sperm an adult man can produce. During male development<br />

the pituritary gland secretes a follicle-stimulating hormone, which is suppressed<br />

with increasing estrogen levels, thereby reducing sertoli cell formation [WWF<br />

CANADA].<br />

Dying <strong>of</strong> sea birds at Clear Lake (California)<br />

Since the 50ies a massive reduction <strong>of</strong> Aechmophorus occidentalis population took<br />

place. For the combat <strong>of</strong> mosquitoes the DDT related pesticide DDD was used several<br />

times with a increasing dosage. In the fatty tissue <strong>of</strong> dead birds high concentrations <strong>of</strong><br />

DDD were found. Than a investigation <strong>of</strong> the fishes in the sea and the whole food chain<br />

followed. The DDD was found in high concentrations as well in the planctonic algae. It<br />

was also be ascertained that the pesticide is passed down from one generation to the<br />

next in algae, fishes, birds, frogs and other organisms [GREENPEACE AUSTRIA].<br />

Dying <strong>of</strong> peregrine falcons in Germany<br />

Through Pesticide contaminated preys (DDT and other) the animals were poisoned and<br />

their population increased in Germany and also on the whole northern hemisphere<br />

since 1950. On the one hand the animals are poisoned through the preys, on the other<br />

hand more and more clutches were lost because <strong>of</strong> brashly egg shells. This was the<br />

reason <strong>of</strong> a hormone disruption <strong>of</strong> the calcium metabolism caused by pesticides<br />

[GREENPEACE AUSTRIA].

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