Emerging Tools Manual

SWIFT-WFD

SScreening methods for WWater data IInFFormaTTion in support of the implementation of the WWater FFramework DDirective

Contract: SSPI CT 2003 - 502492

REPORT: Draft 2

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Editors: Benoit Roig, Ian J. Allan, and Richard Greenwood

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This document aims to provide easy access to the wide range of candidate monitoring methods currently available or under development for supporting the Water Framework Directive (WFD). It is organised with tables containing parameters and pollutants that may need to be monitored (the problems) and these are linked to tables containing summaries of the available methods, both biological and physicochemical, (the solutions). These tables are also linked where appropriate to tables summarising current legislation and standards, and to relevant EU-funded projects that are either current or have been completed. Tables are further linked to a bibliography containing references to key sources providing further detailed information on the properties and use of particular methods. The tables provide information that will allow the user to assess the suitability of various methods for a particular purpose. It provides a list of the tools available in the toolbox, and their utility for the task that needs to be undertaken. This document was edited with the collaboration of:

contributor Affiliation Contact

Benoit Roig [email protected] Catherine Berho

Armines / Ecole des Mines d'Als [email protected]

Richard Greenwood [email protected] Graham Mills [email protected] Ian J. Allan

University of Portsmouth

[email protected]

Marinella Farre [email protected] Damia Barcelo CSIC [email protected]

K. Clive Thompson ALcontrol Labs [email protected]

Fabienne Seby [email protected] David Point University of Pau [email protected]

Helene Budzinski LPTC-University of Bordeaux [email protected]

Jean-Luc Cecile Guillain Pierron Aquametris [email protected]

OVERVIEW OF THE MANUAL (for the non-specialists) Aims of the manual The aim of this operational manual is to present a toolbox of existing and more importantly emerging methods that may respond to the needs of one or more mode of monitoring (surveillance, operational, or investigative monitoring) embedded in the European Water Framework Directive. Their aim is to cost-effectively obtain consistent and reliable data that can be used for water quality management (at the river basin level) and comparison across national boundaries. The objective of this manual is to provide those in charge of water quality monitoring under the WFD with lists of tools and techniques that may be used for the assessment of physico-chemical, biological and chemical quality elements and parameters (not including hydromorphological elements). Overview of the content and structure of the manual The manual uses a problem-based approach by including background information on priority and emerging pollutants as well as contaminants lined out in other significant regulations (e.g. OSPAR, Helcom), the possible technologies for monitoring various quality elements, and finally information on standards and legislation and recommendations to obtain fit for purpose data (See figure below).

Background information covers physico-chemical data for organic and inorganic priority pollutants as well as typical concentrations found in EU waters, major sources and ecological risk assessments of these chemicals. In addition, WFD monitoring information is summarised.

Operational Manual

Background information

Measurement of physico-chemical parameters

Biological assessment techniques

Chemical monitoring techniques

Legislation and standards

Monitoring

The manual covers a range of tools for: physico-chemical monitoring, methodologies for biological/ecological monitoring, water quality evaluation through biological community/diversity

assemblages, non-specific or pollutant-specific biosensors and biological early warning

systems (BEWS), emerging tools for the measurement of time-integrated chemical

concentrations through the use/deployment of passive samplers, available analytical tools for the measurement of chemical levels, and Tools based on the use of biological material for pollutant-specific

concentration measurements. While some of these techniques are commercially available, many currently remain at prototype stage. Tools may be based on the collection of spot samples, passive sampling techniques, or continuous in-situ monitoring and may be more or less suitable depending on the task to be undertaken. The final section of the manual focuses on the collection of fit-for-purpose data, by providing information on quality assurance and control issues, legislative aspect, and the use of standards. Use of the manual Since the Water Framework Directive does not mandate the use of any particular methods for monitoring, this toolbox aims to be a guide to facilitate the choice of a suitable method for water quality monitoring under the WFD. Two important criteria in the choice of a particular monitoring tool or technique are cost-effectiveness and obtaining fit-for-purpose data. This manual is built around a set of tables presenting available tools and techniques for physico-chemical parameter measurements, biological and chemical assessment tools. Tables may be access through the list of content, list of tables or through the use an interface based on the quality element parameters that may be measured. Additional information on tools and technologies such as limits of detection, calibration ranges, costs, measurement methods used, or assay time, when known, is provided for guidance on the choice of a suitable method. This should facilitate the use of novel or emerging techniques to replace standard spot sampling when possible to reduce cost and obtain additional and more meaningful data (e.g. time-averaged concentrations). This manual should also be useful to determine gaps in technological advances, or identify technologies worth further developments.

Executive summary Introduction The Water Framework Directive aims to achieve good quality status for all surface, ground and coastal waters throughout Europe by 2015. In addition, it is expected to contribute to the protection, prevention of deterioration and improvement of all water bodies across the European Union. As the WFD requires a River Basin Approach and many waters cross national boundaries, monitoring under the Water Framework Directive aims to harmonise the collection of water quality information to provide comparable, reliable and consistent data. The success of the implementation of the WFD will depend on the availability and quality of information available to those charged with managing water quality. Monitoring under the WFD is required to cover a number of biological, hydromorphological, physico-chemical and chemical (priority and/or emerging pollutants) quality elements. These, in turn, are dependent on the type of water body being monitored. Three modes of monitoring are specified in the directive. Surveillance monitoring will assess long-term water quality changes and

help providing baseline data on river basins. Operational monitoring aims to provide additional and essential data on

water bodies at risk or failing environmental objectives of the WFD. Finally, the objective of investigative monitoring is to determine causes of

such failure when they are unknown. More generally, information obtained through surveillance monitoring will be used to determine requirements for future monitoring, whether to implement operational or investigative monitoring. The Water Framework Directive does not mandate the use of a particular set of methods, but aims to ensure the establishment of adequate monitoring programmes based on the quality elements outlined above. This manual This operational manual aims to provide those in charge of managing and monitoring water quality with a toolbox of presently available or emerging technologies suitable for at least one or more type of monitoring under the WFD. The manual uses a problem-based approach by including background information on priority and emerging pollutants, the possible technologies for monitoring various quality elements, and finally information on standards and legislation and recommendations to obtain fit for purpose data. The manual covers a range of tools for physico-chemical monitoring, methodologies for biological/ecological monitoring, water quality evaluation through biological community/diversity assemblages, non-specific or pollutant-specific biosensors and biological early warning systems, emerging tools for the measurement of time-integrated chemical concentrations through the use/deployment of passive samplers, available analytical tools for the measurement of chemical levels, and tools based on the use of biological material for pollutant-specific concentration measurements.

This manual, however, does not aim to cover hydromorphological monitoring. It is important to note at this stage that the objective of this manual is to provide extensive lists only of technologies either commercially available, emerging or promising prototypes that may be deployed for monitoring under the WFD. Since different methodologies or techniques measure different pollutant fractions (sorbed and/or dissolved phases, species-specific), and may be field or lab-based, based on spot sampling, on-line, continuous measurements or passive sampling, their applicability to surveillance, operational and investigative monitoring may differ significantly. It is not the aim here to allocate one specific tool or method to a particular type of monitoring as this is highly dependent on situation- and site-specific information or costs. Certain modes of sampling or traditional and emerging monitoring techniques are more or less adapted to tasks such as quantification or detection of presence/absence of specific pollutants present in water. The table below reviews possibilities offered by various monitoring techniques to quantify and identify pollutants in waters. Specificities associated with different monitoring techniques Quantification Identification

Chemical analysis Traditional analysis + + Analyte-specific sensors + +

Screening methods Physico-chemical parameters (TOC, DO) +/- - Analyte group screening (oil, PAHs, metals) +/- +/- Biological effects (toxicity tests, BEWS) +/- -

Emerging techniques Spot sampling - analysis by traditional methods + + - analysis by screening methods +/- - Biological early warning systems +/- +/- Passive sampling + + Continuous monitoring - analysis by non-screening methods + + - analysis by screening methods +/- - (+) adequate, and (-) inadequate for chemical quantification/identification Background information The first section introduces the types of water relevant to the Water Framework Directive, and their relevant quality elements or parameters necessary for the various types of monitoring. Additional information on the design of the three types of monitoring includes monitoring objectives, monitoring site and quality element selection. As outlined above, the problem-based approach of the manual relies on the identification of priority and emerging pollutants and lists of the 11 priority hazardous substances, 14 priority substances under review, and 8 priority substances, and of 94

emerging substances are presented in the manual. Links to the OSPAR list of substances of possible concern, Danube River Protection Convention list, the Barcelona Convention list and to the international commission for the protection of Rhine (ICPR) list are also given. Following these extensive lists of chemicals, a set of tables relates typical levels found in river, ground and sea waters, and the principal uses of priority organic and inorganic pollutants. Links to webpages and references are also added for readers in search of additional information on these chemicals. A section then describes environmental and ecotoxicological risk assessments for these priority substances. This section would not be complete without the final tables relating main physico-chemical characteristics of these pollutants. These include their formula, molecular weight, a measure of their hydrophobicity (Log KOW), their solubility, volatility, toxicity, lability, and finally Henrys constants. Methods for physico-chemical properties and nutrient levels measurements Table 6 presents an extensive (but not totally complete) range of methods and technologies commercially available or in development that may be used for the monitoring of physico-chemical properties of water bodies. Details are given for each technology and include the parameter measured, method used for the measurement, type of water it may be used for, sampling time, cost, fraction measured (total/dissolved), model name, institution/company responsible for production/commercialisation, precision of the measurement, calibration range and maintenance frequency and duration are given. A number of parameters is regrouped here. Nutrients such as ammonium, nitrite, nitrate, phosphate, and more generally total nitrogen and phosphorus may be play an important role in monitoring as they are involved in eutrophication processes or may contaminate groundwater (nitrates) after fertiliser applications. A number of parameters may be used to characterise the oxygenation level of a water body. They include the measurement of dissolved oxygen, the chemical oxygen demand, the biochemical oxygen demand, redox conditions, or respirometry. The acidification status may be obtained through the measurement of pH, while salinity may be given by measuring conductivity. Importantly, the amount of dissolved, suspended organic matter can generally be assessed by measuring total organic matter, total organic carbon, OM aromaticity, and the turbidity of the water. In turn the presence and levels of organic matter strongly influence the chemical oxygen demand of a water sample. For ammonium ions, 42 devices (24 commercially available) are available based on a range of specific electrodes, colorimetric, UV absorption and spectrophotometric, chemiluminescence, and titrimetric methods or ion chromatography. Devices may be based on spot sampling, continuous, in-situ or lab-based measurements. Three devices were found for the measurement of biochemical oxygen demand (BOD), of which 2 are commercially available and one still at the prototype stage. Chemical oxygen demand can be

measured using 14 devices (8 commercially available) in continuous or spot sampling based on electrode, photometric, UV absorption/spectrometric or other titrimetric methods. There are 12 devices for conductivity measurements (10 commercially available); most are based on electrode measurements for probe/continuous or spot sampling. Ten commercially available devices generally based on membrane polarography may be used for dissolved oxygen monitoring. Monitoring of the organic matter content of water may be undertaken using 5 devices (4 commercially available) mostly using photometric methods. Seven devices are available for pH monitoring for continuous or spot sampling measurements. 21 devices (12 commercially available) generally based on colorimetric, optical photometric, spectrometric, ion chromatographic method may be used for monitoring phosphate in water. Six commercial devices all based on electrodes are available to monitor oxidation/reduction conditions in water. Four respirometric devices are also listed in this table. A large number of tools (23 including 14 commercial) is available to measure total organic carbon (TOC). Only one instrument is currently listed for measuring total nitrogen. Five devices (4 are commercially available) may be used to measure total phosphorus in water. Many devices (31 including 21 commercially available), mainly based on continuous in-situ nephelometric measurement, are available for turbidity monitoring. Eleven devices are available for spot sampling and continuous measurement of organic matter aromaticity. Certain devices such as multi-parameter probes allow the in-situ measurement of multiple parameters simultaneously. Biological assessment techniques The use of whole organisms and monitoring of biological responses to assess environmental quality and changes is an important aspect of water quality monitoring under the WFD. Biomonitoring may be qualitative, semi-quantitative or quantitative depending on the tools used. Details on microbiological status testing are initially given in this section while the remaining part of this section examines the possibility for using sentinel organisms, biological organism diversity and community structure, the use of biomarkers, bioassays and biosensors, and finally biological early warning systems. Background information may be found on possible sentinel organisms, assessment methodologies, potential biomonitoring parameters, biotic and diversity indices. In addition advantages and drawbacks of the use of benthic invertebrates, fish and algae for biomonitoring are given. Table 7 summarises certain parameters that may be measured when undertaking biomonitoring, the rationale for the parameter selection, and issues involved in the monitoring. Table 8 presents the main European projects aiming to develop standardised methods for sampling aquatic organisms and the subsequent analysis of sampling result to evaluate water quality. These tools usually assess water condition by evaluating the observed deviation between the sampling site and reference conditions based on monitoring at pristine sites. Importantly, data from pristine sites at different locations across Europe are likely to differ. Hence many of the tools/softwares are very similar in their process, but differ in reference conditions. These tools are usually based on benthic invertebrates (RIVPACS, AQEM, ECOPROF, AusRivAs), fish

(CITYFISH, FAME) or a combination of invertebrates, algae, fish and macrophyte (ECOFRAME and PAEQANN). Most, if not all of these tools are generally for freshwater environments. As for any type of monitoring, results from biomonitoring are totally dependent on the sampling methodology and equipment used. Therefore, it is important to use standard protocols or methods. There are some ISO and CEN standards that describe methodologies for biological sampling of fish or invertebrates. The STAR project collates updated protocols to be use to sample biological organisms. The following two tables provide background information on the major freshwater taxonomic groups and major freshwater ecosystem divisions. It is also possible to use biomarkers as a measure of water quality. A biomarker is defined as a change in a biological response (ranging from molecular through cellular and physiological responses to behavioural changes) which can be related to exposure to or toxic effects of environmental chemicals. Biomarkers may be classed into three main types, (i) biomarkers of exposure covering the detection and measurement of an pollutant or its metabolite or the product of an interaction between a xenobiotic agent and some target molecule or cell that is measured in a compartment within an organism, (ii) biomarkers of effect including measurable biochemical, physiological or other alterations within tissues or body fluids of an organism that can be recognized as associated with an established or possible health impairment or disease, and finally (iii) biomarkers of susceptibility indicating the inherent or acquired ability of an organism to respond to the challenge of exposure to a specific pollutant, including genetic factors and changes in receptors which alter the susceptibility of an organism to that exposure. Table 11 presents a range of studies involving the use of biomarkers listed for each pollutant type studied. Information such as whether measurement may be undertaken in the field or in the lab, the analytical method, the type of water under study, the type and name of the biomarker involved and the organisms used in the study are also given. References are also provided for the reader in case of more information is required. Biosensors are based on the use of whole organisms (yeast, algae or bacteria) or biological material to detect and quantify levels of organic and inorganic pollutants or for more general toxicity of water samples. Both commercial and prototype biosensors are available for laboratory, field measurements, and continuous or spot sampling. Table 12 summarises all commercially available technology and promising prototypes. Entries in the table are similar to those for physico-chemical properties measurements. Seven devices based on algae, yeast and bacteria are available for the measurement of genotoxicity (3 commercially available and 4 prototypes) under continuous or spot sampling with field or lab-based sensors. Eight devices based on bacteria or algae (4 prototypes and 4 commercially available sensors) may be used for the monitoring of general water toxicity with laboratory or field deployment. Five biosensors (2 commercially available and 3 prototypes) are available for on-line/spot monitoring of PAHs. Six devices (1 commercially available and 5 prototypes) have been developed for pesticide monitoring. In addition, six prototype devices based on enzyme assays are also available to monitor phenols and may be automated. Finally

19 devices (4 commercially available and 15 still at the prototype stage) are available to monitor heavy metals. Biological early warning systems rely on the changes in behaviour of the organism used in the assay linked to a change in water quality, assessing the acute toxicity of water under continuous flow or in-situ monitoring. The behaviour of the organism whether it is a mussel, fish, daphnid, or other crustacean, is continuously monitored so that changes due to toxic compounds may be detected and acted upon. A change from its normal behaviour monitored by an electronic sensor system that is capable of detecting it, and is then transformed into a representative electrical signal. These devices are particularly useful for water quality monitoring for example at drinking water, aquaculture intakes and for continuous monitoring of industrial waste waters. The following table presents a list these technologies that are either commercially available or still at the prototype stage. In addition, contact details of the institute/company in charge of the development are also given. The table is organised by names of the system, whole organisms used in the assay, the respond measured (e.g. change in swimming behaviour of fish or daphnids, or respiration rate of mussels). More information on limits of detection for various chemicals may be obtained from the producers. An advantage of these systems is that they may not only be able to detect chemical toxicants but also microbiological pathogens. Six devices rely on freshwater fish behaviour, e.g. ability to swim against a current, swimming behaviour, or ventilation for the detection of a degradation of water quality. 3 devices are based on the behaviour of freshwater and seawater mussels where oxygen consumption and valve movement response are the parameters measured. Other technologies are based on algal respiration or Daphnia magna swimming behaviour. A mixture of commercially available or prototype systems may be found. Chemical sampling Currently the most commonly used method for measuring levels of chemical pollutants for all three modes of monitoring is spot (bottle) sampling. This has a number of disadvantages, including cost, labour, transport and chemical analyses and the fact that it provides only a snapshot of the situation at the instant of sampling. This is an important factor since levels of pollutants can vary with time even at a fixed location, and fluctuations associated with episodic events could be missed, or conclusions could be drawn on the basis of transitory high levels. In order to optimise the full potential of chemical sampling of water, a number of technologies has recently been developed to give time-averaged chemical concentrations. These passive samplers have been the subject of intensive laboratory and field testing and calibration under various conditions, and are presented as commercially available or close to commercially available. Various designs, presented in Table 14, allow sampling for different periods of time ranging from weeks to months, and with typical detection limits ranging

from mg/L to ng/L. These samplers may be deployed in the field and left in water for the amount of time required, before being removed and brought to the lab for chemical analysis. Most of these systems are based on the molecular diffusion of dissolved species or molecules through a diffusion-limiting membrane and immobilisation in a receiving phase (that may be a chromatographic C18 phase or an organic solvent such as triolein or n-hexane). These technologies can provide qualitative information on the presence or absence of specific contaminants for investigative monitoring. In addition, extensive calibration can enable the calculation of time-averaged concentrations over the period of sampling. A total of 3 passive samplers suitable for polar, non-polar organics and inorganic pollutants by using different receiving phase and diffusion-limiting membranes are available. Four samplers (two based on spot samples, and one for continuous on-line monitoring) that can monitor both polar and non-polar organics. One of those can also monitor levels of inorganic compounds. Limits of detection range from mg/L to ng/L. Seven samplers for non-polar organic pollutants are presented with detection limits varying from g/L to ng/L. Finally, only one passive sampler is available for metals/inorganic pollutants only. Laboratory and field-based methods and instruments for the analytical measurement of chemical concentrations in spot samples or extracts from passive samplers are presented in the next table. A table also describes chemical methods and instruments such as membrane polarography to measure PAHs and heavy metals in water samples. Immunoassays comprises the final set of assays or methods for measuring levels of chemical in water samples. They rely on the interaction between biological material, antibodies specific to the analyte under study, bound to magnetic particles in 96-well plates or coated at the bottom of test tubes. An amplification system is incorporated and often provided by an linked-enzyme system that provides a coloured product from a colourless substrate. A spot sample can they be selectively extracted and final reading is being made in the lab or field using a spectrophotometer at an appropriate wavelength. Most of the assays are commercially available, very sensitive techniques, and are applicable to a wide range of compounds, PAHs, pesticides, phenols, surfactant residues, heavy metals, mutagens and other PCBs. Legislation and standards This final section of the manual targets a number of issues regarding the collection of fit for purpose results such as ISO/CEN and SCA standards, quality assurance and control, and method validation. WP2 of the SWIFT-WFD projects also targets quality assurance and validation issues. Firstly, key points about the use standard are given and standards related to water quality are listed in appendices, together with limitations in the use of these standards. A discussion of ISO17025 accreditation may also be found here. Approaches to obtaining fit for purpose results are given as well as comments on method validation. One other important aspect is the legislation involved when undertaking environmental analysis for regulatory purposes. Quality assurance and control issues are tackled as well as the need for low

cost reference materials. Finally, potential screening methods are given and recommendations are made. EU-funded projects on sampling, sensor or biosensor technologies More information on EU-funded samplers, sensor and biosensor technology may be found in appendices and in the supplementary information file. It contains details of the company/institution producing the devices, a presentation of the device, the environmental and commercial relevance, the skills required for implementation, the current state of the device, references to published work and plans for future developments of the technology.

Table of Contents

Introduction ...............................................................................................................................................1 1. Background...........................................................................................................................................6

1.1 - TYPES OF WATER RELEVANT FOR DISCUSSION (SURFACE, GROUND, ESTUARINE, COASTAL, MARINE) ...............................................................................................................................................6 1.2 - LISTS OF SUBSTANCES CURRENTLY OF DIRECT RELEVANCE TO THE WFD ..................................13 1.3 - LISTS OF SUBSTANCES LIKELY TO BE OF RELEVANCE TO THE WFD IN THE FUTURE (EMERGING POLLUTANTS OF INTEREST - EPOCS)..................................................................................................15 1.4 - LISTS OF SUBSTANCES OF INTEREST TO OTHER CONVENTIONS (OSPAR, DANUBE, BARCELONA, RHINE ETC).........................................................................................................................................17

1.4.1 - OSPAR:..............................................................................................................................17 1.4.2 - Danube River Protection Convention................................................................................17 1.4.3 Barcelona Convention: protection of the mediterranean sea ...........................................18 1.4.4 - International Commission For The Protection of Rhine (ICPR) .......................................18

1.5 - OUTLINE OF SOURCES OF THESE SUBSTANCES ............................................................................20 1.6 - SUMMARY OF TYPICAL LEVELS OF THESE IDENTIFIED SUBSTANCES IN EU WATER BODIES .........20 1.7 - ENVIRONMENTAL RISK ASSESSMENT OF THESE SUBSTANCES .....................................................29

1.7.1 - Priority Hazardous Substances: ........................................................................................29 1.7.2 - Priority Substances under Review .....................................................................................32 1.7.3 - Priority Substances............................................................................................................36

1.8 - PHYSICO-CHEMICAL PROPERTIES OF THE IDENTIFIED SUBSTANCES ............................................39 2. Monitoring issues ................................................................................................................................ 53

2.1 - PHYSICO-CHEMICAL ASSESSMENT TOOLS ...................................................................................53 2.2 - BIOLOGICAL ASSESSMENT TECHNIQUES .....................................................................................70

2.2.1 - General microbiological status including viruses .............................................................70 2.2.2 - Biomonitoring with a range of sentinel organisms (e.g. mussels) .....................................71 2.2.3 - Status assessment by biological diversity ..........................................................................80 2.2.4 - Biomarkers.........................................................................................................................85 2.2.5 - Direct toxicity measures (e.g. endocrine damage) (wide range some validated, some still experimental) ................................................................................................................................91 2.2.6 - Biologiocal early warning systems/Whole organism bioassays ......................................103

2.3 - CHEMICAL ASSESSMENT TECHNIQUES ......................................................................................107 3. LEGISLATION AND STANDARDS...................................................................................................124

3.1 - INTRODUCTION AND BACKGROUND ..........................................................................................124 3.2 - STANDARD METHODS...............................................................................................................124 3.3 - PRESCRIBED STANDARDS VERSUS PRESCRIBED PERFORMANCE CHARACTERISTICS...................125 3.4 - ISO17025 ACCREDITATION......................................................................................................129 3.5 - VALIDATION OF ANALYSIS METHODS .......................................................................................129 3.6 - LEGISLATION REQUIREMENTS FOR CARRYING OUT REGULATORY ENVIRONMENTAL ANALYSIS..........................................................................................................................................................132 3.7 - QUALITY ASSURANCE / QUALITY CONTROL ISSUES .................................................................132 3.8 - NEED FOR LOW-COST REFERENCE MATERIALS..........................................................................135 3.9 - POTENTIAL SCREENING METHODS ...........................................................................................136 3.10 - RECOMMENDATIONS ..............................................................................................................138

APPENDIX 1......................................................................................................................................... 140 APPENDIX 2......................................................................................................................................... 161 APPENDIX 3......................................................................................................................................... 167 APPENDIX 4......................................................................................................................................... 186 Bibliography and References................................................................................................................ 225

Introduction

1

Introduction This manual The aim of this operational manual is restricted to provide a toolbox of existing and more particularly emerging tools for the monitoring of physicochemical, chemical and biological parameters/quality elements, and thereby does not provide methodologies/tools for the hydromorphological assessment of water bodies (see Figure 1). The Water Framework Directive (WFD) The Water Framework Directive (WFD) is a legislative framework to protect and improve the quality of all water sources, including lakes, rivers, transitional and coastal waters, and groundwater in the European Union. This overarching Framework will eventually replace most of the existing water legislation, and aims to achieve by 2015 "good status" in all surface, ground and coastal waters in Europe. Other aims associated with this are the prevention of deterioration, and enhancement of aquatic ecosystems, the promotion of sustainable water use, the reduction of pollution, and mitigation of floods and droughts. Since many rivers cross national boundaries, the WFD includes a common plan, and timetable for implementation, and operates on the basis of integrated river basin management. A copy of the European Water Framework Directive published in the Jounal Officiel may be found at: http://europa.eu.int/eur-lex/pri/en/oj/dat/2000/l_327/l_32720001222en00010072.pdf Support of Implementation of WFD The success of the implementation of the WFD will depend on the availability and quality of information available to those charged with managing water quality. There is an urgent need for the development and validation of cost-effective technologies and methodologies that can be adopted by all European states for the routine monitoring of surface waters at the river basin level to provide comparable, consistent and reliable data across the whole of Europe. Monitoring is required to cover a number of quality elements; hydromorphological, physico-chemical, biological, and levels of specific priority pollutants, both anthropogenic and naturally occurring. Three modes of monitoring are specified; surveillance monitoring to assess long term changes, operational to provide extra data on water bodies at risk or failing to meet the environmental objectives of the WFD, and investigative to determine the causes of such failure where they are unknown. The WFD does not mandate any particular monitoring methods, but requires Member States to ensure the establishment of programmes for the monitoring of water status in order to establish a coherent and comprehensive overview of water status within each River Basin District. Monitoring programmes have to be implemented by the end of 2006, and have to cover for surface waters the volume and level, or rate of flow, as far as is relevant for the ecological and chemical status, and the ecological potential. Quality elements include biological elements, and the underpinning hydromorphological, chemical, and physicochemical factors. The Groundwater

Introduction

2

Directive has similar requirements for measuring the chemical and quantitative status of all ground water bodies or groups of groundwater bodies. Currently the most commonly used method for measuring levels of chemical pollutants for all three modes of monitoring is spot (bottle) sampling. This has a number of disadvantages, including cost and the fact that it provides only a snapshot of the situation at the instant of sampling. This is an important factor since levels of pollutants can vary with time even at a fixed location, and fluctuations associated with episodic events could be missed, or conclusions could be drawn on the basis of transitory high levels. There is therefore a need for improved screening methodologies that can provide a complimentary approach to quality monitoring. However, monitoring tools will be useful only if they are affordable, reliable and produce data that are of comparable quality between times and locations across Europe. In order to provide a more representative picture, either automatic sequential sampling to provide composite samples over a period of time (usually 24 hours), or frequent sampling must be used. The former involves the use of equipment that requires a power supply, and needs to be deployed in a secure site, and the latter would be expensive because of transport and labour costs. Biomonitoring, that involves deploying sessile organisms (usually bivalve molluscs) and measuring the accumulation of pollutants of interest over a long deployment period, is another approach used currently to monitor water quality. This approach overcomes the problem of achieving a snapshot of water quality, and can provide a more representative picture of average conditions over a period of weeks to months. However, this method has limitations since organisms can not be placed in aggressive environments such as effluents, and some compounds are metabolised or eliminated at a rate close to the rate of uptake, and thus are not effectively accumulated. In recent years a lot of work has been carried out to develop new methods of monitoring including ecological assessment models, sensors for specific pollutants, and passive samplers. Other technologies available and already in use for monitoring water quality include continuous, on-line monitoring systems (e.g. the SAMOS system). In such installations water is continuously drawn from an input, for instance at a site where drinking water is taken from a river for treatment and automatically fed into an analytical instrument such as a high performance liquid chromatograph linked to a mass spectrometer detector. Where specific pollutants of concern exceed preset limits an alarm is automatically activated. These systems provide extensive, valuable information on levels of a wide range of pollutants over time. These automatic systems require a secure site, and are expensive to install, and have a significant maintenance cost. Low cost, commercially available solutions are provided by field test kits for specific pollutants, and by portable toxicological assay equipment. The range of kits is being widened to include a large range of pesticides, industrial chemicals, and a few inorganic pollutants. A wide range of sensors for use in monitoring water quality has been developed in recent years, and some are commercially available. They can be used as field instruments for spot measurements, or can be incorporated into on-line monitoring systems in for example drinking water or wastewater treatment plants.

Introduction

3

Many of the available range of sensors have been developed in EU funded projects, and the laboratories involved form part of networks such as SENSPOL to provide a large body of expertise that can be used to disseminate information on what is available, and of developments in the area. Direct toxicological assays can provide different information from the measurements of levels of individual pollutants, and can be particularly useful where complex mixtures of pollutants are involved, and where there may be interactions, for instance synergism or antagonism, between components. Again the limitation is often set by the sampling procedure since spot sampling is the source of the test water, and so only an instantaneous assessment of water quality is provided. A further approach to monitoring water quality involves the deployment of passive samplers. These devices require no power source, and can be deployed for extended periods of from days to months, and yield time-averaged concentrations of pollutants to which the samplers have been exposed. Many of the methods introduced above have the potential to be included in the set of useful tools in the toolbox available to those responsible for monitoring and improving water quality under the WFD and its daughter directives. This operational manual provides a working catalogue of the methodologies and technologies available for inclusion in the toolbox, with information, where available, on ranges of applicability, quality, available standards, reliability, and cost. This information is presented in a set of linked tables with appendices containing key references, and some case further details. Where EU funded research, either past or current, has been undertaken in a relevant area, then this is cross-referenced to optimise the use of EU-funded deliverables, and to indicate the location and nature of scientific and technological expertise. Structure of the Manual The manual uses a problem based approach, and the first table contains details of the hydromorphological, chemical, physicochemical, and toxicological properties that may need to be measured for surveillance, operational, and investigative monitoring. Linked to this are tables containing the physicochemical properties of the priority pollutants, lists of methods available for analysing the levels of priority pollutants in samples, chemical (including passive sampling) and biological methods available for monitoring pollutant levels, toxicological assays, endocrine disruption assays, measures of ecological status. Further tables contain lists of relevant legislation and available standards, and links to relevant EU aquatic environmental research projects. Table 1 Quality elements for the classification of ecological status Table 2 List of the 33 priority substances Table 3 List of the 66 emerging substances Table 4a Organic Priority Pollutants with Typical Levels and Principal

Uses Table 4b Inorganic Priority Pollutants with Typical Levels and Principal

Uses Table 5a Physicochemical Properties of Organic Priority Pollutants Table 5b Physicochemical Properties of Inorganic Priority Pollutants

Introduction

4

Table 5c Physicochemical Properties of Other Water Contaminants Table 6 Currently available methods for physico-chemical measurementsTable 7 Biomonitoring "Rapid Assessment Table 8 Selection of biological monitoring tools for the assessment of

water quality Table 9 The major freshwater groups (taxonomically organised) Table 10 The major divisions of freshwater ecosystems Table 11 Biomarkers Table 12 Bioassays/biosensors Table 13 Biological early warning system commercially available or in

development Table 14 Currently available chemical analytical methods to measure

Heavy metals and PAHs Table 15 Non-biological methods available for monitoring environmental

substances Table 16 Chemical analytical methods Table 17 Immunoassay test kits Table 18 Example of some of the performance data in soil cyanide

method Table 19 Graphite Furnace Atomic Absorption (GF-AAS) Performance

Data Table 20 Leap Scheme Potable Water Results Table 21 Parameters in relation to which Methods of Analysis must satisfy

Prescribed Characteristics Table 22 Potential Screening Tests considered relevant to the WFD Table 23 Test Comparison E(L)C50 (mg l-1) of bioscrenning method for

some parameters Appendix 1 Table 24 Main uses of the priority compounds Appendix 2 Table 25 Scientific Works Immunoassays for organic pollutants Appendix 3 Table 26 European Union funded RESEARCH PROJECTS involving

sensors and biosensors for monitoring water pollution Table 27 Main achievements of European Union funded research projects

involving sensors and biosensors for monitoring water pollution Appendix 4 Table 28 Published ISO Water and Effluent Standards Table 29 Draft ISO Water and Effluent Standards Table 30 Published and Draft CEN Water and Effluent Standards Table 31 Published and Draft SCA Water and Effluent Standards Table 32 Standard methods for Inorganic species and metals Table 33 EPA methods for inorganic species and metals Table 34 EPA methods for ground or wastewater (www.speclab.com) Table 35 EPA standard immunoassays Supplementary Information

Supplementary information on European projects on samplers, sensors and biosensors [separate document]

Introduction

5

Factors to be taken into account and discussed Sensitivity/Reliability Sensitivity is not in itself a good criterion for the selection of monitoring methods unless high sensitivity coincides with reliability, ease of use and affordable cost. It is important to take into account a range of factors and this manual attempts to provide easy access to the important variables to be considered. It does not make recommendations. Sensitivity can potentially be a problem in some areas. For example, the recommended environmental limits for some analytes in water (particularly for very non-polar pollutants e.g. the brominated flame retardants) are unrealistically low when compared with the limits of detection of available analytical methods. However, they are also irrelevant since most of the environmental load of these pollutants is bound to particles, and concentrations of dissolved material are very low. This will be flagged in the tables. As the effects of the WFD and related legislation to reduce levels of priority pollutants starts to work, then it may be more cost effective to be able to report not detectable by an accredited method rather than insisting on driving down the limits of detection in order to be able to report an actual level. Quality control In WP2, SWIFT will deliver guidance on method validation and quality assurance, and a set of quality control tools. There must be links to this in the operational manual. While section 3.7 of this operational manual provides information on quality assurance and quality control, additional data and information will become available in the WP2 of the the WFD-SWIFT project that focuses on the validation of chemical analytical methods. Modelling It is important that clearer links are established between SWIFT documentation and the outputs from the modelling community involved in prediction of ecological status as well as the groups (HARMONI-CA) primarily concerned with hydromorphological properties of surface water systems. Linking chemical and biological monitoring A section of the manual will address the developing area of the identification of the causative agents of observed toxicological responses of organisms either in situ, or when exposed to water or sediment samples in the laboratory.

Background

6

1. Background

1.1 - Types of water relevant for discussion (surface, ground, estuarine, coastal, marine) Monitoring of ecological and chemical status for surface waters The monitoring network should be designed to provide a coherent and comprehensive overview of ecological and chemical status within each mapped river basin. Surveillance and operational monitoring programmes should be established for adequate time periods and reviewed according to monitoring results. Monitoring should include parameters (Table 1) which are indicative of the status of each relevant quality element. Definitions of high, good and moderate ecological status in rivers, lakes, transitional, coastal and groundwater may be found on the Water Framework Directive 2000/60/EC: (http://europa.eu.int/eur-lex/pri/en/oj/dat/2000/l_327/l_32720001222en00010072.pdf). Each biological, hydromorphological, physico-chemical or chemical water quality elements will be assessed by monitoring various parameters indicative of these quality elements. Figure 1 shows, for example, the quality elements selected for rivers. For example, phytoplankton monitoring is based on the taxonomic composition of the community, and phytoplankton abundance and blooms in relation to type-specific physico-conditions. Macrophyte assessment is undertaken by investigating taxonomic composition and average changes in abundance, while for benthic invertebrates, the taxonomic composition and abundance, the ratio of disturbance sensitive to insensitive taxa, and the level of diversity all contribute to the assessment. Fish fauna monitoring is based on species composition, and abundance, the presence of disturbance-sensitive species, and on the age structure of the fish community. Hydromorphological monitoring generally relies on the assessment of quantity and dynamics of flow, connections to groundwater, continuity, channel patterns, width/depth variations, substrate conditions, structure and condition of the riparian zone in the case of rivers, residence time, lake depth variation, quantity and structure of the substrate for lakes, the tidal flow regime, depth variations, substrate condition and structure and condition of the intertidal zone, freshwater flow regime and direction and speed of dominant currents for transition/coastal waters. Monitoring of general conditions generally involves measurements of nutrients, levels of salinity, pH, oxygen balance, acid neutralising capacity, temperature, transparency, general toxicity and organic pollution indicators. Investigation into chemical conditions relies on measuring levels of specific synthetic or non-synthetic pollutants.

Background

7

Table 1. Quality elements for the classification of ecological status Type of water

body Type of elements Quality elements / Parameters Rivers Biological Composition and abundance of aquatic flora Composition and abundance of benthic invertebrate fauna Composition, abundance and age structure of fish fauna Hydromorphological Quantity and quality of water flow Connection to groundwater bodies River continuity Depth and width variation Structure and substrate of the river bed Structure of the riparian zone Physico-chemical status Thermal conditions Oxygenation conditions Salinity Acidification status Nutrient status Chemical status Priority hazardous substances Priority substances Other possible significantly discharged pollutants Lakes Biological Composition, abundance and biomass of phytoplankton Composition and abundance of aquatic flora Composition and abundance of benthic invertebrate fauna Composition, abundance and age structure of fish fauna Hydromorphological Quantity and dynamics of water flow Connection to groundwater bodies Residence time Lake depth variation Quantity, structure and substrate of the lake bed Structure of the lake shore Physico-chemical status Thermal conditions Oxygenation conditions Salinity

Background

8

Acidification status Nutrient status Transparency Chemical status Priority hazardous substances Priority substances Other possible significantly discharged pollutants

Biological Composition, abundance and biomass of phytoplankton Transitional waters Composition and abundance of aquatic flora Composition and abundance of benthic invertebrate fauna Composition, abundance and age structure of fish fauna Hydromorphological Depth variation Quantity, structure and substrate of the bed Structure of the intertidal zone Tidal regime Freshwater flow Wave exposure Physico-chemical status Thermal conditions Oxygenation conditions Salinity Nutrient status Transparency Chemical status Priority hazardous substances Priority substances Other possible significantly discharged pollutants Coastal waters Biological Composition, abundance and biomass of phytoplankton Composition and abundance of aquatic flora Composition and abundance of benthic invertebrate fauna Hydromorphological Depth variation Quantity, structure and substrate of the coastal bed Structure of the intertidal zone Tidal regime Direction of dominant currents Wave exposure Physico-chemical status Thermal conditions Oxygenation conditions Salinity Nutrient status Transparency

Background

9

Chemical status Priority hazardous substances Priority substances Other possible significantly discharged pollutants Ground waters Groundwater level Chemical status Conductivity Oxygen content pH value Nitrate levels Ammonium levels Priority hazardous substances Priority substances Other possible significantly discharged pollutants

Background

10

PHYSICO-CHEMICAL

HYDROMORPHOLOGICAL

BIOLOGICAL

SPECIFIC SYNTHETIC POLLUTANTS

SPECIFIC NON SYNTHETIC POLLUTANTS

SELECTION OF QEs - RIVERS Thermal conditionsTemperature

Oxygenation conditionsDissolved oxygen

SalinityElectrical conductivity

Acidification status PHAlkalinity/ANC

Nutrient conditions

Total phosphorusSoluble reactive phosphorusTotal nitrogenNitrate + nitriteAmmonium

Other Suspended SolidsTurbidity

Hydrological regimeQuantity and dymanics of water flow

Historical flowsModelled flowsReal time flows

Connection to groundwater bodies Water table heightSurface water discharge

River continuityNo. and type of barrierProvision for passage of aquatuc organisms

Morphological conditions

River depth & width variation River cross sectionFlow

Structure & substrate of the river bedCross sectionsParticle sizePresence/location of CWD

Structure of the riparian zoneLength/widthSpecies compositionContinuity/ground cover

Current velocityChannel patterns

Invertebrate faunaAbundance

CompositionPresence of sensitive taxa

Diversity

FishAbundance

CompositionLife cycle/age structure

Presence of sensitive taxa

PhytobenthosAbundance

CompositionPresence of sensitive taxa

MacrophytesAbundance

CompositionPresence of sensitive taxa

PhytoplanktonAbundance

CompositionBloom frequency/intensity

Biomass

All WFD priority list substances

Other substances depending on catchment pressures

All WFD priority list substances

Other substances depending on catchment pressures

Legend: Mandatory QE specified in Annex V.1.2 Recommended QE Figure 1. Example of selection of quality elements for rivers

Background

11

Figure 2. User-interface of this operational manual

Quality elements

Physicochemical characteristics

Oxygenation

Dissolved Oxygen

COD

BOD

Acidification status

pH

Redox conditionsHardness/acid/bases

Salinity

Conductivity

Nutrient conditions

Ammonium

Nitrate/nitrite

Total Nitrogen

Phosphate

Total Phosphorus

Respirometry

Organic matter

Organic matter

TOC

OM aromaticity

Turbidity

Ecological/Biological Monitoring

Priority & emerging chemical pollutants

Biological assessment

Microbiological status

Use of sentinel organisms

Tools for ecological monitoring

Refs to sampling strategies

Biological Assessment

Biomarkers

Biosensors

BEWS/Whole organism assays

Chemical Assessment

Non-biological sampling methods

Chemical analytical methods

Immunoassays

EU-funded projects on samplers & (bio)sensors Abstracts/details

Achievements

Supplementary Information

Chemical methods for PAHs & heavy metals

Background

12

Three types of Monitoring are required: Design of surveillance monitoring Objectives The objectives of surveillance monitoring are to provide information (i) to supplement and validate the impact assessment procedure under the WFD, (ii) for the efficient and effective design of future monitoring programmes, (iii) to assess long-term changes in natural conditions, and (iv) to assess long-term changes resulting from widespread anthropogenic activity. Results will be used to determine requirements for monitoring programmes in the current and subsequent river basin management plans. Selection of monitoring sites Adequate number of sampling sites should be selected to provide an appropriate and representative assessment of the overall surface water status within each catchment or subcatchments within the river basin. Sampling should be undertaken where the rate of water flow or volume of water present is significant, where significant bodies of water cross other countries boundaries. Selection of quality elements Surveillance monitoring should be conducted for a period of one year during which parameters indicative of biological, hydromorphological, physico-chemical, or chemical quality elements needs to be assessed. When previous surveillance monitoring resulted in good status for a body of water, and that addition anthropogenic impacts have been identified, surveillance monitoring may be carried out once every three river basin management plans. Design of operational monitoring Objectives Operational monitoring may be undertaken to establish the status of water bodies identified as being at risk of failing to meet their environmental objectives and to assess any changes in the status of such water bodies resulting from the programmes of measures. Flexibility is allowed in light of information obtained with impact and risk assessments in order to reduce the sampling frequency where an impact is found not to be significant or when the relevant pressure has been removed. Selection of monitoring sites Monitoring sites should be selected according to legislation laying down the relevant environmental quality standards. In all other cases including for priority list substances, sufficient sampling sites may be selected to assess the magnitude and impact of a point or diffuse source of pollution and of hydromorphological pressure. When more than one point source or hydromorphological pressure are present, the system also needs to be assessed as a whole. Sampling sites in the case of a diffuse source need to be representative of the relative risks of the occurrence of the diffuse source pressures, and of the relative risk to fail to achieve good water status.

Background

13

Selection of quality elements Parameters representative of quality elements indicative of the pressures the body of water is subjected to need to be selected to assess the impact and magnitude of the pressures. Parameters relevant those quality elements most sensitive to the pressures, all priority substances or other pollutants discharged in significant quantities, and hydromorphological quality elements should be monitored. Design of investigative monitoring Objectives Investigative monitoring may be undertaken when the reason for any exceedances is not known, when surveillance monitoring indicates that water quality objectives are not likely to be met, to understand the causes for a body of water to fail environmental objectives, and to assess the magnitude and impact of accidental pollution. Results from investigative monitoring should contribute to the establishment of a programme of measures to achieve environmental objectives, and specific remediation strategy. Frequency of monitoring Guidelines for monitoring frequency may be found on the Water Framework Directive 2000/60/EC: (http://europa.eu.int/eur-lex/pri/en/oj/dat/2000/l_327/l_32720001222en00010072.pdf). The frequency will depend on the type of body of water (rivers, lakes, transitional, coastal or ground waters), on the quality element being monitored (i.e. biological, hydromorphological, physico-chemical or chemical) and of course for the type of monitoring undertaken. For operational monitoring, the frequency should allow to provide sufficient data for a reliable assessment of the status of the relevant quality element. In general, frequencies should be selected to obtain acceptable level of confidence and precision.

1.2 - Lists of substances currently of direct relevance to the WFD http://europa.eu.int/comm/environment/water/water-framework/priority_substances.htm The Water Framework Directive requires a list of "priority substances selected amongst those which present a significant risk to, or via, the aquatic environment". This list is based on the toxicity, persistence, bioaccumulation potential, human health risk and the monitored and modelled concentration of each substance in the aquatic environment. Substances on the Priority List are to be subject to one of two general targets: a progressive reduction of pollution or inputs, a cessation or phasing out of discharges, emissions and losses.

Background

14

Within the Priority List there are three categories of substance. Priority Hazardous Substances (PHS) are considered such that there must be cessation or phasing out of discharges, emissions and losses of these substances within twenty years of the adoption of measures for that purpose. Priority Substances under Review (PSR) may, if further investigation justifies it, be proposed as PHS. The third category is Priority Substances (PS) which must undergo progressive reduction of discharges, emissions and losses to the environment. The principal benefits expected to result from the Priority List measures are improvements in water quality and protection and enhancement of the aquatic and marine ecosystems, wildlife and predators further up the food chain. As of May 2003, the Priority List contains 33 substances: Table 2. List of the 33 priority substances

11 PRIORITY HAZARDOUS SUBSTANCES

Brominated Diphenylether

Cadmium And Compounds

C10-13- Chloroalkanes

Hexachlorobutadiene Hexachlorocyclohexane (HCH) Hexachlorobenzene

Mercury And Compounds Nonylphenols Pentachlorobenzene

Tributyltin Compounds

Polyaromatic Hydrocarbons

(PAH) Benzo(a)pyrene

Benzo(b)fluoranthene Benzo(g,h,i)perylene Benzo(k)fluoranthene

Indenol(1,2,3-od)pyrene

14 PRIORITY SUBSTANCES UNDER REVIEW

Anthracene (PAH) Atrazine Chlorpyrifos Di(2-

Ethylhexyl)Phthalate (DEHP)

Diuron Endosulfan Isoproturon Lead And Compounds

Naphthalene (PAH) Octylphenols Pentachlorophenol Simazine

Trichlorobenzenes Trifluralin

8 PRIORITY SUBSTANCES:

Alachlor Benzene Chlorofenvinphos 1,2-Dichloroethane

Dichloromethane Fluoranthene Nickel And Compounds Trichloromethane

Background

15

1.3 - Lists of substances likely to be of relevance to the WFD in the future (emerging pollutants of interest - EPOCs)

The ecological and human health impact of EPOCs in wastewater effluent has in recent years come to the attention of scientists as well as environmental regulators. The USGS (2002, Vol. 36, Environmental. Science & Technology) has identified 95 emergent pollutants of concern (EPOCs). The list of these compounds may be divided into the following four categories:

1. Veterinary and human antibiotics 2. Prescription and non-prescription pharmaceuticals 3. Household and industrial wastewater compounds 4. Hormones and sterols

Many of these compounds may be found at low concentrations in treated wastewater and sometimes in potable water. Although this is a relatively novel area of research, evidence gathered has shown that exposure to EPOCs may cause cancer as well as physiological changes in humans and animals. Of particular concern, is human and animal exposure to so-called Endocrine Disrupting Chemicals (EDCs). Recently, Safe Drinking Water Act amendments have included requirements for testing drinking water supplies for EDCs. The following table lists organic compounds potentially presenting endocrine disrupting effects, e.g. veterinary and human antibiotics, certain (non)-prescription drugs, and other substances that may be found in wastewater. In addition to emerging substances listed in Table 3 (below), more information may be found on an endocrine disrupters EEA homepage at: http://europa.eu.int/comm/environment/endocrine/index_en.htm A list of 66 prioritised substances may also be found at: http://europa.eu.int/comm/environment/docum/bkh_annex_15.pdf Table 3. List of the 94 emerging substances

VETERINARY AND HUMAN ANTIBIOTICS

Carbodox Chlortetracycline Ciprofloxacin Doxycycline

Enrofloxacin Erythromycin-H2O Erythromycin

Metabolite Lincomycin

Norfloxacin Oxytetracycline Roxithromycin Sarafloxacin

Sulfachloropyridazine Sulfadimethoxine Sulfamerazine Sulfamethizole

Sulfamethoxazole Sulfathiazole Tetracycline Trimethoprim

Tylosin Virginiamycin

PRESCRIPTION DRUGS

Albuterol Cimetidine Codeine Dehydronifedipine

Background

16

(Salbutamol)

Digoxin Digoxigenin Diltiazem Enalaprilat

Fluoxetine Gemfibrozil Metformin Paroxetine Metabolite

Ranitidine Warfarin

NONPRESCRIPTION DRUGS

Acetaminophen Caffeine Cotinine Ibuprofen

OTHER WASTEWATER-RELATED COMPOUNDS

1,4-Dichlorobenzene 2,6-Di-Tert-Butylphenol 2,6-Di-Tert-Butyl-1,4-Benzoquinone

5-Methyl-1h-Benzotriazole

Acetophenone Anthracene Benzo[a]Pyrene 3-Tert-Butyl-4-Hydroxy Anisole Butylated Hydroxy

Toluene Bis(2-Ethylhexyl)

Adipate Bis(2-Ethylhexyl)

Phthalate Bisphenol A

Carbaryl Cis-Chlordane Chlorpyrifos Diazinon

Dieldrin Diethylphthalate Ethanol,2-Butoxy-Phosphate Fluoranthene

Methyl Parathion 4-Methyl Phenol Naphthalene N,N-Diethyltoluamide 4-Nonylphenol Monoethoxylate

4-Nonylphenol Diethoxylate

4-Octylphenol Monoethoxylate

4-Octylphenol Diethoxylate

Phenanthrene Phenol Phthalic Anhydride Pyrene

Tetrachloroethylene (4) Triclosan

Tri(2-Chloroethyl) Phosphate

Tri(Dichlorisopropyl) Phosphate

Triphenyl Phosphate

STEROIDS AND HORMONES

Cis-Androsterone Cholesterol Coprostanol Equilenin

Equilin 17-Ethynyl Estradiol 17-Estradiol Estriol

Estrone Mestranol 19-Norethisterone Progesterone

Stigmastanol Testosterone

Background

17

1.4 - Lists of substances of interest to other conventions (OSPAR, Danube, Barcelona, Rhine etc)

1.4.1 - OSPAR: The OSPAR List of Substances of Possible Concern is a dynamic working list that is being regularly revised, as new information becomes available. This may lead to exclusion of substances present on the current version of the OSPAR List of Substances of Possible Concern and to inclusion of other substances if data on persistence, toxicity and liability to bioaccumulate (or evidence that they give rise to an equivalent level of concern) show that they should be added. This version of the OSPAR List of Substances of Possible Concern was last revised on 13 May 2003. 16 groups according to function or use category substances were defined and represent 380 compounds.

OSPAR LIST OF SUBSTANCES

Aliphatic hydrocarbons

Aromatic hydrocarbons Drugs Hormones

Metallic compounds Organic nitrogen compounds Organic Esters Organohalogens

Organometallic compounds Organophosphate Organosilicon PAHs

Pesticides Phenols Phthalate esters Synthetic musk The exhaustive list is available at the following web address: http://www.ospar.org/eng/html/welcome.html

1.4.2 - Danube River Protection Convention www.rec.org/DanubePCU/drpc.html Guiding List of hazardous substances and groups of substances: A. Priority groups of substances (a) heavy metals and related compounds (b) organohalogen compounds (c) organic compounds of phosphorus and tin (d) plant protection agents, pesticides (fungicides, herbicides, insecticides, algicides) and chemicals used for the preservation of wood, cellulose, paper, hides and textiles etc. (e) oils and hydrocarbons of petroleum origins (f) other organic compounds especially harmful to the aquatic environment (g) inorganic nitrogen and phosphorus compounds (h) radioactive substances (including wastes).

Background

18

B. Single hazardous substances As considerable differences in risk posed by substances exist within certain groups of chemicals, it may necessary also to emphasise certain single substances, which in practice, may play a priority role.

DANUBE CONVENTION LIST OF SUBSTANCES

Arsenic Atrazine Azinphos-ethyl Azinphos-methyl

Boron n.a. Cadmium Carbontetrachloride Chloroform

Chromium n.a Cobalt n.a. Copper DDT

1,2 Dichloroethane Dichlorvos Dioxins n.a. Drins

Endosulfan Fenitrothion Fenthion HCH

Hexachlorobenzene Hexachlorobutadiene Lead Malathion

Mercury Nickel Parathion Parathion-methyl

Pentachlorophenol Selenium Silver n.a Simazine

Tetrachloroethylene Tributyltin-compounds Trichlorobenzene Trichloroethane

Trichloroethylene Trifluralin Triphenyltin-compounds Zinc n.a

1.4.3 Barcelona Convention: protection of the mediterranean sea http://europa.eu.int/scadplus/leg/en/lvb/l28084.htm This protocol only covers pollution caused by ships and aircrafts around the Mediterranean Sea. While dumping of certain types of waste and matter (toxic organohalogen and organosilicon compounds, mercury, cadmium, plastics, crude oil, etc.) is prohibited, dumping of other material or types of waste (arsenic, lead, copper, zinc, chrome, nickel, containers, scrap metal, certain types of pesticides, etc.) is subject to the prior issue of a special or general permit by competent national authorities. Such permits may be issued only after careful consideration of a number of factors (characteristics and composition of the matter, characteristics of dumping site and method of deposit, general considerations and conditions). Ships and aircraft used for other than governmental and non-commercial purposes are excluded from the scope of the Protocol.

1.4.4 - International Commission For The Protection of Rhine (ICPR) http://www.iksr.org/ Target values for priority substances in Rhine water (based on monitoring data 1990 to 2000, ICPR 2002: report no. 123)

Background

19

NOT ACHIEVED

Cadmium Copper Diuron Fenitrothion

Hexachlorobenzene (HCB)

PCBs (7 congeners) Lindane (-HCH) Zinc

ALMOST ACHIEVED

Ammonium-nitrogen AOX Arsenic Atrazine

Bentazon Benzo(a)pyrene Chromium Isoproturon

Lead Mercury Nickel Total phosphorous

Tributyltin cation (TBT)

CLEARLY ACHIEVED

Aldrin Azinphos-ethyl Benzene 2- chloroaniline

3-chloroaniline 1-chloro-2-nitrobenzene 1-chloro-3-

nitrobenzene 1-chloro-4-

nitrobenzene

2-chlorotoluene 4-chlorotoluene 3,4-dichloroaniline Dibutyltin cation

1,2-dichloroethane DDT-group Dieldrin Endrin

-HCH -HCH -HCH HexachlorobutadieneIsodrin Malathion Pentachlorophenol (PCP) Simazine

Tetrabutyltin Tetrachloroethylene (PER) Tetrachloromethane 1,2,3-

trichlorobenzene 1,2,4-

trichlorobenzene 1,3,5-

trichlorobenzene 1,1,1-trichloroethane Trichloroethylene

Triphenyltin cation (TPT)

NOT DETECTABLE (BELOW LIMITS OF DETERMINATION)

Azinphos-methyl 4-chloroaniline 2,4-

dichlorophenoxyacetic acid

Dichlorvos

1,4-dichlorobenzene Endosulfan Fenthion Mecoprop-p

Parathion-ethyl Parathion-methyl Trichloromethane (chloroforme) Trifluralin

Background

20

1.5 - Outline of sources of these substances

Uses and principal sources of these substances may be found in Tables 4a and 4b .

1.6 - Summary of typical levels of these identified substances in EU water bodies Tables 4a and 4b summarise typical levels found in three major types of waters, namely river, ground and sea waters and the principal uses of each compounds more detail concerning the uses are given in appendix 1. Concentrations are given in nanograms per litre of water.

Background

21

Table 4a. WFD Organic Priority Pollutants with Typical Levels and Principal Uses

Typical level in water

Substances Link and Ref River water (ng/L)

Ground water (ng/L)

Sea water (ng/L)

Principal uses*

PESTICIDES 1

Atrazine 14 to 1200 10 to 6000 * n/a Pre- and post-emergence herbicide

Simazine

www.ksgrains.com/triazine/links.html

www.pesticideinfo.org www.epa.gov

< 5 to 124 200 to 1000 n/a Pre-emergence herbicide

Alachlor www.inchem.org http://extoxnet.orst.edu 10 < 100 to 16600 n/a Pre- and post-emergence pesticide

Chlorfenvinphos www.inchem.org www.atsdr.cdc.gov n/a n/a n/a Insecticide (control of cattle tick, control of root flies,

rootworms, ...)

Chlorpyrifos (-ethyl, -methyl) www.chlorpyrifos.com

www.epa.gov www.atsdr.cdc.gov

nd to 10 nd Nd Broad-spectrum insecticide (control of mosquitoes, flies, various crop pests in soil and on foliage), also used for

control of ectoparasites on cattle and sheep.

-HCH (Lindane) www.headlice.org

http://extoxnet.orst.eduwww.pan-uk.org

10 to 100 3 to 163 n/a Insecticide and therapeutic pesticide

Isoproturon www.pan-uk.org 100 to 125 50 to 100 n/a Systemic herbicide

DDT http://extoxnet.orst.edu

www.epa.gov www.atsdr.cdc.gov

nd to 0.2 nd n/a Insecticide with a broad spectrum

Aldrin www.atsdr.cdc.gov www.scorecard.org < 0.1 not present n/a Insecticide for soil-dwelling pests and for wood against

termites

Endrin www.atsdr.cdc.gov www.scorecard.org 7 to 150 Max. 200 < 0.01 to 10 Non-systemic and persistent insecticide used mainly on

fieldcrops

Background

22

Isodrin www.pesticideinfo.org www.scorecard.org 300000 n/a n/a Discontinued insecticide

Dieldrin www.inchem.org < 10 not present n/a Insecticide for wood against termites

Trifluralin www.epa.gov

www.scorecard.org www.inchem.org www.pan-uk.org

nd to 550 generally nd n/a pre-emergence herbicide

POLYAROMATIC HYDROCARBONS (PAHS) www.atsdr.cdc.gov/

Benzo(a)pyrene www.epa.gov 1 n/a 0.01 to 0.1 No industrial uses except in analysis or toxicology

laboratories - Produces by incomplete combustion of organic material.

Benzo(b)fluoroanthene www.epa.gov < 50 < 5 n/a No industrial uses. Produces by incomplete combustion of organic material. Benzo(g,h,i)perylene www.epa.gov 0.3 to 25 0.7 to 10 n/a No industrial uses. Produces by incomplete combustion of organic material.

Benzo(k)fluoroanthene www.epa.gov < 50 < 10 < 5 No industrial uses. Produces by incomplete combustion of organic material.

Indeno(1,2,3-cd)-pyrene www.scorecard.org < 100 nd to 100 < 0.1 No industrial uses. Produces by incomplete combustion of organic material.

Naphthalene www.eco-

usa.net/toxics/naph.shtml

nd to 1000 nd to 10000 < 10

Used for the synthesis of a lot of organic compounds (colouring, phthalic anhydrous, solvents, chloronaphthalene, nitronaphthalene, ...). Also used for wood preservation and

as a moth repellent.

Anthracene www.scorecard.org 0.006 to 10 < 100 n/a Chemical intermediate in the preparation of colour products

and resins. Also used as a diluent in wood preservation, insecticide and fungicide products.

VOCs & SVOCs

Benzene www.epa.gov < 1000 < 30 < 5 to 20

Benzene is used in the chemical industry for the production of styrene/ethylbenzene, cumene/phenol and cyclohexane. Its use as a solvent has been greatly reduced in the last few years. Benzene is used as an additive in petrol to increase

the octane number.

Hexachlorobenzene (HCB) www.epa.gov nd to 0.04 nd Nd to 0.03 Selective fungicide, wood preservative, manufacture of pentachlorophenol, used in the production of aromatic

fluorocarbons.

Pentachlorophenol www.epa.gov www.scorecard.org 100 to 1000 < 500 1 to 5 Wood Preservative, fungicide, molluscicide, pre-emergent

herbicide, biocide in industrial water system.

Background

23

www.epa.gov

2,4,6-Trichlorophenol www.epa.gov

www.scorecard.org www.epa.gov

n/a n/a Nd Anti-microbial agent, herbicide, bactericide and used to

prepare fungicide and wood preservation. Chemical intermediate for synthesis of phytosanitary substances.

2,4,5-Trichlorophenol www.epa.gov

www.scorecard.org www.epa.gov

n/a n/a Nd Used as a fungicide in paper and pulp mills, as an herbicide

and as an intermediate in the manufacture of other pesticides

1,2-Dichloroethane www.epa.gov www.atsdr.cdc.gov < 200 < 200 nd to 210 The major use is in the production of vinyl chloride. It is also

used as a solvent, in the synthesis of other chlorinated solvents and as a lead scavenger in leaded petrol.

Dichloromethane www.epa.gov

www.scorecard.org www.atsdr.cdc.gov

100 to 743000 3000 n/a Widely used as an organic solvent and is found in paints,

insecticides, degreasing and cleaning fluids, and other products.

Pentachlorobenzene www.epa.gov

www.scorecard.org www.inchem.org

0.1 to 1 n/a n/a Chemical intermediate in the production of the fungicide quintozene.

1,2,3-trichlorobenzene www.inchem.org 10 n/a 1 1,2,4-trichlorobenzene www.inchem.org 1 to 10 1 0.3

1,3,5-trichlorobenzene www.inchem.org V n/a 1

1,2,4-TCB is economically the most important isomer. Industrial-grade TCB, which consists of 93-98% 1,2,4-TCB and the remainder 1,2,3-TCB, is used as an intermediate in chemical synthesis, a solvent, a coolant, a lubricant and a heat-transfer medium; it is also used in polyester dyeing, in

termite-control preparations and as an insecticide

Trichloromethane (chloroform) www.epa.gov www.atsdr.cdc.gov 100 to 30000 nd to 5000 < 0.05 to 8

Chemical intermediate for the synthesis of fluorohydrocarbons. General solvent for adhesives and

pesticides, solvent for essential oils, oils, rubbers, resins, alkaloids, antibiotics, hormone, nicotine, vitamins ... and as

a purification agent for plastic materials.

Tetrachloroethene www.epa.gov www.atsdr.cdc.gov 50 70 to 2000 0.1 to 0.8

Used primarily as a solvent in the dry-cleaning industry. Also used as a degreasing solvent in metal industries, as a heat

transfer medium, and in the manufacture of fluorohydrocarbons

Tetrachloromethane www.epa.gov www.atsdr.cdc.gov 10 to 50 200 0.12 to 0.85

Intermediate for chlorofluoromethanes manufacturing. Metal degreasing, cleaning agent, solvent for rubber cement,

cable and semiconductor manufacture. Also used in soap perfumery and insecticides.

Trichloroethene www.epa.gov www.atsdr.cdc.gov 1000 to 24000 1000 n/a

Mainly used in dry cleaning, for the degreasing of fabricated metal parts, as a solvent for fats, waxes, resins, oils, rubber,

paints and varnishes, and as an inhalation analgesic and anaesthetic

Background

24

POLYCHLORINATED BIPHENYLS (PCBs): mixture of up to 209 congeners

PCB 77 (3,3',4,4'-TCB) PCB 81 (3,4,4',5-TCB)

PCB 126 (3,3',4,4'5-PeCB) PCB 169 (3,3',4,4',5,5'-HxCB) PCB 105 (2,3,3',4,4'-PeCB) PCB 114 (2,3,4,4',5-PeCB) PCB 118 (2,3',4,4',5-PeCB) PCB 123 (2',3,4,4',5-PeCB)

PCB 156 (2,3,3',4,4',5-HxCB) PCB 157 (2,3,3',4,4',5'-HxCB)

PCB 167 (2,3,3',4,4',5,5'-HxCB) PCB 189 (2,3,3',4,4',5,5'-HxCB)

www.scorecard.org http://pops.gpa.unep.org/1

9pcbs.htm www.atsdr.cdc.gov

Sum of PCBs: nd to 1 n/a

Sum of PCBs: 0.05 to 0.6

PCBs have been used as coolants and lubricants in transformers capacitors and other electrical equipment. Though their use has now ceased, they are still present

in many older electrical installations

DIOXINS AND FURANS 2, 3

PCDD/Fs PCDD: 0.04 - PCDF: 0.004 0.003 0.025

2378-TCDD n/a n/a < 0.0005 123478-HxCDD n/a n/a < 0.00006 123789-HxCDD n/a n/a < 0.00025

HxCDD n/a n/a 1234678-HpCDD n/a n/a 0.0027

HpCDD n/a n/a OCDD n/a n/a 0.0164

2378-TCDF n/a n/a < 0.00154 23478-PeCDF

www.ejnet.org/dioxin/ www.dioxinfacts.org www.atsdr.cdc.gov

www.epa.gov/opptintr/pbt/dioxins.htm

n/a n/a 0.00017

By-product of a lot of combustion processes (e.g. household refuse incineration). Secondary product produces during production of pesticides or TCP.

PHTALATE

Di(2-ethylhexyl)phthalate (DEHP) www.epa.gov www.atsdr.cdc.gov 80-500 nd to 1000 nd to 100

Used primarily as a plasticizer in many flexible PVC products and in vinyl chloride co-polymer resins. Also used as a replacement for PCBs in dielectric fluids for

small electrical capacitors. FLAME RETARDANTS

(BROMINATED 4, 5, 6

Background

25

DIPHENYLETHERS)

Bis(pentabromophenyl)ether www.cdc.gov n/a n/a 0.0001 to 0.004

Diphenyl ether, octabromo derivative

http://ecb.jrc.it/DOCUMENTS/Existing-

Chemicals/RISK_ASSESSMENT/SUMMARY/oct

asum014.pdf

n/a n/a n/a

Diphenyl ether, pentabromo derivative

http://ecb.jrc.it/DOCUMENTS/Existing-

Chemicals/RISK_ASSESSMENT/SUMMARY/pen

ta_bdpesum015.pdf

0.004 to 0.013 n/a 0.0005

Principal uses in descending order of importance are flame retardants in high impact polystyrene, flexible polyurethane foam, textile coatings, wire and cable

insulation and electrical connectors. Also used in resins and polymers at levels ranging from 5 up to 30 %.

ALKYLPHENOLS 7, 8

Nonylphenols (mixed isomers) 50 to 1000 n/a < 100

Octylphenols (mixed isomers)

www.defra.gov.uk

5 to 150 n/a < 10

Primary degradation products of nonylphenol ethoxylates (NPEs) and octylphenol ethoxylates

(OPEs). These two products are one of the most widely used classes of surfactants used in domestic

detergents, pesticide formulations and industrial products (paper, textiles, coatings, oils and fuels, metal

and plastics). TRIBUTYLTIN COMPOUNDS

Tributyltin chloride (TBTCl) www.chemindustry.com www.pesticideinfo.org Tributyltin bromide (TBTBr) www.atsdr.cdc.gov

Tributyltin chlorate (TBTClO4) www.atsdr.cdc.gov Tributyltin nitrate (TBTNO3) www.atsdr.cdc.gov

Tributyltin hydroxide (TBTOH) www.atsdr.cdc.gov

bis(tri-n-butyltin)oxide (TBTO) www.atsdr.cdc.gov

nd to 5 n/a nd to 5 (high value

close to harbours e.g. 200)

Fungicide used in agriculture. Used as biocide antifouling paints, for wood treatment, in paper industry, for leather and textiles preservation, in cooling systems

*Keys: Principal uses: I = Industrial; A = Agricultural; P = Pharmaceutical; * after application on agricultural areas; V: wide variation of data; nd: not detected, n/a: not available at our knowledge; NC: not concerned

Background

26

Table 4b. WFD Inorganic Priority Pollutants with Typical Levels and Principal Uses

Typical level in water

Substance Link and Ref River water (ng/L)

Ground water (ng/L)

Sea water (ng/L)

Principal uses

CADMIUM and its

compounds

Elemental cadmium www.osha.gov www.jtbaker.com

Cadmium oxide (CdO) www.chemindustry.com www.inchem.org

Cadmium chloride (CdCl2) www.jtbaker.com www.cdc.gov Cadmium sulfide (CdS) www.inchem.org

20 n/a < 1

Cadmium metal is used mainly as an anticorrosive, electroplated on to steel. Cadmium sulfide and

selenide are commonly used as pigments in plastics. Cadmium compounds are used in electric batteries,

electronic components and nuclear reactors.

LEAD and its compounds

Elemental lead www.jtbaker.com

Lead acetate (Pb(C2H3O2)2 www.jtbaker.com

www.cdc.gov

Lead carbonate (PbCO3) www.chemindustry.com

www.inchem.org

Lead oxide (PbO) www.jtbaker.com www.chemindustry.com

Lead dioxide (PbO2) www.jtbaker.com www.inchem.org

Pb3O4 www.chemindustry.com Lead sulfide (PbS) www.reptox.csst.qc.ca Lead sulfate (PbSO4) www.reptox.csst.qc.ca

80 n/a 10

Used in the production of lead acid batteries, solder, alloys, pigments, rust inhibitors, ammunition, glazes

and plastic stabilizers. Lead compounds are also used in plumbing fittings and as solder in water

distribution systems.

Background

27

MERCURY and its compounds

9

Elemental mercury www.hgtech.com/HSE/merc

ury.htm www.atsdr.cdc.gov

0.01 to 5 0.5 to 15 0.05 to 3

Methyl-mercury (CH3HgCl) www.epa.gov

www.reptox.csst.qc.ca 0.04 to 0.8 n/a 0.008 to 0.2

The largest consumers of mercury are chloralkali, electrical equipment and paint industries (55 %). Mercury has a variety of other uses in industry, agriculture, military applications, medicine and

dentistry.

NICKEL and its compounds

Elemental nickel www.nsc.org www.jtbaker.com

Nickel oxide (NiO) www.jtbaker.com www.chemindustry.com Nickel hydroxide (Ni(OH)2) www.chemindustry.com

Nickel carbonate (NiCO3) www.chemindustry.com

www.inchem.org Nickel chloride hexahydrate (NiCl2,6H2O)

www.jtbaker.com www.chemicalland21.com

Nickel nitrate hexahydrate (Ni(NO3)2,6H2O)

www.jtbaker.com www.chemicalland21.com

Nickel sulfate hexahydrate (NiSO4,6H2O)

www.jtbaker.com www.chemindustry.com

< 2000 n/a 200

Used in a large number of alloys, including stainless steel, in batteries, chemicals, and catalysts, and in the electrolytic coating of items such as chromium-

plated taps and fittings used for tap water.

*Keys: Principal uses: I = Industrial; A = Agricultural; P = Pharmaceutical; * after application on agricultural areas; V: wide variation of data; nd: not detected, n/a: not available at our knowledge; NC: not concerned; Typical levels may be a mixt