Emerging Tools Manual

Sixth Framework Programme
SWIFT-WFD
Screening methods for Water data InFormaTion in support of the implementation of the Water Framework Directive
Contract: SSPI CT 2003 - 502492
REPORT: Draft 2
A TOOLBOX OF EXISTING AND EMERGING METHODS FOR WATER MONITORING UNDER THE WFD
Editors: Benoit Roig, Ian J. Allan, and Richard Greenwood
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 Benoit Roig Catherine Berho Richard Greenwood Graham Mills Ian J. Allan Marinella Farre Damia Barcelo K. Clive Thompson Fabienne Seby David Point Helene Budzinski Jean-Luc Cecile Guillain Pierron
Affiliation
Armines / Ecole des Mines d'Als University of Portsmouth CSIC ALcontrol Labs University of Pau LPTC-University of Bordeaux Aquametris
Contact
Benoit.Roig@ema.fr Catherine.Berho@ema.fr Richard.Greenwood@port.ac.uk Graham.Mills@port.ac.uk Ian.Allan@port.ac.uk mfuqam@cid.csic.es dbcqam@cid.csic.es Clive.Thompson@alcontrol.co.uk fabienne.seby@univ-pau.fr David.Point@univ-pau.fr h.budzinski@lptc.u-bordeaux1.fr aquametris@wanadoo.fr
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).
Operational Manual
Background information
Monitoring
Measurement of physico-chemical parameters
Biological assessment techniques
Chemical monitoring techniques
Legislation and standards
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.
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 pollutantspecific 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 problembased 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, semiquantitative 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 diffusionlimiting membrane and immobilisation in a receiving phase (that may be a chromatographic C18 phase or an organic solvent such as triolein or nhexane). 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 SWIFTWFD 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
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
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
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 Table 2 Table 3 Table 4a Table 4b Table 5a Table 5b Quality elements for the classification of ecological status List of the 33 priority substances List of the 66 emerging substances Organic Priority Pollutants with Typical Levels and Principal Uses Inorganic Priority Pollutants with Typical Levels and Principal Uses Physicochemical Properties of Organic Priority Pollutants Physicochemical Properties of Inorganic Priority Pollutants
Introduction
Table 5c Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 Table 22 Table 23
Physicochemical Properties of Other Water Contaminants Currently available methods for physico-chemical measurements Biomonitoring "Rapid Assessment Selection of biological monitoring tools for the assessment of water quality The major freshwater groups (taxonomically organised) The major divisions of freshwater ecosystems Biomarkers Bioassays/biosensors Biological early warning system commercially available or in development Currently available chemical analytical methods to measure Heavy metals and PAHs Non-biological methods available for monitoring environmental substances Chemical analytical methods Immunoassay test kits Example of some of the performance data in soil cyanide method Graphite Furnace Atomic Absorption (GF-AAS) Performance Data Leap Scheme Potable Water Results Parameters in relation to which Methods of Analysis must satisfy Prescribed Characteristics Potential Screening Tests considered relevant to the WFD Test Comparison E(L)C50 (mg l-1) of bioscrenning method for some parameters Main uses of the priority compounds Scientific Works Immunoassays for organic pollutants European Union funded RESEARCH PROJECTS involving sensors and biosensors for monitoring water pollution Main achievements of European Union funded research projects involving sensors and biosensors for monitoring water pollution Published ISO Water and Effluent Standards Draft ISO Water and Effluent Standards Published and Draft CEN Water and Effluent Standards Published and Draft SCA Water and Effluent Standards Standard methods for Inorganic species and metals EPA methods for inorganic species and metals EPA methods for ground or wastewater (www.speclab.com) EPA standard immunoassays Supplementary information on European projects on samplers, sensors and biosensors [separate document]
Appendix 1 Table 24 Appendix 2 Table 25 Appendix 3 Table 26 Table 27 Appendix 4 Table 28 Table 29 Table 30 Table 31 Table 32 Table 33 Table 34 Table 35 Supplementary Information
Introduction
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
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
Table 1. Quality elements for the classification of ecological status Type of water body
Rivers
Type of elements
Biological Hydromorphological
Quality elements / Parameters

Composition and abundance of aquatic flora Composition and abundance of benthic invertebrate fauna Composition, abundance and age structure of fish fauna 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 Thermal conditions Oxygenation conditions Salinity Acidification status Nutrient status Priority hazardous substances Priority substances Other possible significantly discharged pollutants 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 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 Thermal conditions Oxygenation conditions Salinity
Physico-chemical status
Chemical status
Lakes
Biological
Hydromorphological
Physico-chemical status
Background Acidification status Nutrient status Transparency Priority hazardous substances Priority substances Other possible significantly discharged pollutants 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 Depth variation Quantity, structure and substrate of the bed Structure of the intertidal zone Freshwater flow Wave exposure Thermal conditions Oxygenation conditions Salinity Nutrient status Transparency Priority hazardous substances Priority substances Other possible significantly discharged pollutants Composition, abundance and biomass of phytoplankton Composition and abundance of aquatic flora Composition and abundance of benthic invertebrate fauna Depth variation Quantity, structure and substrate of the coastal bed Structure of the intertidal zone Direction of dominant currents Wave exposure Thermal conditions Oxygenation conditions Salinity Nutrient status Transparency
Chemical status
Transitional waters
Biological
Hydromorphological
Tidal regime Physico-chemical status
Chemical status
Coastal waters
Biological Hydromorphological
Tidal regime Physico-chemical status
Background Chemical status Priority hazardous substances Priority substances Other possible significantly discharged pollutants Conductivity Oxygen content pH value Nitrate levels Ammonium levels Priority hazardous substances Priority substances Other possible significantly discharged pollutants
Ground waters
Groundwater level Chemical status
Background
Historical flows Modelled flows Real time flows Water table height Surface water discharge
Quantity and dymanics of water flow
Hydrological regime
Connection to groundwater bodies No. and type of barrier Provision for passage of aquatuc organisms River depth & width variation
Abundance Composition Presence of sensitive taxa Diversity
River continuity Invertebrate fauna HYDROMORPHOLOGICAL Fish
Abundance Composition Life cycle/age structure Presence of sensitive taxa Abundance Composition Presence of sensitive taxa Abundance Composition Presence of sensitive taxa Abundance Composition Bloom frequency/intensity Biomass
River cross section Flow Cross sections Particle size Presence/location of CWD
Structure & substrate of the river bed
Morphological conditions BIOLOGICAL

Structure of the riparian zone Current velocity
Channel patterns
Phytobenthos Macrophytes
Length/width Species composition Continuity/ground cover
Phytoplankton
SELECTION OF QEs - RIVERS
Thermal conditions Oxygenation conditions
Temperature Dissolved oxygen
All WFD priority list substances Other substances depending on catchment pressures
Salinity SPECIFIC SYNTHETIC POLLUTANTS PHYSICO-CHEMICAL
Electrical conductivity PH Alkalinity/ANC Total phosphorus Soluble reactive phosphorus
Acidification status
Nutrient conditions
All WFD priority list substances Other substances depending on catchment pressures
Total nitrogen Nitrate + nitrite Ammonium
SPECIFIC NON SYNTHETIC POLLUTANTS
Other
Suspended Solids Turbidity
Legend: Mandatory QE specified in Annex V.1.2
Recommended QE
Figure 1. Example of selection of quality elements for rivers
10
Background
Biological assessment
Ecological/Biological Monitoring
Physicochemical characteristics
Oxygenation
Use of sentinel organisms Dissolved Oxygen Refs to sampling strategies Microbiological status
Acidification status
pH
Salinity
Respirometry BOD
Tools for ecological monitoring
Hardness/acid/bases
Conductivity Redox conditions
Priority & emerging chemical pollutants
Organic matter
COD
Quality elements
TOC
Nutrient conditions
Nitrate/nitrite
Biological Assessment
Chemical Assessment
Immunoassays Organic matter Chemical analytical methods
Total Nitrogen OM aromaticity
Biomarkers Non-biological sampling methods Biosensors Chemical methods for PAHs & heavy metals BEWS/Whole organism assays Turbidity Total Phosphorus Ammonium
Abstracts/details
EU-funded projects on samplers & (bio)sensors
Achievements Phosphate Supplementary Information
Figure 2. User-interface of this operational manual
11
Background
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.
12
Background
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/waterframework/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.
13
Background
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 Cadmium And C10-13Compounds Chloroalkanes Hexachlorocyclohexane Hexachlorobutadiene Hexachlorobenzene (HCH) Mercury And Nonylphenols Pentachlorobenzene Compounds Tributyltin Compounds 14 PRIORITY SUBSTANCES UNDER REVIEW Anthracene (PAH) Diuron Naphthalene (PAH) Trichlorobenzenes 8 PRIORITY SUBSTANCES: Alachlor Dichloromethane Benzene Fluoranthene Chlorofenvinphos Nickel And Compounds 1,2-Dichloroethane Trichloromethane Atrazine Endosulfan Octylphenols Trifluralin Chlorpyrifos Isoproturon Pentachlorophenol Di(2Ethylhexyl)Phthalate (DEHP) Lead And Compounds Simazine Brominated Diphenylether Polyaromatic Hydrocarbons (PAH)
Benzo(a)pyrene Benzo(b)fluoranthene Benzo(g,h,i)perylene Benzo(k)fluoranthene Indenol(1,2,3-od)pyrene
14
Background
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. 2. 3. 4. Veterinary and human antibiotics Prescription and non-prescription pharmaceuticals Household and industrial wastewater compounds 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 Enrofloxacin Norfloxacin Sulfachloropyridazine Sulfamethoxazole Tylosin PRESCRIPTION DRUGS Albuterol Cimetidine Codeine Dehydronifedipine Chlortetracycline Erythromycin-H2O Oxytetracycline Sulfadimethoxine Sulfathiazole Virginiamycin Ciprofloxacin Erythromycin Metabolite Roxithromycin Sulfamerazine Tetracycline Doxycycline Lincomycin Sarafloxacin Sulfamethizole Trimethoprim
15
Background
(Salbutamol) Digoxin Fluoxetine Ranitidine Digoxigenin Gemfibrozil Warfarin Diltiazem Metformin Enalaprilat Paroxetine Metabolite
NONPRESCRIPTION DRUGS Acetaminophen Caffeine Cotinine Ibuprofen
OTHER WASTEWATER-RELATED COMPOUNDS 1,4-Dichlorobenzene Acetophenone Butylated Hydroxy Toluene Carbaryl Dieldrin Methyl Parathion 4-Nonylphenol Monoethoxylate Phenanthrene Tetrachloroethylene (4) Triphenyl Phosphate STEROIDS AND HORMONES Cis-Androsterone Equilin Estrone Stigmastanol Cholesterol 17-Ethynyl Estradiol Mestranol Testosterone Coprostanol 17-Estradiol 19-Norethisterone Equilenin Estriol Progesterone 2,6-Di-TertButylphenol Anthracene Bis(2-Ethylhexyl) Adipate Cis-Chlordane Diethylphthalate 4-Methyl Phenol 4-Nonylphenol Diethoxylate Phenol Triclosan 2,6-Di-Tert-Butyl1,4-Benzoquinone Benzo[a]Pyrene Bis(2-Ethylhexyl) Phthalate Chlorpyrifos Ethanol,2-ButoxyPhosphate Naphthalene 4-Octylphenol Monoethoxylate Phthalic Anhydride Tri(2-Chloroethyl) Phosphate 5-Methyl-1hBenzotriazole 3-Tert-Butyl-4Hydroxy Anisole Bisphenol A Diazinon Fluoranthene N,NDiethyltoluamide 4-Octylphenol Diethoxylate Pyrene Tri(Dichlorisopropyl) Phosphate
16
Background
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 Metallic compounds Organometallic compounds Pesticides Aromatic hydrocarbons Organic nitrogen compounds Organophosphate Phenols Drugs Organic Esters Organosilicon Phthalate esters Hormones Organohalogens PAHs 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).
17
Background
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 Boron n.a. Chromium n.a 1,2 Dichloroethane Endosulfan Atrazine Cadmium Cobalt n.a. Dichlorvos Fenitrothion Azinphos-ethyl Carbontetrachloride Copper Dioxins n.a. Fenthion Lead Parathion Silver n.a Trichlorobenzene Triphenyltincompounds Azinphos-methyl Chloroform DDT Drins HCH Malathion Parathion-methyl Simazine Trichloroethane Zinc n.a
Hexachlorobenzene Hexachlorobutadiene Mercury Pentachlorophenol Tetrachloroethylene Trichloroethylene Nickel Selenium Tributyltincompounds Trifluralin
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)
18
Background
NOT ACHIEVED Cadmium Hexachlorobenzene (HCB) ALMOST ACHIEVED Ammoniumnitrogen Bentazon Lead Tributyltin cation (TBT) CLEARLY ACHIEVED Aldrin 3-chloroaniline 2-chlorotoluene 1,2-dichloroethane -HCH Isodrin Tetrabutyltin 1,2,4trichlorobenzene Triphenyltin cation (TPT) Azinphos-ethyl 1-chloro-2nitrobenzene 4-chlorotoluene DDT-group -HCH Malathion Tetrachloroethylene (PER) 1,3,5trichlorobenzene Benzene 1-chloro-3nitrobenzene 3,4-dichloroaniline Dieldrin -HCH Pentachlorophenol (PCP) Tetrachloromethane 1,1,1-trichloroethane 2- chloroaniline 1-chloro-4nitrobenzene Dibutyltin cation Endrin Hexachlorobutadiene Simazine 1,2,3trichlorobenzene Trichloroethylene AOX Benzo(a)pyrene Mercury Arsenic Chromium Nickel Atrazine Isoproturon Total phosphorous Copper PCBs (7 congeners) Diuron Lindane (-HCH) Fenitrothion Zinc
NOT DETECTABLE (BELOW LIMITS OF DETERMINATION) Azinphos-methyl 1,4dichlorobenzene Parathion-ethyl 4-chloroaniline Endosulfan Parathion-methyl 2,4dichlorophenoxyacetic acid Fenthion Trichloromethane (chloroforme) Dichlorvos Mecoprop-p Trifluralin
19
Background
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.
20
Background
Table 4a. WFD Organic Priority Pollutants with Typical Levels and Principal Uses
Typical level in water
Substances
Link and Ref
River water Ground Sea water (ng/L) water (ng/L) (ng/L)
Principal uses*
PESTICIDES
Atrazine Simazine Alachlor Chlorfenvinphos Chlorpyrifos (-ethyl, -methyl) -HCH (Lindane) Isoproturon DDT Aldrin Endrin
1 www.ksgrains.com/triazi ne/links.html www.pesticideinfo.org www.epa.gov www.inchem.org http://extoxnet.orst.edu www.inchem.org www.atsdr.cdc.gov www.chlorpyrifos.com www.epa.gov www.atsdr.cdc.gov www.headlice.org http://extoxnet.orst.edu www.pan-uk.org www.pan-uk.org http://extoxnet.orst.edu www.epa.gov www.atsdr.cdc.gov www.atsdr.cdc.gov www.scorecard.org www.atsdr.cdc.gov www.scorecard.org 14 to 1200 < 5 to 124 10 n/a nd to 10 10 to 100 100 to 125 nd to 0.2 < 0.1 7 to 150 10 to 6000 * 200 to 1000 < 100 to 16600 n/a nd 3 to 163 50 to 100 nd not present Max. 200 n/a n/a n/a n/a Nd n/a n/a n/a n/a < 0.01 to 10 Pre- and post-emergence herbicide Pre-emergence herbicide Pre- and post-emergence pesticide Insecticide (control of cattle tick, control of root flies, rootworms, ...) 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. Insecticide and therapeutic pesticide Systemic herbicide Insecticide with a broad spectrum Insecticide for soil-dwelling pests and for wood against termites Non-systemic and persistent insecticide used mainly on fieldcrops
21
Background
Isodrin Dieldrin
Trifluralin
www.pesticideinfo.or g www.scorecard.org www.inchem.org

www.epa.gov www.scorecard.org www.inchem.org www.pan-uk.org
www.atsdr.cdc.gov/
300000 < 10
nd to 550
n/a
n/a n/a n/a
Discontinued insecticide Insecticide for wood against termites

pre-emergence herbicide
not present
generally nd
POLYAROMATIC HYDROCARBONS (PAHS)

Benzo(a)pyrene Benzo(b)fluoroanthene Benzo(g,h,i)perylene Benzo(k)fluoroanthene Indeno(1,2,3-cd)-pyrene
www.epa.gov www.epa.gov www.epa.gov www.epa.gov www.scorecard.org www.ecousa.net/toxics/naph.sht ml www.scorecard.org
1 < 50 0.3 to 25 < 50 < 100
n/a <5 0.7 to 10 < 10 nd to 100
0.01 to 0.1 n/a n/a <5 < 0.1
No industrial uses except in analysis or toxicology laboratories - Produces by incomplete combustion of organic material. No industrial uses. Produces by incomplete combustion of organic material. No industrial uses. Produces by incomplete combustion of organic material. No industrial uses. Produces by incomplete combustion of organic material. No industrial uses. Produces by incomplete combustion of organic material. 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. Chemical intermediate in the preparation of colour products and resins. Also used as a diluent in wood preservation, insecticide and fungicide products.
Naphthalene
nd to 1000
nd to 10000
< 10
Anthracene
0.006 to 10
< 100
n/a
VOCs & SVOCs

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. Selective fungicide, wood preservative, manufacture of pentachlorophenol, used in the production of aromatic fluorocarbons. Wood Preservative, fungicide, molluscicide, pre-emergent herbicide, biocide in industrial water system.
Benzene
www.epa.gov
< 1000
< 30
< 5 to 20
Hexachlorobenzene (HCB) Pentachlorophenol
www.epa.gov www.epa.gov www.scorecard.org
nd to 0.04 100 to 1000
nd < 500
Nd to 0.03 1 to 5
22
Background
www.epa.gov www.epa.gov www.scorecard.org www.epa.gov www.epa.gov www.scorecard.org www.epa.gov www.epa.gov www.atsdr.cdc.gov www.epa.gov www.scorecard.org www.atsdr.cdc.gov www.epa.gov www.scorecard.org www.inchem.org www.inchem.org www.inchem.org www.inchem.org Anti-microbial agent, herbicide, bactericide and used to prepare fungicide and wood preservation. Chemical intermediate for synthesis of phytosanitary substances. Used as a fungicide in paper and pulp mills, as an herbicide and as an intermediate in the manufacture of other pesticides 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. Widely used as an organic solvent and is found in paints, insecticides, degreasing and cleaning fluids, and other products. Chemical intermediate in the production of the fungicide quintozene. 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 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. 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 Intermediate for chlorofluoromethanes manufacturing. Metal degreasing, cleaning agent, solvent for rubber cement, cable and semiconductor manufacture. Also used in soap perfumery and insecticides. 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
2,4,6-Trichlorophenol
n/a
n/a
Nd
n/a
n/a
Nd
1,2-Dichloroethane
< 200
< 200
nd to 210
Dichloromethane Pentachlorobenzene 1,2,3-trichlorobenzene 1,2,4-trichlorobenzene 1,3,5-trichlorobenzene
100 to 743000 0.1 to 1 10 1 to 10 V
3000 n/a n/a 1 n/a
n/a n/a 1 0.3 1
Trichloromethane (chloroform)
www.epa.gov www.atsdr.cdc.gov
100 to 30000
nd to 5000
< 0.05 to 8
Tetrachloroethene
50
70 to 2000
0.1 to 0.8
Tetrachloromethane
10 to 50
200
0.12 to 0.85
Trichloroethene
1000 to 24000
1000
n/a
23
Background
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 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
n/a
DIOXINS AND FURANS

PCDD/Fs 2378-TCDD 123478-HxCDD 123789-HxCDD HxCDD 1234678-HpCDD HpCDD OCDD 2378-TCDF 23478-PeCDF
2, 3
PCDD: 0.04 PCDF: 0.004 n/a www.ejnet.org/dioxin/ www.dioxinfacts.org www.atsdr.cdc.gov www.epa.gov/opptintr/p bt/dioxins.htm n/a n/a n/a n/a n/a n/a n/a n/a 0.003 n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.0164 < 0.00154 0.00017 0.0027 0.025 < 0.0005 < 0.00006 < 0.00025 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 4, 5, 6 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
24
Background
DIPHENYLETHERS)
Bis(pentabromophenyl)ether Diphenyl ether, octabromo derivative www.cdc.gov http://ecb.jrc.it/DOCUME NTS/ExistingChemicals/RISK_ASSES SMENT/SUMMARY/oct asum014.pdf http://ecb.jrc.it/DOCUME NTS/ExistingChemicals/RISK_ASSES SMENT/SUMMARY/pen ta_bdpesum015.pdf 7, 8 50 to 1000 www.defra.gov.uk Octylphenols (mixed isomers) 5 to 150 n/a < 10 n/a < 100 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). n/a n/a 0.0001 to 0.004 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 %.
n/a
n/a
n/a
Diphenyl ether, pentabromo derivative
0.004 to 0.013
n/a
0.0005
ALKYLPHENOLS
Nonylphenols (mixed isomers)
TRIBUTYLTIN COMPOUNDS
Tributyltin chloride (TBTCl) Tributyltin bromide (TBTBr) Tributyltin chlorate (TBTClO4) Tributyltin nitrate (TBTNO3) Tributyltin hydroxide (TBTOH) bis(tri-n-butyltin)oxide (TBTO) www.chemindustry.com www.pesticideinfo.org www.atsdr.cdc.gov www.atsdr.cdc.gov www.atsdr.cdc.gov www.atsdr.cdc.gov www.atsdr.cdc.gov nd to 5 n/a nd to 5 (high value Fungicide used in agriculture. Used as biocide close to harbours e.g. antifouling paints, for wood treatment, in paper industry, 200) 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
25
Background
Table 4b. WFD Inorganic Priority Pollutants with Typical Levels and Principal Uses
Typical level in water River water (ng/L)
Substance
Link and Ref
Ground water (ng/L)
Sea water (ng/L)
Principal uses
CADMIUM and its compounds

Elemental cadmium Cadmium oxide (CdO) Cadmium chloride (CdCl2) Cadmium sulfide (CdS) www.osha.gov www.jtbaker.com www.chemindustry.com www.inchem.org www.jtbaker.com www.cdc.gov www.inchem.org 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.
20
n/a
<1
LEAD and its compounds

Elemental lead Lead acetate (Pb(C2H3O2)2 Lead carbonate (PbCO3) Lead oxide (PbO) Lead dioxide (PbO2) Pb3O4 Lead sulfide (PbS) Lead sulfate (PbSO4) www.jtbaker.com www.jtbaker.com www.cdc.gov www.chemindustry.com www.inchem.org www.jtbaker.com www.chemindustry.com www.jtbaker.com www.inchem.org www.chemindustry.com www.reptox.csst.qc.ca 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.
26
Background
MERCURY and its compounds

Elemental mercury
9
www.hgtech.com/HSE/merc ury.htm 0.01 to 5 0.5 to 15 0.05 to 3 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.
www.atsdr.cdc.gov
Methyl-mercury (CH3HgCl) www.epa.gov www.reptox.csst.qc.ca 0.04 to 0.8 n/a 0.008 to 0.2
NICKEL and its compounds

Elemental nickel Nickel oxide (NiO) Nickel hydroxide (Ni(OH)2) Nickel carbonate (NiCO3) Nickel chloride hexahydrate (NiCl2,6H2O) Nickel nitrate hexahydrate (Ni(NO3)2,6H2O) Nickel sulfate hexahydrate (NiSO4,6H2O) www.nsc.org www.jtbaker.com www.jtbaker.com www.chemindustry.com www.chemindustry.com www.chemindustry.com www.inchem.org www.jtbaker.com www.chemicalland21.com www.jtbaker.com www.chemicalland21.com 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 chromiumplated 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 mixture of dissolved and total concentrations.
27
Background
1.7 - Environmental Risk assessment of these substances

A report on the socio-economic impact of the identification of priority pollutants may be found at: http://europa.eu.int/comm/environment/enveco/chemicals/haz_sub_report.pdf
1.7.1 - Priority Hazardous Substances:

Penta Brominated Diphenylether (pentBDE) See section on Poly Brominated Diphenylethers. C10-13 chloroalkanes (SCCPs) Short chain chlorinated paraffins (SCCPs) are used in the tanning industry in leather finishing as liquid greasing agents. They can represent 20% of the greasing liquor, and 95% of them is absorbed by the leather which would mean that 5% is incorporated into the waste water. They are also used in the rubber industry and in the textile industry as flame retardant, as well as in the formulation of hot-melt adhesives and in some fluids used for metal finishing. SCCPs are not toxic through contact with the skin. They are persistent agents which are not easily degradable by natural mechanisms, therefore they are bioaccumulative substances which concentrate mainly in aquatic animal tissues, and enzymatic disrupters which alter the hormonal system of living organisms causing carcinogenic processes to take place. They have toxic effects on aquatic animals through the prolonged exposure to higher concentrations than normal (0,12 - 1,45 g/L) while the effects on humans are not yet clear. The carcinogenic effect of these substances has been tested on rodents but not on human beings. Cadmium and compounds Cadmium poses a number of important problems in terms of designation as a PHS. Cessation of the use of Cd in most of its applications appears feasible (at least in the long term) but at a significant cost for some applications. However, unintentional sources of Cd are very important and there is presently little information on the consequences of a cessation option on these unintentional sources. The most significant of these unintentional releases are in metals production and the combustion of iron and steel. As Cd is present in ores, it is difficult to envisage any metals production that does not involve some release of Cadmium. Cadmium itself is only produced commercially as a by-product of zinc refining. In the case of uses of cadmium being banned, it would need to be disposed off safely. The presence of Cd in fossil fuels also raises concern in terms of a cessation target, as the concept of cessation does not appear to be conducive with the continued use of fossil fuel resources. In farming there is likely to be potential for reducing Cd emissions through switching to low Cd fertilisers. However, cessation would require the introduction of technologies such as de-cadmination which would add significantly to fertiliser costs (10%+). Hexachlorobenzene (HCB) HCB is no longer produced or used in Europe and as such on face value a target of zero emissions of HCB to the aquatic environment would not be expected to entail any costs to UK business. However, emissions continue because they arise as an 29
Background
unintentional by-product of a number of activities. Emissions have been substantially reduced in recent years. No comprehensive risk assessment is available. A risk assessment prepared by industry (undertaken according to European guidelines) concludes there is no need for further action to reduce risks. However, if a very strict interpretation of the cessation target was applied, all activities from which HCB unintentionally arises, would need to cease as it is not possible to carry out the activities without producing at least some HCB. According to the industry's risk assessment the elimination of these sources of HCB would secure only a very marginal reduction in HCB risk. Hexachlorocyclohexane (HCH) Lindane (the most important isomer of HCH) has been around for almost half a century during which mounting evidence of its undesirable properties has emerged. It is now almost obsolete with its main use (as a plant protection product) being phased out across Europe. There are some very minor other uses (in wood treatment and for non-agricultural insect control) but only very minor costs would be expected as alternatives are readily available. Given its use in the developing world there is concern over future emissions arising from imported materials (especially fleeces). A system of import control, recognising the needs of small businesses would therefore need to be developed. Hexachlorobutadiene (HCBD) HCBD is no longer produced or used in Europe and as such on face value a target of zero emissions of HCBD to the aquatic environment would not be expected to entail any costs to UK business. However, emissions continue as they arise from an unintentional by-product of a number of activities. Emissions have been substantially reduced in recent years. No comprehensive risk assessment is available; however, a risk assessment by industry (undertaken according to European guidelines) concluded that there is no need for further action to reduce risks. As it is not feasible to undertake those activities where HCBD arises unintentionally, without emitting at least some HCBD, potentially these activities would need to cease in order to meet the zero emissions target. Cessation of discharges, emissions and losses from these activities would apparently secure only a very marginal reduction in HCBD risk. Mercury and compounds In all but a few specialist areas, alternatives exist for mercury used in commercial products. Reducing anthropogenic emissions to zero would involve limited costs for the product groups by which it is used (e.g. dentistry, batteries, instrumentation and lighting), although there would be many issues to be resolved. Evidence from other countries which are far more advanced than the UK in eliminating their emissions of mercury show that for most intentional uses the consequences of a ban are not large. The experiences of Sweden in particular have shown that a ban can be implemented successfully if this ban includes time-limited exemptions which allow industries to make the necessary structural changes and/or carry out research and testing so as to introduce new processes or substances to replace mercury. Costs associated with this method have been incurred mainly in specialist areas such as laboratory measuring equipment.
30
Background
However, alternatives exist to the use of mercury in the chloroalkali industry and a phase out of this process is underway on the basis of the North Sea Conference resolution, which has been followed up by OSPAR and the EC IPPC Directive. Notwithstanding these concerns, possibly the greatest problem relates to unintentional emissions. As an elementary substance mercury is present as an impurity in ores and in fossil fuels and a number of waste streams. The concept of zero anthropogenic emissions is inconsistent with an economy based on fossil fuel use and the transformation of ores. There are no alternatives to the use of fossil fuels or the transformation of ores. A target of zero emissions is therefore not achievable if these industries are to continue. Nonylphenols (NP/NPE) There would also be additional costs in the case of Octylphenols which cannot be identified without further data on the identified risks (which is currently ongoing). From these costs the costs of any restrictions introduced through marketing and use controls proposed under the Existing Substances Regulation and cost incurred by the introduction of technology and environmental quality standards would need to be deduced. The uses include the production of NP and its derivatives and the use of NPE in a number of applications such as plastics, paints, photography and engineering. These uses do not pose a significant threat to the aquatic environment, a fact recognised by the existing risk reduction strategy, which opted to control these uses through technology and environmental quality standards rather than banning them. As the majority of these uses do not pose a threat to the aquatic environment, a cessation of their use under the WFD would lead to considerable costs, limited additional benefits and may prove unpopular with the businesses concerned. Perhaps of most concern is the use of NPE as a spermicide because of the present lack of substitutes. Polyaromatic Hydrocarbons (PAHs) A target of zero emissions from all sources is not feasible. The cost of such a move is incalculable as the concept of zero discharges, emissions and losses of PAH is inconsistent with an economy which relies heavily on fossil fuels (for energy and derived products). Although reducing the dependency on fossil fuels is an aim of government policy, the use of the WFD to achieve this goal would not seem to be appropriate. The concept of a strictly applied cessation target for PAHs clearly has its difficulties. High emissions of PAH are concentrated in a handful of sectors - notably the aluminium industry, where coal tar products such as coke and pitch are used extensively. Emissions to water are negligible, as this is inherently a dry process. However, even with current application of BAT substantial volumes of PAH are emitted to the atmosphere and end up on land or water through deposition. While emissions will be reduced in the future, it is not presently practicable to eliminate emissions of PAH from these processes and hence controls aimed at cessation would threaten a substantial market value (2 Billion). Such controls would inevitably impact on the producers of coal tar products (coke and pitch). Such an outcome would be a consequence of a very strict definition of cessation that encompasses discharges emissions and losses to the water environment indirectly from atmospheric pollutants. It is recommended that clarification is sought as to whether the WFD is seen as leading to the control of indirect inputs in this manner.
31
Background
A more pragmatic approach would involve the banning and substitution of products, which contain high concentrations of PAH, which through use and disposal do lead to a more direct impact on the water environment. Examples include the use of creosote to protect wood and bitumen for roofing. There are significant differences in the risks associated with different PAHs, which would argue for their differential treatment. This is already recognised by the Priority Substances List by having anthracene and naphthalene (both PAHs) separately identified. Of the PAH group there is an argument for a differential treatment particularly of fluoranthene. Fluoranthene, which is a constituent part of the linings of water pipes, and has been removed from the PAH parameter in the Drinking Water Directive, has now been categorised as a Priority Substance only. However, while there is an argument for differential treatment, it is not clear that attaching a cessation target to some members of this group is consistent with the continued production of other members of the group as they tend to occur all together. As PAHs occur so widely as unintentional contaminants it is illogical to aim to completely cease some emissions while allowing other emissions to continue. Pentachlorobenzene A cessation target applied to pentachlorobenzene would not cause any costs in the UK. It is not produced in the UK and its only remaining use is about to be withdrawn. It may be released as a by-product from other processes. The risk assessment currently being carried out will identify whether there is a need to control any other unintentional release of pentachlorobenzene. Tributyltin compounds The assignment of TBT as a PHS under the WFD is for the most part cost neutral as the major use of the substance (anti-fouling paints) is to be banned internationally by 2008. Other sectors affected by a ban would incur some costs but these would not be expected to be high as alternatives exist for most applications.
1.7.2 - Priority Substances under Review

Anthracene and Naphthalene Anthracene and naphthalene have been identified as Priority Substances under Review and may therefore receive PHS status at a later date. Due to the unintentional sources of both products (which accounts for the majority of emissions) there would be great problems in applying the elimination target to these substances. Fossil fuel use is not consistent with a zero emission standard for anthracene and naphthalene. In addition even if beneficial use of these substances ceased they would still be produced as a by-product of coal tar production and would therefore need to be disposed of safely. If the elimination target were applied to intentional sources a wide range of sectors would be affected in the UK in particular for naphthalene. Such impacts need to be seen in the context of the available risk assessment data, which suggests that for naphthalene only one current use gives rise to unacceptable risks. It is recommended that the RIA is revised once the risk assessments and the strategies for risk reductions have been completed, and the measures to be adopted by the WFD have been finalised.
32
Background
Atrazine Atrazine is the mainstay of weed control in maize. It has a broad-spectrum application and is available cheaply. Alternatives are available for all uses. However, these are both more expensive and because of the broad spectrum of atrazine's application it is likely that a range of alternatives would need to be applied to replace a single application of atrazine. As a result the main cost would be expected to fall on maize growers through additional costs of alternative pesticides and additional operational costs in their application (e.g. mixing, more frequent application). In addition to agricultural use a range of home and garden uses would be affected. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance. Chlorpyrifos Chlorpyrifos is a widely used, important insecticide with a large number of applications in both major and niche markets. While alternatives are available for some applications there are a large number of crop/pest situations in which there is no currently authorised alternative. Given the size of the market for chlorpyrifos it would be likely that industry would attempt to develop an alternative (for example especially to replace chlorpyrifos in the protection of brassicas and cereals). However, the fact that chlorpyrifos has dominated the market for decades indicates that this will not be an easy task. Inevitably there will be some niche markets where no suitable and cost-effective alternative can be found. In these cases these crops will be likely to lose market value because of the inability to manage the pests. In addition to agricultural use a range of home and garden uses would be affected. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance. Di (ethylhexyl) phthalate (DEHP) DEHP is an important chemical given its widespread use in plastics manufacture. It serves a role in making plastics products for a wide variety of uses. Concern has been raised about the substance for a number of reasons. There is generally a high level of consumer concern regarding phthalate plasticisers in general because of their ubiquitous use in children's toys. Other concerns have been raised about its endocrine disrupting potential. However, the inclusion of DEHP on the list has received substantial criticism from industry on technical grounds - principally that the conclusions of the as yet unpublished risk assessment will most likely conclude that DEHP does not pose a risk and would not require any further risk reduction measures. If this conclusion is confirmed, and the results of the risk assessment are not reflected in the measures adopted for progressive reduction, then potentially quite significant costs would be incurred to control discharges, emissions and losses of DEHP with limited benefit. It is recommended that steps are taken to reflect in any future Daughter Directive for DEHP the outcome of the risk assessment so that any costs to the UK are proportional to the benefits likely to result from additional control measures.
33
Background
Diuron Alternatives are available in most situations. In its main application (amenity) the alternative is to use contact acting substances such as glyphosate and paraquat more frequently. This would increase operational costs (mixing, more frequent application) for users. However, in some specific applications there are currently no authorised alternatives and hence there would be additional costs in developing authorisations for the crop/pest situations. In addition to agricultural use a range of home and garden uses would be affected. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance. Endosulfan Endosulfan currently has a very limited use in the UK protecting berries and bulbs from attack by mite pests. Alternatives are very limited and the size of the market would probably be insufficient to bring forth the development of a new, replacement active. As a result the main costs would be expected to be borne by berry and bulb growers as crop value diminishes because of their inability to protect crops against pests. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance. Isoproturon Isoproturon is the mainstay of weed control in cereals in the UK. It is the most effective substance for a range of pests and is available cheaply. Alternatives are available in most applications but are less effective (particularly in barley) and more expensive. Isoproturon's broad application would mean that in many cases a range of substances would be needed to replace a single application of isoproturon. The size of the market, however, would be expected to bring forward the introduction of new actives - some of which are already in development. However, there may remain some important crop/pest situations in which no viable alternative is available. In the short term the main costs would be expected to fall on cereal producers who would be forced to use a range of alternative, more expensive and less efficient substances. In the longer term cereal producers would face increased costs from newly developed alternatives and in some cases from reduced market value because of the inability to protect crops in specific circumstances. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance. Lead and compounds Lead is a very widely used metal with a wide range of applications. Most of its uses are already heavily regulated. In addition, however, there are a number of unintentional and diffuse sources of lead to the environment, where it also occurs naturally. As lead is released to the environment as an unintentional by-product (including trace lead in fuels and as an impurity in ores), it is not considered feasible to eliminate all emissions discharges and losses of lead. Such a target could be
34
Background
inconsistent with an economy based on the fossil fuel combustion and the transformation and processing of ores and metals. PHS status would also cause severe economic implications for the intentional uses of lead. In addition it would inevitably mean the need to find a replacement for lead acid batteries - a widely used technology, with considerable future promise, which has no current feasible alternatives. Lead emissions also occur from the widespread use of lead in buildings - particularly flashing. Addressing this source would lead to considerable cost increases and diminish the architectural value of many buildings. As a result an elimination target, which is incapable of recognising the different risk benefit trade-offs associated with lead uses, would be expected to lead to disproportionate costs. It is recommended that the RIA should be refined once the measures to be adopted under the WFD have been finalised. Octylphenols See section on Nonylphenols. Pentachlorophenol (PCP) PCP is already a heavily regulated substance. It is banned outright in many Member States and its current use in other Member States (including the UK) arises only as the result of derogations which will cease in 2008. As a result the WFD will be cost neutral in relation to production and use. Depending on the eventual status of PCP (PHS or PS) there may be further costs in relation to controlling the import of PCP in finished products (wood, textiles and leather). PHS status would seem to imply that this source of emissions discharges and losses would also need to be ceased. In most cases alternatives are available, however, these tend to be inferior in the case of current military applications. PS status would however increase the flexibility with which this source of problem could be controlled. The banning of imports containing PCP may be too complex to be feasible in which case only an international ban could achieve zero emissions. Simazine Simazine is mainly used in the protection of field beans. There are alternatives in all uses and in addition it would be expected that herbicides being developed for use on soya beans could be applied to current simazine uses. In addition to agricultural use a range of home and garden uses would be affected. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance. Trichlorobenzenes 1,2,4-Trichlorobenzene (the identified indicator substance for the group of substances known as trichlorobenzenes) has had a widespread use historically mainly as a carrier substance for dyes. It remains a high volume substance with European production of around 7000 tonnes - 80% of which is exported. Currently the UK use is very limited with around 5 tpa specialist applications where 1,2,4-TCB confers special properties in conjunction with other products (e.g. to provide high performance insulation in wire and cable and as a brightening solution in metal plating). A risk assessment is underway for this substance but is not yet available. Analysis of the available data by industry (according to the agreed EC method)
35
Background
indicates the substance does not occur in the aquatic environment at levels, which pose a risk. Trichlorobenzenes have been identified as a PHS under review. PHS status would mean that current uses would need to cease. Across Europe the main impact would be in the loss of export revenues. Should the industry assessment of the risk to the environment be confirmed by the full risk assessment then the additional controls should be restricted to meeting a progressive reduction target, which should take into account the actual risks posed to the environment. Trifluralin Trifluralin is used on a wide range of minor crops. Current alternatives are available for all uses but these are generally less effective and more expensive. Trifluralin is particularly inexpensive and as a result has been used for crop protection in a range of low margin crops. The extent of the impacts depends on the controls and the market dynamics, which are difficult to judge at this stage. It is clear, however, that in understanding the risk, cost and benefit trade-offs, attention must be paid to the specific crop/pest situations and not only the properties of the substance.
1.7.3 - Priority Substances

(nb the following risk assessments were carried out on the basis of cessation of discharges, although Priority Substances would in fact be subject to progressive reduction rather than cessation.) Alachlor Alachlor was used as a pesticide. Any cost implications would be negligible, as it is not currently approved for use. Benzene No comprehensive risk assessment is currently available for benzene and as a result it is not possible to make any estimate of the extent of current risks from benzene or of the benefits of additional controls which would be aimed at progressive reduction. CEC (2000) in their analysis of the socio-economic implications of additional controls on possible priority hazardous substances concluded that the socio-economic implications would be extensive at the European level. This is confirmed for the UK in the present analysis. Benzene is a hugely important basic organic chemical that is ultimately important for a large number of products and services. Benzene, however, is also a natural substance being a constituent of fossil fuels. There are therefore natural emissions of benzene as well as unintentional releases. Benzene has been very important in allowing the introduction of unleaded petrol and the content in petrol is tightly regulated (currently 1%). Benzene in petrol is the main source of atmospheric emissions and is likely to be an important source of benzene in the aquatic environment (through dry and wet deposition, run-off). The introduction of catalytic converters has enabled significant reductions in benzene emissions and the costs of further controls on the fuel sector are likely to rise exponentially. In benzene's role as a basic chemical one of the most important downstream markets is in the production of polystyrene. Releases from these plants arise to both the atmosphere and water. Polystyrene production is not a high value market but the volume of use means that additional controls on emissions may have significant repercussions for this sector.
36
Background
At present, however, there is insufficient information on the risks posed by benzene to the aquatic environment and the reduction measures to be adopted to provide further details of the possible implications of additional controls. Poly Brominated Diphenylether (PolyBDPE) (including pentaBDPE) PolyBDPEs are a range of important substances used for their flame retarding properties. The main uses are in the plastics and textiles industries. Three distinct commercial substances are involved - deca-, octa- and penta- of which deca- is by far the most significant. Of these penta- is the only substance to receive PHS status. It is also the only substance for which additional costs would not be required because adequate control measures (a phase-out) are already being instigated as a result of the Existing Substances Regulation. For deca- and octa- additional controls will be required to reach the target of progressive reduction. For both substances, however, a main use (in electrical and electronic equipment) may already be phased out because of the proposed EU WEEE Directive. It is presently unclear whether these controls would deliver additional benefits because the conclusions of the risk assessments are at present uncertain - risks directly to water are considered to be low but cannot be ruled out in relation to sediments. In addition more information is required in relation to disposal and in sewage treatment works. The main benefits are likely to arise in the long term as a result of reduced bioaccumulation of these substances in the environment. A loss of an important flame retardant, without equally effective replacement, could, potentially increase the risk of fire related injuries. The impacts would fall largely on producers of high impact polystyrene (deca- and octa), flame retardant coated textiles and upholstery (deca-) and producers of ABS polymers (octa-). Presently, however, it is impossible to determine what the impact of these controls will be as this will depend on the nature of the progressive reduction target which has yet to be established. Chlorfenvinphos Chlorfenvinphos is an insecticide that is a colourless liquid with a mild odour. Commercial preparations commonly sold in stores were usually 90% chlorfenvinphos. Most of the chlorfenvinphos used was in liquid form. Chlorfenvinphos was widely used to control household pests such as flies, fleas, and mice. The chemical is manufactured and does not occur naturally in the environment. Chlorfenvinphos enters the environment from runoff after rainfall and leaching from hazardous waste sites. It may leach into soil and underground water, found in surface waters from rain. Chlorfenvinphos may move from soil to the air by evaporation. It does not appear to accumulate in plants, fish, or freshwater animals. The most common way to be exposed is by eating imported agricultural products contaminated with it. Another way to be exposed is by using pharmaceutical products that contain lanolin, a natural grease from sheeps wool (chlorfenvinphos is often used to control flies in animal buildings and can contaminate sheeps wool). The major effect of chlorfenvinphos is on the nervous system. Ingesting large doses may cause nausea and vomiting, abdominal cramps, diarrhoea, difficulty in breathing, and fainting. Lower doses may cause headaches, dizziness, weakness, confusion, runny nose, and inability to see clearly. These symptoms may start within 30-60 minutes and reach their maximum effect after 6-8 hours.
37
Background
There is no evidence that long-term exposure to small amounts of chlorfenvinphos causes any harmful health effects in people. The Department of Health and Human Services (DHHS), the International Agency for Research on Cancer (IARC), and the EPA have not classified chlorfenvinphos for carcinogenicity. Dichloromethane (DCM) and Trichloromethane (chloroform) The conclusion of the European Commission (CEC, 2000) report on the socioeconomic impact of the identification of DCM and chloroform as a PHS would be extensive. However, as the two substances have been assigned PS status the impact will be much less, as any additional controls will focus on meeting a progressive reduction target. These risks posed by DCM and chloroform stem mainly from their uses (particularly for DCM). No comprehensive risk assessments are presently available, but results of industry's own investigations suggest there is no need for further concern. Should this result be confirmed then it is anticipated that there would be minimal, if any, benefits from additional controls. This result needs also to be seen in terms of the costs to producers, formulators and users of these substances. In the main for DCM substitutes are available and use could be reduced with limited additional costs in many circumstances. The situation is somewhat different for chloroform as according to industry there is currently no substitute technology available for the main application of chloroform, the production of HCFC22. However, it is likely that the main impacts of reduced use would be on the producers, through reduced demand. DCM and chloroform production is intimately linked and further controls could potentially lead to a rationalisation of the industry. The industry is presently geared towards substantial export production resulting in a large excess capacity in Europe. Further controls could potentially mean a shift in this activity overseas. As the different activities will pose widely different potential risks to the aquatic environment, any reduction measures need to be tailored to the risks of the individual activity. 1,2-Dichloroethane (EDC) EDC is an important basic chemical most of which is used in PVC production. Limited data on UK production and use are available, although it is known that production and use takes place at several sites. There is at present no comprehensive risk assessment available, although a risk evaluation has been undertaken by industry, which indicates no concern with present production and use of the substance. If the results of the industry risk assessment are confirmed this would indicate limited additional benefits from controls. Given the potentially large socio-economic impact, any additional controls should therefore take into account the results of the risk assessment. Fluoranthene (PAH) See section on Polyaromatic Hydrocarbons. Nickel and compounds Nickel is a relatively abundant natural material that has been used widely since its discovery in a very large number of applications. Most importantly nickel in conjunction with other metals gives the resulting alloys some very commercially appealing properties (strength, toughness, corrosion resistance). As a result there
38
Background
are an enormous number of products in which nickel is a component (c.300,000). As a naturally occurring substance emissions of nickel occur as a result of natural processes. In addition there are unintentional releases of nickel because it is a contaminant of other products (e.g. fossil fuels). Concern over nickel has arisen from a number of sources and culminated in the controls on nickel in jewellery because of health concerns. A full risk assessment is currently underway and although the results of this are not yet available it is likely to conclude that there is a large variation in the risk associated with different nickel compounds and their uses - suggesting a targeted approach to risk reduction will be most effective. Controls are likely to involve a tightening of BAT (for example in production) together with substitution where this is possible. The value of downstream product sales (stainless steel etc.) runs into the billions. This production may relocate as a result of stricter controls. There are possibilities for substitution of downstream nickel containing products which could arise either as a result of marketing and use controls or increases in the costs to cover additional abatement requirements. However, the substitution possibilities will be severely limited in a number of applications (especially safety critical applications such as in aerospace).
1.8 - Physico-chemical properties of the identified substances

Tables 5a, 5b and 5c summarise the main physico-chemical properties of organic priority substances, inorganic priority substances and other water contaminants.
39
Background
Table 5a. Physicochemical Properties of Organic Priority Pollutants [1- 9]
Physico-chemical properties Substance (CAS N) Formula Molecular weight (g/mol) Solubility Volatility (mg/L) (mmHg) 20 25 C 20 25 C Henry's Constant ( Atm.m3 / mol) 20 25 C
Log P / Kow
Toxicity
Labile
PESTICIDES
Atrazine (1912-24-9) Simazine (122-34-9) Alachlor (15972-60-8) Chlorfenvinphos (470-90-6) Chlorpyrifos (-ethyl, -methyl) (2921-88-2) -HCH (Lindane) (58-89-9) Isoproturon (34123-59-6) DDT (50-29-3) Aldrin (309-00-2) Endrin (72-20-8) Isodrin (465-73-6) Dieldrin (60-57-1) C8H14ClN5 215.69 C7H12ClN5 201.66 C14H20ClNO3 269.8 C12H14Cl3O4P 359.6 C9H11Cl3NO3PS 350.59 C6H6Cl6 290.83 C12H18N2O 206.3 C14H9Cl5 354.49 C12H8C6 364.91 C12H8Cl6O 380.90 C12H8Cl6 364.91 C12H8Cl6O 2.61 2.18 2.6-3.5 3.81 4.96 3.72 2.5 6.91 6.50 5.34 6.82 5.4 34.7 5 240 145 1.12 7.3 72 0.025 0.017 0.25 0.017 0.195 3.04 x 10
-7
B,ED B, ED C,M N, B N B, N B B N, B N, B N, C, E
Y Y Y n/a Y Y ND Y
2.36 x 10-9 9.42 x 10-10 8.32 x 10-9 2.89 x 10-8 2.93 x 10-6 5.14 x 10-6 1.12 x 10-10 8.32 x 10-6 4.4 x 10-5
2.21 x 10-8 2.2 x 10-5 1.7 x 10

-7
1.87 x 10-5 4.2 x 10

-6
2.47 x 10
-8
1.6 x 10-7 1.2 x 10

-4
2.0 x 10-7 7.77 5.89 x 10

-6
6.36 x 10 0.091
-6
N, B
1.0 x 10-5
40
Background
380.91 Trifluralin (1582-09-8) C13H16F3N3O4 335.28 4.14 0.6 1.0 x 10

-4
E, B
Nd
0.002
POLYAROMATIC HYDROCARBONS (PAHs)

Benzo(a)pyrene (50-32-8) Benzo(b)fluoranthene (205-99-2) Benzo(g,h,i)perylene (191-24-2) Benzo(k)fluoranthene (205-99-2) Indeno(1,2,3-cd)-pyrene (193-39-5) Naphthalene (91-20-3) Anthracene (120-12-7) C20H12 252.32 C20H12 252.3 C22H12 276.34 C20H12 252.3 C22H12 276.34 C10H8 128.19 C14H10 178.2 6.13 6.04 6.5 6.84 6.60 3.29 4.45 3.8x10
-3
5.5 x 10-9 5.0 x 10-7 1.03 x 10-10

-11 9.88 x 10 to -7 5.32 x 10
M, C, E B B B B O B
Y Y Y Y Y Y Y
4.57 x 10-7 6.57 x 10-7 3.31 x 10-7 6.81 x 10

-7
0.0012 2.6 x 10 7.6 x 10 0.062 31.7 0.0434

-4
-4
9.88 x 10 8.5 x 10 2.7 x 10
-11
2.86 x 10-7 4.8 x 10-4 4.97 x 10-5
-2
-6
SEMI-VOLATILE AND VOLATILE ORGANIC CHEMICALS (SVOCs)

Benzene (71-43-2) Hexachlorobenzene (HCB) (118-74-1) Pentachlorophenol (87-86-5) 2,4,6-Trichlorophenol (88-06-2) 2,4,5-Trichlorophenol (95-95-4) C6H6 78.11 C6Cl6 284.76 C6HCl5O 266.35 C6H3Cl3O 197.46 C6H3Cl3O 197.46 2.13 5.73 5.10 3.69 3.72 1830 0.0062 14 800 1200 76.2 1.1 x 10-5 1.1 x 10 0.008 0.0075
-4
C, N, E B B B B
Y Y Y Y Y
5.51 x 10 0.0017
-3
2.45 x 10-8 2.6 x 10

-6
1.62 x 10
-6
1,2-Dichloroethane (107-06-2) Dichloromethane (75-09-2) Pentachlorobenzene (608-93-5)
C2H4Cl2 98.96 CH2Cl2 84.93 C6HCl5
1.48 1.3 5.21
8.69 x 10-3 13200 0.831
79.1 354 1.01 x 10-3
N,B N,B B
Y Highly flammable Y ND
1.18 x 10-3 3.25 x 10

-3
7.03 x 10-4
41
Background
250.34 1,2,3-trichlorobenzene (87-61-6) 1,2,4-trichlorobenzene (120-82-1) 1,3,5-trichlorobenzene (108-70-3) Trichloromethane (67-66-3) Tetrachloroethene (127-18-4) Tetrachloromethane (56-23-5) Trichloroethene (79-01-6) C6H3Cl3 181.45 C6H3Cl3 181.45 C6H3Cl3 181.45 CHCl3 119.40 C2Cl4 165.83 CCl4 153.82 C2HCl3 131.4 4.05 4.02 4.19 1.93 3.4 2.83 2.42 15 49 6.0 8000 150 793 1070 0.21 0.46 0.24 161.9 18.47 115 69 E, C N, B N, C, E B, N Not very toxic Y Y Y Y But light sensitive Y Y Y 1.25 x 10 1.42 x 10
-3
-3
1.89 x 10 6 x 10
-4
-3
1.77 x 10-2 2.94 x 10-2 9.85 x 10

-3
POLYCHLORINATED BIPHENYLS (PCBs): mixture of up to 209 congeners

PCB 77 (3,3',4,4'-TCB) (32598-13-3) PCB 81 (3,4,4',5-TCB) (70362-50-4) PCB 126 (3,3',4,4'5-PeCB) (57465-28-8) PCB 169 (3,3',4,4',5,5'-HxCB) (32774-16-6) PCB 105 (2,3,3',4,4'-PeCB) (32598-14-4) PCB 114 (2,3,4,4',5-PeCB) (74472-37-0) PCB 118 (2,3',4,4',5-PeCB) (31508-00-6) PCB 123 (2',3,4,4',5-PeCB) (65510-44-3) PCB 156 (2,3,3',4,4',5-HxCB) (38380-08-4) PCB 157 (2,3,3',4,4',5'-HxCB) (69782-90-7) PCB 167 (2,3,3',4,4',5,5'-HxCB) (52663-72-6) C12H6Cl4 291.99 C12H6Cl4 291.99 C12H5Cl5 326.44 C12H4Cl6 360.88 C12H5Cl5 326.44 C12H5Cl5 326.44 C12H5Cl5 326.44 C12H5Cl5 326.44 C12H4Cl6 360.88 C12H4Cl6 360.88 C12H4Cl6 360.88 6.63 6.34 6.98 7.41 6.79 6.98 7.12 6.98 7.62 7.62 7.62 0.000569 n/a n/a 0.00051 0.0034 0.016 0.0134 n/a 0.00533 n/a 0.00223 1.64 x 10 n/a n/a 5.81 x 10-7 6.53 x 10 n/a 8.97 x 10-6 n/a 1.61 x 10-6 n/a 5.81 x 10
-7 -6 -5
C, ED, N
No
9.4 x 10-6 n/a n/a 6.85 x 10-5 8.25 x 10-4 n/a 2.88 x 10-4 n/a 1.43 x 10-4 n/a 6.85 x 10
-5
42
Background
PCB 189 (2,3,3',4,4',5,5'-HxCB) (39635-31-9)
C12H3Cl7 395.33
8.27
0.000753
n/a
n/a
DIOXINS AND FURANS

PCDD/Fs 2378-TCDD (1746-01-6) 123478-HxCDD (39227-28-6) 123789-HxCDD (19408-74-3) HxCDD 1234678-HpCDD (35822-46-9) HpCDD OCDD (3268-87-9) 2378-TCDF (51207-31-9) 23478-PeCDF (57117-31-4) 203 - 460 C12H4Cl4O2 321.98 C12H2Cl6O2 390.87 C12H2Cl6O2 390.87 390.87 C12HCl7O2 425.20 425.20 C12Cl8O2 459.76 C12H4Cl4O 305.98 C12H3Cl5O 340.40 6.8 - 8.2 6.8 7.8 8.21 8.21 7.92 7.78 8.2 6.53 6.79 2.0 x 10-6 4.4 x 10
-6
1.5 x 10 to -13 8.25 x 10 1.5 x 10-9 3.83 x 10-11 4.88 x 10-11 4.4 x 10-11 2.01 x 10-8 5.65 x 10-10 8.25 x 10-13 1.53 x 10-6 3.46 x 10-6
-9
C, ED C, ED C, ED C, ED C, ED C, ED C, ED C, ED C, ED C, ED
no no no no no no no no no no
0.86 x 10 to -6 6.5 x 10 5 x 10-5 3.95 x 10-6 1.94 x 10-6 5.7 x 10-6 6.28 x 10-6 2.18 x 10-5 6.47 x 10-6 1.54 x 10-5 1.14 x 10-5
-4
2.65 x 10 4 x 10-6
-5
1.35 x 10-6 1.41 x 10-6 4 x 10-7 at 6.94 x 10

-4
8.74 x 10-4
PHTALATE
Di(2-ethylhexyl)phthalate (DEHP) (117-81-7) C24H38O4 390.54 7.5 0.023 to 0.34 1.42 x 10-7 B, E Y 2.7 x 10-7
FLAME RETARDANTS (BROMINATED DIPHENYLETHERS)

Bis(pentabromophenyl)ether (1163-19-5) Diphenyl ether, octabromo derivate (32536-52-0) Diphenyl ether, pentabromo derivate (32534-81-9) C12Br10O 959.17 C12H2Br8O 802.00 C12H5Br5O 565.00 >5 5.5-8.9 7.24-7.37 0.02 0.03 < 0.01 9 x 10
-7
< 5.71 x 10-11 5.71 x 10

-12
B, ED C, ED C, ED
Y Y Y
1.82 x 10-6 n/a n/a
5.32 x 10-4
ALKYLPHENOLS
Nonylphenols (mixed isomers) (25154-52-3) C15H24O 220.4 4.48 5.43 1.57 x 10
-4
ED
n/a
-6 8.28 x 10 to -5 1.29 x 10
43
Background
Octylphenols (mixed isomers) (1806-26-4)
C14H22O 206.00
4.12
12.6
n/a
O, ED
n/a
TRIBUTYLTIN COMPOUNDS
Tributyltin chloride (TBT Cl) (683-18-1) Tributyltin bromide (TBTBr) (1461-23-0) Tributyltin chlorate (TBTClO4) Tributyltin nitrate (TBTNO3) Tributyltin hydroxide (TBTOH) (1067-97-6) bis(tri-n-butyltin)oxide (TBTO) (56-35-9) (C4H9)2SnCl2 325.49 [(CH3CH2)3]3SnBr 369.9 389.49 352.01 307 C24H54OSn2 596 4.76 5.07 4.18 3.49 4.09 3.2 70 21.2 n/a n/a n/a 0.7 - 7 at pH 5-7 n/a n/a n/a ED n/a n/a 6.4 x 10
-7
n/a n/a n/a n/a n/a Y n/a
*Keys: C = carcinogenic; ED = endocrine disruptor; M = mutagen; B = possible human carcinogen; N = neurotoxic; K = kidney disorders; E = embryotoxic; O = ocular disorder; T= teratogen n/a = not available at our knowledge
44
Background
Table 5b. Physicochemical Properties of Inorganic Priority Pollutants [1 9]
Physico-chemical properties Substance (CAS N) Formula Molecular weight (g/mol) Solubility Volatility Log P / (mg/L) (mmHg) Kow 20 25 C 20 25 C Henry's Constant ( Atm.m3 / mol) 20 25 C
Toxicity
Labile
CADMIUM and its compounds

Elemental cadmium Cadmium oxide (1306-19-0) Cadmium chloride (10108-64-2) Cadmium sulfide (1306-23-6) 112.4 CdO 128.40 CdCl2 183.30 CdS 144.50 n/a n/a n/a n/a insoluble 5 1.4 x 106 1.3 4.14 x 10-9 n/a n/a n/a K, B B, K, poison B, T, E, very toxic n/a Y Y n/a 0.0308 n/a n/a n/a
LEAD and its compounds

Elemental lead Lead acetate (301-04-2) Lead carbonate (598-63-0) Lead oxide (1317-36-8) Lead dioxide (1309-60-0) Lead oxide (1314-41-6) 207.20 Pb(C2H3O2)2 325.29 PbCO3 267.20 PbO 223.21 PbO2 239.20 Pb3O4 685.60 n/a n/a n/a n/a n/a n/a insoluble 5 4.43 x 10 at 20C very low solubility very low solubility insoluble insoluble n/a n/a n/a n/a n/a n/a
N
B O, Cumulative poison B, M B, M E Chronic poison Y Y Y Y Y
n/a n/a n/a n/a n/a n/a
45
Background
Lead sulfide (1314-87-0) Lead sulfate (7446-14-2)
PbS 239.26 PbSO4 303.26
n/a n/a
insoluble very low solubility
n/a n/a
n/a K, O, E, Cumulative poison
Y Y
n/a n/a
MERCURY and its compounds

Elemental mercury Inorganic mercury (7487-94-7) Methylmercury (2269-92-6) 200.6 HgCl2 271.52 CH3HgCl 251.10 0.62 0.5 2.5 0.0567 69000 6000 1.3 x 10-3 6.84 x 10-5 0.014 N N N, B Y but light sensitive n/a 7.2 x 10-3 3.6 x 10
-10
6.6 x 10-7
NICKEL and its compounds

Elemental nickel Nickel oxide (1313-99-1) Nickel hydroxide (12054-48-7) Nickel carbonate (3333-67-3) Nickel chloride hexahydrated (7791-20-0) Nickel nitrate hexahydrated (13478-00-7) Nickel sulphate hexahydrated (10101-97-0) 58.69 NiO 74.69 Ni(OH)2 92.70 NiCO3 118.72 NiCl2,6H2O 237.69 Ni(NO3)2,6H2O 290.79 NiSO4,6H2O 262.84 n/a n/a n/a n/a n/a n/a n/a 4.22 x 10-5 1 100 100 2.54 x 106 2.38 x 106 6.5 x 105 4.24 x 10-9 n/a n/a n/a n/a n/a n/a B B by inhalation Y Y Y Y Y Y 0.0245 n/a n/a n/a n/a n/a n/a
*Keys: C = carcinogenic; ED = endocrine disruptor; M = mutagen; B = possible human carcinogen; N = neurotoxic; K = kidney disorders; E = embryotoxic; O = ocular disorder; T= teratogen n/a = not available at our knowledge
46
Background
Table 5c. Physicochemical Properties of Other Water Contaminants [1 9]
Physico-chemical properties Substance (CAS N) Formula Solubility Molecular Log P Volatility (mg/L) weight / Kow (mmHg) (20 25 C) (g/mol) Henry's Constant ( Atm.m3 / mol)
Toxicity
Labile
PAHs
Acenaphthene (83-32-9) Acenaphthylene (208-96-8) Benzo(a) Anthracene (56-55-3) Chrysene (218-01-9) Dibenzo(a,h)anthracene (53-70-3) Fluoranthene (206-44-0) Fluorene (86-73-7) Phenanthrene (85-01-8) Pyrene (129-00-0) C12H10 154.21 C12H8 152.20 C18H12 228.29 C18H12 228.28 C22H14 278.33 C16H10 202.26 C13H10 166.21 C14H10 178.22 C16H10 202.26 3.92 3.94 5.76 5.81 6.75 5.16 4.18 4.46 4.88 3.9 16.1 0.0094 0.002 0.00249 0.26 1.89 1.15 0.135 7.8 x 10 2.1 x 10
-9
0.0037 0.029
None Harmful if swallowed C, M n/a n/a B, Harmful if swallowed O, O n/a
Y Y Incompatible with oxidizing agents Y n/a n/a Y Y Y Y but light-sensitive
1.55 x 10-4 1.48 x 10-3 3.35 x 10

-6
9.46 x 10-5 1.47 x 10-8 1.61 x 10 1.98 2.3 x 10-5 1.1 x 10

-5 -5
-11
8.133 x 10 0.0032 6.8 x 10
-6
-4
4.25 x 10
-6
VOLATILE ORGANICS
Acrolein (107-02-8) Acrylonitrile (107-13-1) C3H4O 56.064 C3H3N 53.0634 -0.1 0.209 212500 7450 265 110 M, O C, M, O Y but very readily polymerizes NO 1.22 x 10 1.1 x 10
-4
-4
47
Background
Bromodichloromethane (75-27-4) Bromoform (75-25-2) Bromomethane (74-83-9) Chlorobenzene (108-90-7) Chloroethane (75-00-3) 2-Chloroethyl vinyl ether (110-75-8) Chloromethane (74-87-3) Dibromochloromethane (124-48-1) 1,2-Dichlorobenzene (95-50-1) 1,3-Dichlorobenzene (541-73-1) 1,4-Dichlorobenzene (106-46-7) Dichlorodifluoromethane (75-71-8) 1,1-Dichloroethane (75-34-3) 1,2-Dichloroethane (107-06-2)
CHBrCl2 163.8289 CHBr3 252.7309 CH3Br 94.9387 C6H5Cl 112.5585 C2H5Cl 64.5145 C4H7ClO 106.5517 CH3Cl 50.4877 CHBr2Cl 208.2799 C6H4Cl2 147.0036 C6H4Cl2 147.0036 C6H4Cl2 147.0036 CCl2F2 120.9138 C2H4Cl2 98.9596 C2H4Cl2 98.9596 C2H2Cl2 96.9438 C2H2Cl2 96.9438 C2H2Cl2 96.9438 C3H6Cl2 112.9864 C3H4Cl2
1.61 1.79 1.176 2.637 1.577 1.88 1.087 1.7 3.28 3.28 3.28 1.815 1.758 1.831
4500 3200 15200 502 20000 5023 7250 5250 150 110 73.8 280 5500 8700
58.4 5.6 1635 12.1 1200 26.01 3765 15 1.36 2.3 1.06 4800 228 81.3 O C, O fatal by ingestion, inhalation B n/a n/a M, C, T n/a O O B ND O C, M, E
n/a Y but light-sensitive Y Y Incompatible with oxidizing agents Y n/a Y Highly flammable n/a Y but light-sensitive Y Y Y Y Highly flammable. Y Highly flammable Y Rapidly absorbs oxygen from the air and forms explosive peroxides. Light and water promote selfpolymerisation
1.6 x 10
-3
5.35 x 10-4 1.42 x 10 3.7 x 10

-2
-3
8.8 x 10-3 6.25 x 10-4 4.52 x 10

-2
7.83 x 10-4 1.9 x 10-3 1.8 x 10

-3
2.43 x 10 2.6
-3
5.62 x 10-3 9.79 x 10

-4
1,1-Dichloroethene (75-35-4)
2.12
2400
591
C, T, E
2.61 x 10
-2
cis-1,2-Dichloroethene (156-59-2) trans-1,2-Dichloroethene (156-60-5) 1,2-Dichloropropane (78-87-5) cis-1,3-Dichloropropene (10061-01-5)
1.86 2.07 2.25 1.53
4930 6300 2800 2700
175 352 50 37
n/a n/a n/a n/a N Highly flammable n/a n/a
4.08 x 10-3 9.38 x 10-3 2.8 x 10-3
48
Background
110.9706 trans-1,3-Dichloropropene (10061-02-6) Ethylbenzene (100-41-4) 1,1,2,2-Tetrachloroethane (79-34-5) Toluene (108-88-3) 1,1,1-Trichloroethane (71-55-6) 1,1,2-Trichloroethane (79-00-5) Trichlorofluoromethane (75-69-4) Vinyl chloride (75-01-4) Xylenes (1330-20-7) C3H4Cl2 110.9706 C8H10 106.167 C2H2Cl4 167.8498 C7H8 92.1402 C2H3Cl3 133.4047 C2H3Cl3 133.4047 CCl3F 137.3684 C2H3Cl 62.4987 C24H30 318.501 1.53 3.03 2.19 2.54 2.679 2.01 2.128 1.623 3.087 2800 169 2970 530 1330 4420 1100 2760 198 30 9.6 5.17 28.2 124 25.2 687 2800 8.06 O O, T M, C, E, O cause death within 12 hours of exposure T M, E C NOTHING C ND Y Y Incompatible with oxidizing agents Y Y Highly flammable Y Y Y Y Highly flammable Y Highly flammable 7.88 x 10-3 3.45 x 10 6.64 x 10
-4
-3 -2
1.72 x 10 9.13 x 10 0.13
-4
2.7 x 10-2 6.04 x 10

-3
PESTICIDES/PCB CONGENERS
Aroclor 1016 (12674-11-2) Polychlorinated biphenyls Aroclor 1221 (11104-28-2) Polychlorinated biphenyl Aroclor 1232 (11141-16-5) Aroclor 1242 (53469-21-9) Polychlorinated biphenyl Aroclor 1248 (12672-29-6) Polychlorinated biphenyl Aroclor 1254 (11097-69-1) Polychlorinated biphenyl Aroclor 1260 (11096-82-5) Polychlorinated biphenyl Alpha-HCH (319-84-6) beta-HCH (319-85-7) C24H13Cl7 549.54 C12H9Cl 188.66 C12H9Cl 188.66 C12H6Cl4 291.99 C24H11Cl9 618.43 C12H5Cl5 326.44 C12H3Cl7 395.33 C6H6Cl6 290.8314 C6H6Cl6 290.8314 5.69 4.65 4.40 6.34 6.20 6.50 7.55 3.80 3.78 0.42 15 1.45 0.277 0.1 0.043 0.0144 2 0.24 7.71 x 10-5 4.05 x 10
-5
4 x 10
-4
n/a n/a n/a n/a n/a n/a n/a B, B, ED
n/a n/a n/a n/a n/a n/a n/a n/a n/a
2.9 x 10-4 3.5 x 10-3 n/a 5.2 x 10-4 n/a 2 x 10-3 4.6 x 10-3 1.06 x 10-5 7.43 x 10-7
6.7 x 10
-3
4.6 x 10-3 4.06 x 10

-4
4.26 x 10-5 4.9 x 10

-7
49
Background
delta-HCH (319-86-8) 4,4'-DDD (72-54-8) 4,4'-DDE (72-55-9) Endosulfan sulphate (1031-07-8) Endrin aldehyde (7421-93-4) Endosulfan-I (959-98-8) Endosulfan-II (33213-65-9) Heptachlor (76-44-8) Heptachlor epoxide (1024-57-3) Methoxychlor (72-43-5) Toxaphene (8001-35-2)
C6H6Cl6 290.8314 C14H10Cl4 320.045 C14H8Cl4 318.0292 C9H6Cl6O4S 422.922 C12H10Cl6O 382.9284 C9H6Cl6O3S 406.9226 C9H6Cl6O3S 406.9226 C10H5Cl7 373.3205 C10H5Cl7O 389.3199 C16H15Cl3O2 345.6523 C10H9Cl9 448.26
4.14 6.02 6.51 3.66 4.80 3.83 3.83 6.10 4.98 5.08 5.90
10 0.09 0.04 0.48 0.024 0.51 0.45 0.18 0.2 0.1 0.55
2.87 x 10
-7
B n/a n/a No data available n/a n/a n/a n/a n/a n/a C, T
n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a Y Heat and light sensitive
1.4 x 10-5 4 x 10-6 2.1 x 10

-5
8.66 x 10-7 5.66 x 10

-6
1.617 x 10
-7
1.459 x 10-5 2.75 x 10

-6
1.84 x 10-6 3.26 x 10-4 4.34 x 10

-6
1.09 x 10-3 9.5 x 10-6 1.58 x 10-5 6 x 10-6
1.23 x 10-6 4.19 x 10-6
SEMI VOLATILE ORGANICS

2-Chlorophenol (95-57-8) 4-Chloro-3-methyl phenol (59-50-7) 2,4-Dichlorophenol (120-83-2) 2,4-Dimethylphenol (105-67-9) 2,4-Dinitrophenol (51-28-5) 4,6-Dinitro-o-cresol (534-52-1) 2-Nitrophenol (88-75-5) 4-Nitrophenol (100-02-7) C6H5C1O 128.56 C7H7ClO 142.58 C6H4Cl2O 163.00 C8H10O 122.16 C6H4N2O5 184.11 C7H6N2O5 198.13 C6H5NO3 139.11 C6H5NO3 139.11 2.15 3.10 3.06 2.30 1.67 2.12 1.79 1.91 1.13 104 3830 4500 7870 2790 198 2500 1.16 104 1.42 0.0097 0.0715 0.126 1.14 x 10 2.87 x 10 0.05 1.912 x 10-5
-4
K Inhalation may be fatal, O, Harmful by inhalation, ingestion n/a n/a Toxic by inhalation and ingestion n/a O M
Y Y n/a n/a Y n/a Y Y
3.91 x 10 4 x 10
-7
-4
3.16 x 10-6 2 x 10-6 4.43 x 10-7 4.3 x 10-7 3.5 x 10

-6
-5
50
Background
Phenol (108-95-2) Benzidine (92-87-5) 4-Bromophenyl phenyl ether (101-55-3) Butyl benzyl phthalate (85-68-7) 2-Chloro naphthalene (91-58-7) 4-Chloroaniline (106-47-8) Bis (2-Chloroethoxy)methane (111-91-1) 1,2-Diphenylhydrazine (122-66-7) 2,4-Dinitrotoluene (121-14-2) 2,6-Dinitrotoluene (606-20-2) 3,3'-Dichlorobenzidine (91-94-1) Di-n-butyl phthalate (84-74-2) Di-n-octyl phthalate (117-84-0) Diethyl phthalate (84-66-2) Dimethyl phthalate (131-11-3) Hexachlorobutadiene (87-68-3) Hexachlorocyclopentadiene (77-47-4) Hexachloroethane (67-72-1) Isophorone (78-59-1) Nitrobenzene (98-95-3) n-Nitrosodimethylamine (62-75-9)
C6H6O 94.11 C12H12N2 184.23 C12H9BrO 249.11 C19H20O4 312.39 C10H7C1 162.61 C6H6ClN 127.58 C5H10Cl2O2 173.05 C12H12N2 184.24 C7H6N2O4 182.14 C7H6N2O4 182.14 C12H10C12N2 253.13 C16H22O4 278.34 C24H38O4 390.56 C12H14O4 222 C10H10O4 194.19 C4Cl6 260.76 C5Cl6 272.77 C2Cl6 236.74 C9H14O 138.2 C6H5NO2 123.11 C2H6N2O
1.46 1.34 4.94 4.73 3.90 1.83 1.30 2.94 1.98 2.10 3.51 4.50 8.10 2.42 1.60 4.78 5.04 4.14 1.70 1.85 -0.57
8.28 10 322 1.45 2.69 11.7 3900 7800 221 270 182 3.1 11.2 0.02 1080 4000 3.2 1.8 50 12000 2090
0.463 8.36 x 10-8 5.85 x 10 1.2 x 10 0.017 0.0235

-4
Highly toxic by inhalation C n/a None n/a C n/a
Y Y Y Y n/a Y n/a Y Y Y but shock sensitive Y but light sensitive Y Y Y Y Y Y but light-sensitive Y Y Y Y
3.97 x 10-7 3.9 x 10-11
-5
1.26 x 10-6 3.1 x 10-4
2.6 x 10-5 1.74 x 10-4 5.7 x 10

-4
C C, O C, N Highly toxic B None O None T None O, Toxic if inhaled None C, O C, E Highly toxic C, T, E
9.26 x 10-8 7.47 x 10 4 x 10-9 9.38 x 10-10 6.68 x 10

-5 -7
2.2 x 10-7 4.25 x 10 n/a 1.65 x 10-3 9.12 x 10 0.177 0.0732 0.472 0.41 0.244 5.365
-3 -5
4.5 x 10-7 5.78 x 10-7 8.15 x 10

-3
2.7 x 10-2 3.89 x 10

-3
6.64 x 10-6 2.4 x 10-5
1 x 106
51
Background
74.08 N-Nitroso diphenylamine (86-30-6) C12H10N2O 198.23 3.13 35 0.0988 M, C, O
but light-sensitive N 5 x 10
-6
*Keys: C = carcinogenic; ED = endocrine disruptor; M = mutagen; B = possible human carcinogen; N = neurotoxic; K = kidney disorders; E = embryotoxic; O = ocular disorder; T= teratogenic n/a = not available to our knowledge
52
Monitoring issues
2. Monitoring issues
2.1 - Physico-chemical assessment tools

Table 6 summarises the main chemical methods available for on site and/or on line analysis for the measurement of water quality global parameters. The table indicates in particular the different types of monitoring embodied within the WFD including frequency of sampling and some commercial data. The estimated price/cost of the various devices has been expressed as a range of categories from A to G as described below: A = 0 1000 B = 1000 5000 C = 5000 10000 D = 10000 20000 E = 20000 30000 F = 30000 40000 G = 40000 50000
53
Monitoring issues
Table 6. Currently available methods for physico-chemical and nutrient measurements
Calibration Range
Maintenance Frequency (Days)

7 30 7
Precision of the measurement
Parameter
Method
Type of water
Sampling time (min)
Costs
Model
Company / institution
Response
Cycle duration
AMMONIUM
Membranes: Specific Electrode Membranes: Specific Electrode Membranes: Specific Electrode Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Membranes: Specific Electrode Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric SE, R, IE All All All All All All All SE, R, IE All D D D D D D 15 10 to 15 6-7 6-7 15 0 10 15 0 5-10 15 15 15 E D D AMMONIA ISE ABB Repeatability: MONITOR 8232 INSTRUMENTATION 5% FPA 200 FPA 300 FPA 800 SENTINEL ISE SENTINEL COLORIMETRE MICROMAC E MICROMAC C MICROMAC Hp Poly Nat C POLYMAC ANAEL ANAEL ANAEL ANAEL ANAEL ANHYDRE ANHYDRE ANHYDRE ANHYDRE 2% some g/L to 100 mg/L 0.5 Mol 0.5 Mol 0.5 Mol 30 2-5 % 2-5 % 2% 30 0 0.05 to 1000 mg/L - NNH4
54
Maintenance duration (min)
Measurement method*
Legislation / Standards
Monitoring issues
Membranes: Specific Electrode Membranes: Specific Electrode Optical: Photometry Optical: Photometry: UV Absorption Optical: Spectrophotometry 194730 nm Membranes: specific electrodes Titrimetry Optical: Photometry: UV Spectrometry Optical: Photometry (at 660 mm, ref at 880 mm) Membranes: Specific Electrode
IE
Ammonia Controller
APOLLO INSTRUMENTS AQUALYSE AQUAMS AWA INSTRUMENTS BRAN + LUEBBE FRANCE BRAN + LUEBBE FRANCE BRAN + LUEBBE FRANCE DATALINK ENDRESS HAUSER
All SE, R, IE All SE, R, IE SE All D SE, R, IE D 0 0 D D D 0 5 12 0.17 1 12 6 6 0.17 0 D D ISO D D E
MEMODAT 9 ACA ANALYSER SERIES 1000 DIAMON MONITOR 90 S Ionometre MONITOR 90S TITROMETRE AM 200 STAMOLYS CA71 AM
Detection limit: 10 g/L Accuracy: +/0.3 g/L +/- 10 % or +/- 0.14 to 14000 2 mg/L N mg/L N 0-1 / 2 / 5 / <2% of the 10 / 20 / 50 / range 100mg/L +/- 0.1 mg/L < 3% of the range < 2 % of the range < 1% of the range detection limit: 0,1mg/L 2% +/- 5 % / Minimal detected value: 1 mg/L 5 % of measured value or 2mg/L N 2 % of measured value 2% / Detection limit: 0.003 mg/L 2% of measured value Detection limit: 0.2 mg/L 0-100 mg/L 0-4 to 0-25 mg/L N 0-2.5 mg/L 0-2000 mg/L 0-100 g/L to 0-40 mg/L 0-10 and 0500 mg/L 0.02-5 / 0.215 / 0.2-100 mg/L NH4-N 010/100/500/1 000 mg/L 0.14 to 14 000 mg/L N 0.01-17000 mg/L 0 - 12610 mg N-NH4/L 0 30 0 60
30
All
ES 9010
ENVIRONNEMENT SA
Membranes: Specific Electrode Membranes: Specific Electrodes: Ion specific electrode Optical: Photometry: Visible: Colorimetric Titrimetry Membranes: Specific Electrode
SE, R, IE
TROLL 9000
EQUIPEMENTS SCIENTIFIQUES SA
All
ADI 2018
BRASTEN APPLIKON
SE
15
ADI 2019
BRASTEN APPLIKON
SE, IE IE
ADI 2016 MINICAL II
BRASTEN APPLIKON GFG
0-10/0-100/01000 mg/L
55
Monitoring issues
Ion-selective electrodes
Ground and fresh waters
Intervals <1min : 15, 30, In situ and 60, 120 flowmin through 22-86d 5 3 3-5
DataSonde 4a and MiniSonde 4a
Hydrolab, PO Box 389, Greater of +/FieldFieldLoveland, CO 805390 to 100 mg/L 5% of reading servicea servicea 0389 N or +/- 2 mg/L ble ble Hydrolab STIP ISCO STIP ISCO STIP ISCO STIP ISCO METROHM METROHM OTT < 50 ng/L +/-5 % or +/2mg/L N 0-100 mg/L 0-100 mg/L NH4-N 0.01 mg/L 0.01 to 100 mg/L 0.3-10/3reproducibility: 300/10-1000 2% mg/L reproducibility 0.1-50 mg/L 4% N-NH4 Reproducibility 0.1-50 mg/L :3% N-NH4 reproducibility: 0.1-50 mg/L 4% N-NH4
Membranes: Specific Electrode Membranes: Specific Electrode Membranes: Specific Electrode Membranes: Specific Electrodes: Ionic specific electrode Ionic chromatography Ionic chromatography Membranes: Specific Electrode Membranes: Specific Electrode Membranes: Specific Electrodes: Gasselective Electrode Optical: Photometry: Visible: Colorimetry/Potentiometr y/ Nephelometry Colour/Titrimetry Optical: Photometry: Visible:Colorimetry/Titrim etry/ Potentiometry Optical: Chemiluminescence Optical: Chemiluminescence Membranes: Specific Electrode
SE SE SE, R SE All All R
GENION 1 GENION 3 PBS 1 SPECTRON PO4 - NH4 Compact Online Analyser IC 821 Online Analyser IC 811 DATAPROBE 4 A ACQUISITION LOGOSENS MINIPROBE 4a Acquisition Logosens ANALYSER 8810
OTT
SE, R, IE
POLYMETRON
SE, R, T
4 to 20
20
SERES 2000
SERES
Cycle 1 to 2% of the duration 4 to range 20 min
SE, R, T
4-20
20
SERES 1000
SERES
1 to 2% of the range 4% of the range +/-4 % of the range 10 % of measured value 0-1 to 0-200 mg/L 0-1 to 0-200 mg/L 0.1 to 1000 mg/L 7 0
All All SE
D D
0 3
4 0
G G
TOCN 4110 TN 4110 Sensor Ammonia - Fam Ammonia
SHIMADZU SHIMADZU SWAN
56
Monitoring issues
Membrane: Ion selective electrodes Membranes: specific electrodes
All
YSI 6000 series probes TRESCON/MOD ULE OA 110
YSI Hydrodata, Letchworth SG6 2HB UK YSIhydrodata WTW
SE
<3
10% of reading or 2 0 to 200 mg/L mg/L, -N whichever is greater 0.1-1000 3-5% mg/L
6 mth
ON-LINE BOD MICROBIAL BIOSENSOR, RESPIROMETRY

Waste Water Treatment Plants, Drinking water, Industrial estates water
BOD
3-7 sec
BOD-TOX
Biosensores SL
<3%
3-200mg/L
BOD
3-15
BIOX 1010 RODTOX2000 (KELMA)
Isco GmbH, GroUmstadt, University of Ghent / Kelma
3% reproducibility
BOD, toxicity
water
5 - 100000 mg/L 0 - 500 000mgBOD/l, 0 - 100 % TOXICITY
COD
Electrodes: electrochemical oxydation measurement (Pb oxyde) Electrodes: Zirconium probe Optical: Photometry: Photometry: UV Spectrometry Optical: Chemiluminescence (NO detection) Optical: Photometry: UV Absorption Optical: Spectrophotometry 194730 nm SE, IE 2 ELOX 100 ANAEL 5% 1-100 to 1100 000 mg/L COD
SE, IE
1-4
QUICK COD
ANAEL
1-500/20reproducibility 12000/4002% 150000 mg/L COD 0.05 - 10 000 mg/L 0-200 mg/L N 0-100/020000 mg/L COD < 3% of the range 0 0
30 s
0 ISO/TR 11905-2
SPECTROLYSE R SCAN TNb QUICK TON ANALYSER SERIES 1000 DIAMON
ANAEL
SE, R, IE
ANAEL
All
< 10 s
AWA INSTRUMENTS BRAN + LUEBBE FRANCE
SE, R, IE
12
12
57
Monitoring issues
Optical: Spectrophotometry multiwavelength Optical: Photometry: UV/Visible Spectrometry
SE, R, IE
OPTILIS
SE, R, IE
OPTILIS 201
E.F.S. LAC Instruments et systmes E.F.S. LAC Instruments et systmes
0-500 mg/L
30
0-1000 mg/L
90
Titrimetry Optical: Photometry: UV Spectroscopy (200-350 mm) Membranes: Specific Electrodes: Gas specific electrode Dissolved ozone PROBE Optical: Photometry: IR Catalytical oxydation Optical: Photometry: UV/Visible Spectroscopy 190-720 mm Optical: Photometry: Visible: Colorimetric (after microwave oxydation)
SE
ADI 2040 DCO
2% of the range / BRASTEN APPLIKON 0-3500 mg/L detection limit: 5 mg/L SECOMAM 10-350 / 1003500 mg/L reproducibility 10-1500/105% 100 000 mg/L 4-1000 / 40Reproductibilit 4000 / 100y4% 10000mg/L Reproducibility 10-200 mg/L :3% 3% of the range 0 0 0 0
SE
10-240
IXO 510
SE, IE
3-15
PHOENIX 1010
MARTEC
SE, IE
30 s
PHOENIX THERMCAT STIP-SCAN
MARTEC
SE
1 to 5
MARTEC
SE, R, IE
4 to 20
20
AFNOR 90-101
COD MICROWAVES
SERES
30-700 mg/L
CONDUCTIVITY
Electrodes: Induction electrode Electrodes: 2 electrodes IE PROBE SI 315 / TRANSMITTER C 3655 PROBE SI 301 / TRANSMITTER C 3645 PROBE SZ 312.4 / TRANSMITTER C 3645 PROBE ECS37 CONDUCTIMET RE HI 9033 (field) AQUACONTROL 2 mS/cm - 20 S/cm 0-2 mS/cm 0.2-200 mS/cm 0-200S/cm 02000mS/cm +/- 1% 0199.9mS/cm
IE, R, T
AQUACONTROL
Electrodes: 4 electrodes Electrodes: Induction electrode Electrodes: 4 electrodes
All
AQUACONTROL
IE, R, T
AQUALYSE
All
HANNA Instruments
58
Monitoring issues
Electrodes: 2 electrodes
All Ground and fresh waters O Intervals : 15, 30, 60, 120 min 22-86d
PROBE SO 5 / TRANSMITTER LM 1000 DataSonde 4a MiniSonde 4a and Quanta PROBE ACS-X0I / TRANSMITTER ACM-X PROBE TB 454 / TRANSMITTER 440 PROBE 8398 / TRANSMITTER MONEC D 9125 PROBE TETRACON 325 / TRANSMITTER COND 315i (field) YSI 6000 series probes
HEYL Hydrolab, PO Box 389, Loveland, CO 805390389 Hydrolab KOBOLD
5-10000 S/cm Fieldservicea ble
Non corroding graphite electrodes
+/-1%
0 to 100 mS/cm
Electrodes: Induction electrode Electrodes: 2 electrodes Electrodes: Induction electrode
All
5S/cm 2000mS/cm 1-20000 S/cm 0.1S/cm 2S/cm 0.0 500mS/cm
All
PANAMETRICS
All
POLYMETRON
Electrodes: 4 electrodes
All
WTW
0,005
Electrodes
All
YSI Hydrodata, 0.5% of Letchworth SG6 2HB reading UK +0.001 mS/cm YSIhydrodata
0 to 100 mS/cm
DISSOLVED OXYGEN
Membranes: Polarography Membranes: Polarography Membranes: Specific Electrodes: Amperometric sensor with membrane (potentiostatic principle) Membranes: Polarography Optical SE, R PROBE SI 181 / TRANSMITTER OD 3645 PROBE CLARK / TRANSMITTER PRO Y AQUACONTROL 0-199.9% sat 0-99.99 mg/L 0-999.9% sat 0.035mg/L (20C) 20mg/L 0-19.9 mg/L 0-500M // 0-120% sat
SE, R
AQUALYSE
0,001
SE, R
PROBE COS 3 / ENDRESS HAUSER / TRANSMITTER AQUAMS COM121/151 OXYMETRE HI 9142 (field) OXYGEN OPTODE 3830 HANNA instruments NEREIDES
<0.5%
SE, R SE, R D
+/- 15% <8M // <5%
59
Monitoring issues
Ground and fresh waters Membrane: Clark cell O
Intervals : 15, 30, 60, 120 min 22-86 days
DataSonde 4a MiniSonde 4a and Quanta OXISTAT T MODEL 9181 ECOLINE OXI 170 PROBE CellOx 325 / TRANSMITTER OXI 315i (field) YSI 6000 series probes
Hydrolab, PO Box 389, Loveland, CO 805390389 Hydrolab POLYMETRON LANGEui VWR
0.2 mg/L
0 to 20 mg/L
Membranes: Polarography Membranes: Polarography Membranes: Polarography: Oxygen galvanic probe, with membrane Rapid pulse oxygen sensor
SE, R SE, R
0-20 mg/L 0.1% or 1% 0.0-60.0mg/L // 0-600% sat 0-90mg/L
SE, R All
WTW YSI Hydrodata, Letchworth SG6 2HB UK YSIhydrodata
0.5%
0 to 200%: 0 to 500% 2% air sat; saturation 200 to 500%: 6% air sat 0 to 50 mg/L
HARDNESS, ACIDS, BASES

Optical: Photometry: Visible: Titro-Colorimetry 10-15 FPA 400 ANAEL(TYTRONICS) 2%
ORGANIC MATTER
Optical: Photometry: UV Spectroscopy 254 nm Optical: Photometry: UV Spectrometry Optical: Photometry: UV Absorption SE, R, IE All 0,5 0 D ANALYSER 7320 ABB INSTRUMENTATION 1-10% 0-100 mg/L C 0 2% of the 0-50/0-700 range mg/L 3% of 0.01 0 60 mmeasured 1 (50 nm) 0.1 value +/- 0,5 to 600 m-1 (5 mg/L nm) 0.01 to 60 m3% of 1(50 nm) / measured 0.1 to 600 mvalue +/- 0,5 1 (5 nm) / 1 mg/L to 1500 m-1 5% of the range 0
STAMOSENS ENDRESS HAUSER CSM 750/CSS70 UVAS PLUS POLYMETRON
SE, R, IE
30
60
Optical: Photometry: UV Absorption Optical: Spectrophotometry 190 - 820 nm
SE, R, IE
15
UVAS PLUS BYPASS
POLYMETRON
30
SE, R
0,17
SPECTROFLUX
SERES
pH
Electrodes: Glass electrode All PROBE EMK 20 / TRANSMITTER pH 1000 HEYL 1-13 pH
60
Monitoring issues
Electrodes: Glass electrode
R Ground and fresh waters Intervals : 15, 30, 60, 120 min 22-86 days
WQ 201
IRIS INSTRUMENTS
0,01
Electrodes: LIS and reference
DataSonde 4a MiniSonde 4a and Quanta PROBE APS-Z / TRANSMITTER APM-Z INPRO 4010 PROBE 8350 / TRANSMITTER MONEC D 9100 YSI 6000 series probes
Hydrolab, PO Box 389, Loveland, CO 80539+/- 0.2 units 0389 Hydrolab
0 to 14
Electrodes: Glass electrode Electrodes: Polymer electrolyte electrode Electrodes: Glass electrode
All All All All
KOBOLD METTLER TOLEDO POLYMETRON YSI Hydrodata, Letchworth SG6 2HB UK YSIhydrodata ABB INSTRUMENTATION ANAEL ANAEL ANHYDRE ANHYDRE ANHYDRE AQUAMS BRAN + LUEBBE FRANCE BRAN + LUEBBE FRANCE <2% of the range <1% of the range < 3% of the range
0-12 pH 2-12 pH 0-14 pH
Electrodes
0 to 14
0.2 unit
PHOSPHATE
Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric Optical: Photometry Optical: Photometry Optical: Spectrophotometry 194-730 nm Optical: Photometry SE, R, IE All All D D D D SE, R, IE D D SE, R, IE IE SE, R, IE D D D 0 5 8 12 11 10-15 11 6-7 11 0 0 0 15 0 5 10 12 ISO D D F B E D Phosphate Analyser 8242 FPA 800 SENTINEL COLORIMETRE MICROMAC C MICROMAC Hp Poly Nut C POLYMAC ACA MONITOR 90S COLORIMETRE DIAMON 0,05 mg/L 2%0,02 2% 0.2 mol-P/L 7 30 0-60 mg/L PO4 0 0 0 0 0 7
0-1 / 2 / 5 / 10 / 20 / 50 / 100mg/L 0-05 to 0-60 mg/L P 0-3 to 0-16 mg/L P 0.05 to 2.5 / 0.5 to 20 mg/L
30 0
60 0
SE, R, IE
STAMOLY CA71 ENDRESS HAUSER PH
61
Monitoring issues
Optical: Photometry: Visible: Colorimetric Optical: Photometry analyser + controller Optical cell Optical: Photometry: Spectrometry 380-780 nm Optical: Photometry: Spectrometry 380-780 nm Optical: Photometry: Spectrometry 380-780 nm Ion chromatography Ion chromatography Optical: Photometry: Visible: Colorimetric Optical: Photometry: Visible: Colorimetric/Titrimetry/ Potentiometry Optical: Photometry: Visible: Colorimetry/Potentiometr y/ Nephelometry Colour/Titrimetry Optical: Photometry
SE SE
D D
7 6-8
0 8
D E
ADI 2019 HELIOS PHOSPHATE SPECTRON P04 JAUNE SPECTRON PO4 - NH4 SPECTRON PO4 VERT Compact Online Analyser IC 821 Online Analyser IC 811
GE PANAMETRICS MARTEC
1% / 0,005 mg/L
0 - 12610 mg P-PO4/L
0 0
0 0
Reproducibility 0.05-5 mg/L 3% P-P04 0.1-16 / 1.0Reproducibility 80 / 2.02% 100mg/L PPO4 0.1-16 / 1.0Reproducibility 80 / 2.0-100 2% mg/L P-PO4 Reproducibility 2%
SE
6 to 12
MARTEC
SE
6 to 12
MARTEC
D All All SE, R, IE D
MARTEC METROHM METROHM POLYMETRON
< 50 ng/L Repeatability 0.1 mg/L 1 to 2% of the range 0-5 mg/L PPO4 0 0
ANALYSER 8810
SE, R, T
4 to 20
20
SERES 1000
SERES
SE, R, T
4 to 20
20
SERES 2000
SERES
Cycle 1 to 2% of the duration 4 to range 20 min 005 - 300 / 01 - 10 / 01 25 mg/L PO4-P
SE, R
TRESCON MODULE OP 210
WTW
0.02 mg/L
RedOx
Electrodes: Ag/AgCl conduction All Ground and fresh waters Intervals : 15, 30, 60, 120 min 22-86d PROBE RMK 20 / TRANSMITTER ORP 1000 DataSonde 4a, MiniSonde 4a and Quanta HEYL Hydrolab, PO Box 389, Loveland, CO 805390389 Hydrolab -999mV to +999mV Fieldservic eable
Electrodes: LIS and reference electrodes
20 mV
-999 to 999 mV
62
Monitoring issues
Electrodes: Glass electrode Electrodes: Glass electrode
WQ 600 PROBE ARS-Z / TRANSMITTER ARM-Z
IRIS INSTRUMENTS KOBOLD YSI Hydrodata, Letchworth SG6 2HB UK YSIhydrodata POLYMETRON <15%
-100 to +100mV -1999mV +1999mV -999 to +999 mV -1500 to +1500 mV
All Electrodes YSI 6000 series probes PROBE 8351 / TRANSMITTER MONEC D 9100 BIOMONITOR LAR NITRITOX MONITOR BIOX 1010
20 mV
Electrodes: Platine electrode
All
RESPIROMETRY
Respirometry Respirometry SE SE <3 LAR LARL 20-1500 Detection limit: mg/L BOD / 5 mg/L DBO 20-100000 mg/L BOD reproducibility 0-100 % of <5% inhibition 0.1-200 / 5Reproducibility 2000 / 1002% 50000 mg/L 0.05 - 10 000 mg/L 1-50/1-200 000 mg/L
Respirometry
SE
3-15
STIP ISCO
Respirometry
SE
STIPTOX
STIP ISCO
TOC
Optical: Photometry: NDIR Cell Optical: Photometry: Photometry: UV Spectrometry Optical: Photometry: IR SE, IE 3 to 5 5 ISO825 4 F QUICK TOC SPECTROLYSE R SCAN BIOTECTOR 970 BIOTECTOR 990 PLUS MONITOR 90 S Ionometre G BIOMON LAR 7 60
SE
30 s 0
0 0
D F
ANAEL APOLLO INSTRUMENTS APOLLO INSTRUMENTS BRAN + LUEBBE FRANCE BRAN + LUEBBE FRANCE DATALINK 3% of the measured value or +/-5 mg/L < 2 % of the range Reproducibility < 5% or < 3 mg/L C 0.6 Abs/m
0 7
0 15
Optical: Photometry: IR Membranes: specific electrodes Optical: Photometry: IR Optical: Photometry: UV Spectrometry (254 mm)
SE
<3
0-10 / 025000 mg/L 0-2.5 mg/L 0-2000 mg/L 0-50 mg/L C to 0-5000 mg/L C 0-1000 abs/m
30
SE SE, R, IE 15
6 min 15
All
15
CT 200
63
Monitoring issues
Optical: Photometry: UV/Visible Spectrometry Optical: Spectrophotometry multi-wavelength Membranes: Specific Electrode Optical: Photometry: NDIR Optical: Photometry: IR Optical: Photometry: UV Spectroscopy (200-350 mm) Optical: Photometry: UV/Visible Spectroscopy 190-720 mm Optical: Photometry: IR
SE, R, IE
OPTILIS 201
SE, R, IE SE, R
OPTILIS COT 9010
E.F.S. LAC Instruments et systmes E.F.S. LAC Instruments et systmes ENVIRONNEMENT SA GE PANAMETRICS MARTEC
0-300 mg/L
0 - 300 mg/L Repeatability: 5% 0-220 mg/L 0 30 0 0
0,17 All 0 10
D E
STAR-VOC EZ TOC
0-10000 mg/L Repeatability: 0-10 to 01% of the 10000 mg/L range C 10-300 / 1003000 mg/L Reproducibility 4-800 mg/L :3% Reproducibility 2-500/2004%/ 2000/50Detection limit 90000/1002mg/L 10000 mg/L 0-5 nm/L to 2 % of the 0-20000 range mg/L (for TOC et TC) 0-4 / 0-10 / 0Repeatability 20 /0 -40 / 02% of the 100 / 0-200 / range 0-400 / 01000mg/L +/-2% of the 0-5 to 0-1000 range mg/L 2% of the 0-5 to 0-1000 range mg/L <1% 0-2 mg/L C 0-5 mg /L C 0Detection limit: <1% of the 10/100/1000/ 10000 mg/L range
SE
IXO 510
MARTEC
SE
STIP-SCAN
MARTEC
SE, R, IE
12
12
STIP-TOC
MARTEC
Optical: Photometry: NDIR Optical: Photometry: IR Optical: Photometry: IR (measuring CO2) Optical: Photometry: NDIR Optical: Photometry: NDIR Optical: Photometry: NDIR Optical: Photometry: NDIR Analyser Optical: Photometry: IR
SE
2-5 mn Reproducti bility<2 min 0
5 30
ISO 8027
F C
Astro TOC UV BWAM S 751
POLYMETRON SERES
7 0
60 0
SE, R
COT
SERES
30
All All SE, R, IE R, IE All
0 10 s 10 11 0
0,17 0,17 10 11 0
G G
TOC 4110 TOCN 4110 TOCOR 200 TH TOCOR 200 UV
SHIMADZU SHIMADZU SICK MAIHAK SICK MAIHAK WTW
0 0 0 0 0
0 0 0 0 0
PROTOC 200
64
Monitoring issues
TOTAL NITROGEN
Optical: Spectrophotometry 194-730 nm D 24 24 F DIAMON TN/TP BRAN + LUEBBE FRANCE <3% of the range 0-7 mg N/L 0 0
TOTAL PHOSPHORUS
Optical: Photometry: Visible: Colorimetry Optical: Photometry Optical: Spectrophotometry 194-730 nm Optical: Photometry: Visible: Colorimetry/Potentiometr y/ Nephelometry Colour/Titrimetry Optical: Photometry SE, R, IE D 0 0 10-15 min MICROMAC MP POLY Ph az MONITOR 90 S COLORIMETRE PHOSPHORE TOTAL DIAMON TN/TP ANHYDRE BRAN + LUEBBE FRANCE BRAN + LUEBBE FRANCE <3% of the range 0-05 to 0-60 mg P/L
SE, R
SE, R, T
12
28
4-20 min colo 4-8 min potentio
20
SERES 2000 Total Phosphorus
SERES
1 to 2% of the range
SE, IE
TRESCON MODULE PHOSPHATES TOTAUX OP510
WTW
1,5%
0.01-3 mgP/L 2/year
TURBIDITY
Optical: Nephelometry Optical: Photometry: Photometry: UV Spectrometry Ultrasound waves All SE, R, IE T 2 0.17 B +/-2% 0SENSOR 4670 / ABB 100NTU TRANSMITTER 06250 NTU INSTRUMENTATION +/-5% 100-250 7997 NTU SPECTROLYSE R SCAN MONITEK CAPTEUR AS3 / TRANSMETTEU R AT3 PROBE TU810/MONITEU R TU7685 ANAEL 0-5g/L 0 0
0.02
30
12 to 120
ANAEL
0-1mg/L 0-30000mg/L +/- 5% between 4-400 4-400 / 40NTU +/- 10% 4000 NTU between 4004000 NTU
Optical: Nephelometry
All
10 s
0.17
EN 27027ISO702 7
AQUACONTROL
65
Monitoring issues
All
0,5
0.5
PROBE TU8182 / MONITEUR TU7685
AQUACONTROL
All
ISO 9027
MEMODAT 9
AQUALYSE
Optical: Photometry: IR (860 mm)
R, T
10 ISO 7027 / EN 27027
SERVO 5M
AQUALYSE
+/- 5% between 0-400 4-400 / 40NTU +/- 10% 4000 NTU between 400/4000 NTU +/- 5 % of meabetween 0-2000 NTU value or +/-2 NTU +/- 5 % repeatability : 0-1000 NTU 0.1 % of the range 2 % of the range 0-10 / 0-1000 NTU
All
0,13
MICRO TURB ANALYSER SERIES 1000 IR 102
AQUAMS
All
0,17
AWA INSTRUMENTS
Optical: Photometry: IR Optical: Photometry: UV Spectrometry (254 mm)
R, IE, T
BAMO MESURES
+/- 0.01 to +/0-1500 NTU 5NTU 110 % of the 100/200/300 range 200-1000 FNU 0.6 Abs/m 0-100 / 01000 NTU
60
All
CT 200
DATALINK
SE, R, IE
10 s
ISO 7027
TURBIDIMETRE 8832
E.F.S. LAC Instruments et systmes
Optical: Nephelometry (IR LED 850 nm) Optical: Spectrophotometry multi-wavelength Optical: Nephelometry 90 IR
All
0,02
ISO 7027
TURBIDIMETRE 8300
E.F.S. LAC Instruments et systmes E.F.S. LAC Instruments et systmes
1 FTU between 101000 FTU / 0-1000 FTU 0.1 FTU between 0-10 0,1 NTU between 0-10 0 to 1000 NTU / 1 NTU NTU between 10100 NTU 0-1000 NTU 1 % of measured 0-9999 FNU value (Repeatability)
15
SE, R, IE
OPTILIS PROBE TURBIMAX CUS41-Transm Liquisys CUM223/253 TROLL 9000
SE, R, IE
10
EN 27027
ENDRESS HAUSER
SE, R, IE
a few secondes
EQUIPEMENTS SCIENTIFIQUES SA
66
Monitoring issues
SE Ground and fresh waters
TURBIDIMETRE EQUIPEMENTS D15/76 SCIENTIFIQUES SA
5% of measured 0-40 / 0-400 / value or 0.02 0-4000 NTU NTU
Nephelometric: Infrared emittor (880nm) and photodiode
Intervals : 15, 30, ISO 60, 120 7027 min complia 22-86 nt days 0 0 0,17 10
DataSonde 4a MiniSonde 4a and Quanta
1% Hydrolab, PO Box 389, (<100NTU) Loveland, CO 80539- 3% (<400NTU) 0389 5% Hydrolab (>400NTU) MARTEC MARTEC
Self cleaning (require 0-3000 NTU s Turner Minutes. Design SCUFA)
Optical: Light dispersion Optical: Photometry: IR Optical: Retrodiffusion Monofibre PROBE
SE, R, IE
T T
4 ISO7027/DI N38404 ISO 7027/ DIN 38404 ISO 7027/DI N 38404
IE
0,17
ANALYSER MULTIFONCTIO NS OMD7 AFP-TU PONSELLE PROBE INPRO 8100 TRANSMITTER TRB 8300 DATAPROBE 4 A ACQUISITION LOGOSENS MINIPROBE 4a Acquisition Logosens PROBE QUANTA Aquisition Logosens Surface Scatter 6
0-1000 FTU
0 30
0 0
METTLER TOLEDO
OTT
+/- 5 % of the range +/- 5 % of the range
0-100 / 01000 NTU 0-100 / 01000 NTU
0,17
OTT
10 s
0,17
OTT
+/- 5 % of the 0-100 / 100range 1000 NTU +/- 5% de 1 to 2000 NTU and 0.1 to 9999 +/-10% over 2000 <1% 2% of measured value or 0.5 NTU 0.001 - 4000 FNU
Optical: Nephelometry Optical: Photometry: IR diffused at 90 and 150 Optical: Photometry: IR light diffused at 90
SE, IE
0,17
HACH
All
SOLITAX Sensors WP260/262 Transmitter TX PRO-2
HACH
SE, IE
<8
ISO 7027
POLYMETRON
0-2000 NTU
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Monitoring issues
Optical: Nephelometry 90
0,17
TURBIPROBE 90
SERES
All
0,17
ISO 7027 USEPA 180.1 EN ISO 7027
MICROTOL PROBE VISOTURB 700 IQ TRANSMITTER MIQ S 184 YSI 6000 series probes
COLE PARMER
1% of the range / Minimal 0-50 NTU 02000 NTU detectable value: 0,5 NTU 5 % of mean between value 0-1000 NTU or 0.020 over 40 NTU
Optical: Nephelometry 90
R, IE, T
a few secondes
0,17
WTW
0-4000 FNU
Optical: nephelometric
All
ISO 7027
YSI Hydrodata, Letchworth SG6 2HB UK YSIhydrodata
5% of reading or 2 mg.L, whichever is greater
0 to 1000NTU
ORGANIC MATTER AROMATICITY

Optical: Photometry: Photometry: UV Spectrometry Optical: Photometry: UV/Visible Spectrophotometry Optical: Photometry: Spectrometry Optical: Photometry: UV/Visible Spectrometry Optical: Spectrophotometry multiwavelength Optical: Photometry: UV Spectroscopy (200-350 mm) Optical: Photometry: UV/Visible Spectroscopy 190-720 mm Optical: Photometry: UV Spectrometry T 30 s 0 D SPECTROLYSE R SCAN FPA 1100 ProPS OPTILIS 201 ANAEL 190-750 nm 210 to 400 nm 200-385 nm 0 0
All
T T
1 to 5 6 to 12 1
0 12 0
D D D
ANAEL AQUAMS E.F.S. LAC Instruments et systmes E.F.S. LAC Instruments et systmes SECOMAM
0,02 0.2 nm
SE, R, IE
SE, R, IE
OPTILIS
IXO 510
IE, SE
1 to 5
STIP-SCAN
STIP ISCO
Reproductibilit 190 720 nm y:3% 190-1100 nm 5190-825 et 350-1100 nm 0 0
IE
PSS UV
POLYTEC-PI
68
Monitoring issues
Optical: Photometry: UV/Visible Spectrometry Optical: Spectrophotometry 190 - 820 nm Optical: Spectrophotometry
T SE, R IE T T
0 0 0 to 20
0,17 0,17 0
E D E
SENTROPOC UV/VIS SPECTROFLUX MCS 100
SENTRONIC FRANCE - GETSPEC SERES SICK MAIHAK 5% of the range 2 % of the range 190-820 nm
Keys: Method: S = Spot sampling, O = Continuous monitoring, T = Test kits, P = Passive sampling Types of waters: T = Treated water, R = Raw waters, SE = Sewage Effluent, IE = Industrial Effluent, L = leachate
69
Monitoring issues
2.2 - Biological assessment techniques

2.2.1 - General microbiological status including viruses
(www.water.ncsu.edu/watershedss/info/biomon.html)
Microbiological testing of water is particularly important as it offers the most sensitive methods for the detection of faecal and therefore potentially dangerous pollution. Biological examination is used to detect the presence of algae and animal life, where these may gain access to water supplies through deficiencies in water treatment or because of faults in the distribution network. While the proper operation of water treatment works is of the utmost importance, frequent bacteriological tests are necessary in order to ensure adequate assessment of the bacterial purity and safety of drinking water. Chemical and biological tests, other than those required for treatment control purposes, can be made less frequently. Monitoring for the presence of specific pathogenic bacteria, viruses and other agents in water is impracticable and is indeed not considered necessary for routine control purposes. Any pathogenic micro-organisms present in water are usually greatly outnumbered by, and in general also tend to die out more rapidly than, the normal commensally bacterial flora of the human or animal intestine. Although it may be possible to isolate microbial pathogens from contaminated water, especially when it is heavily polluted, large amounts (e.g. several litres) of the water may need to be examined using conventional techniques, selective media are required for isolation, and the subsequent identification of the organisms involves biochemical, serological and other tests on pure cultures. Reliance is therefore placed on relatively simple and more rapid (indicator) bacteriological tests for the detection of certain commensal intestinal indicator bacteria (in particular, Escherichia coli and other coliform organisms). These are easier to isolate and characterise since they are always present in large numbers in human and warm-blooded animals (and hence in sewage),faeces. The presence of faecal indicator organisms in a sample of drinking water thus denotes that intestinal pathogens could be present, and that the supply therefore potentially presents a health risk. It is far more important to microbiologically examine a water supply frequently by a simple test than occasionally by a test or series of tests more complex to implement. However, there is no absolute correlation between the numbers of E. coli or other coliform organisms and the actual presence or numbers of enteric pathogens, nor between the risks of illness occurring and the numbers of E. coli present in a given sample. The detection of E.coli in a properly treated water sample indicates the presence of material of faecal origins and thus a potentially dangerous situation, the nature and extent of which is best determined by on-site and laboratory investigations. Conversely, the absence of faecal organisms is an indication that, in all probability, intestinal pathogens are also absent in the relevant sample. Of the pathogens and facultative pathogenic types of bacteria which can occur in contaminated water, bacteria of the Enterobacteriaceae family are of particular importance. Species including Salmonella, Shigella and Escherichia, the so-called coliform bacteria, and Proteus, Yersinia and Erwinia all belong to this family. Salmonella and Shigella are classed as extremely pathogenic, whereas most of the others are considered as facultative pathogenic. When testing the microbiological quality of water, analysis mainly focuses on E.coli and coliforms, with lesser emphasis being placed on Clostridium perfringens and Enterococci, employing
70
Monitoring issues
total viable counts at 22 and 37 C In addition, the eggs/cysts/oocysts of various parasites can be present in water.
2.2.2 - Biomonitoring with a range of sentinel organisms (e.g. mussels)

Biological monitoring, or biomonitoring, is the use of biological responses to assess changes in the environment, generally changes due to anthropogenic causes. Biomonitoring programs may be qualitative, semi-quantitative, or quantitative. Biomonitoring is a valuable assessment tool receiving increased interest and use in water quality monitoring programs of all types. There are two types of biomonitoring. One type of biomonitoring is surveillance before and after a project is completed or before and after a toxic substance enters the water. The second type of biomonitoring is to ensure compliance with regulations or guidelines or to ensure water quality is maintained. Biomonitoring involves the use of indicators, indicator species or indicator communities. Generally benthic macroinvertebrates, fish, and/or algae are used. Certain aquatic plants have also been used as indicator species for pollutants including nutrient enrichment. There are advantages and disadvantages to each. Macroinvertebrates are most frequently used. Biochemical, genetic, morphological, and physiological changes in certain organisms have been noted as being related to particular environmental stressors and can be used as indicators. The presence or absence of an indicator, an indicator species or an indicator community reflects environmental conditions. Absence of a species is not as meaningful as it might seem as there may be reasons, other than pollution, that result in its absence (e.g., predation, competition, or geographic barriers which prevented it from ever being at the site). Absence of multiple species of different orders with similar tolerance levels that were present previously at the same site is more indicative of pollution than absence of a single species. It is clearly necessary to know which species should be found at the site or in the system. Sentinel organisms Sentinel organisms, or indicator species that accumulate pollutants in their tissues from the surrounding environment or from food, are important biomonitoring devices . The Mussel Watch is one such use of a sentinel species. Filter feeders, such as bivalves (clams and mussels), tend to concentrate metals in their gills or other tissues. The widespread blue mussel (Mytilus edulis) accumulates metals in certain tissues over time. As a result, M. edulis became a species monitored in U.S. waters as well as internationally for changes in levels of pollution. Seaweeds, (e.g., Fucus spp.) accumulate metals. Older algal tissue can be compared to newer tissue in the same individual to determine the history of contaminants in an area. Metals and organochlorines accumulate in finfish and territorial species or non-migratory species such as pike, largemouth bass, can be used for an accurate identification of mercury and organochlorine pollution in a water body. Extreme Uptake Barnacles Bivalve mollusks Gastropod mollusks Isopods, amphipods Polychaetes Zinc (Zn) Copper (Cu), iron (Fe), manganese Cu, Zn Cu, Fe, Pb, Zn Cu
71
Monitoring issues
Moderate Uptake Macroalgae (seaweeds) Mussels/other bivalves Polychaetes Decapods (crayfish) Finfish
Most metals Metals, metallothioneins Cadmium (Cd), Pb Cd, Pb Cd, Pb
Assessment Methodology When the pollutant type is known or well understood, certain indicators are more effectively used or are less expensive. However, when stressors are not known and/or less is known about species tolerance levels, multiple level assessment and more intensive and expensive studies that may include toxicity tests may be necessary. Multiple-level assessment involves the monitoring of indicators and behavioural changes of organisms. Indicators must display a biochemical, genetic, morphological, or physiological change. Behavioural indices are determined by particular species, population dynamics, or community changes. Community level biomonitoring provides information on the magnitude and ecological effects of the stressor on the system. Cause and effect relationships are difficult to establish and few definitely exist, because possible confounding factors are often present. Using indicators at different organisational levels (for example, individuals, species, community, ecosystem) may be more reliable. Biomonitoring measures may be used at the different, but related, levels of analysis: Levels of Organisation and Associated Biomonitoring Parameters Individual : Organism, genetic mutations, reproductive success, physiology, metabolism, oxygen consumption, photosynthesis rate, enzyme/protein activation/inhibition, hormones, growth and development, disease resistance, tissue/organ damage, bioaccumulation Population: survival/mortality, sex ratio, abundance/biomass, behaviour (migration), predation rates, population decline/increase Community: Abundance ("evenness") of an organism or organisms, Biomass, Density of an organism or organisms, Richness (variety), number of species, size classes, or other functional groups, per unit area or volume, or per number of individuals, Diversity, the richness given the relative abundance of each species or group. Ecosystem : Mass balance of nutrients. Assessment Indices There are various indices used to assess the effects of stressors on (aquatic) populations and communities: Biotic Indices: generally specific to the type of pollution or the geographical area; they are used to classify the degree of pollution by determining the tolerance of an indicator organism to a pollutant. Indicator species are assigned scores for their tolerance level. Biotic indices assume that polluted sites or systems will contain fewer species than unimpacted sites or systems and the species that are present will reflect their particular sensitivity to a pollutant. The measures are generally weighted and may include indices such as richness, pollution tolerance, trophic levels present, abundance, and deformities. These indices were originally devised for, and are most useful for, organic pollution. 72
Monitoring issues
Diversity Indices: a measure of the richness, or number of distinct taxa (e.g., orders, families, species) at a site, and the evenness, the relative abundance of different taxonomic groups, determined by counts of all organisms collected. Comparison, or Similarity Indices - the comparison of the community structure in richness and/or evenness over time or over space. Both the diversity index and the similarity index may use the functional feeding group (e.g. herbivores, detrivores, carnivores) as a measure of the community integrity rather than taxa (i.e. species, genus, family). On the level of the individual or species, biochemical and physiological indicators may be examined. Some benthic macroinvertebrates such as stoneflies (plecoptera), caddisflies (trichoptera), mayflies (ephemeroptera), and shellfish, show increases or decreases of certain enzymes, changes in DNA, RNA, amino acids, and protein production, oxygen consumption and ion concentration, in response to environmental stressors such as temperature shifts, metals, and pesticides. Physiological indicators of contamination include deformities, sores, or lesions. The EPA Rapid Bioassessment Protocol for Use in Streams and Rivers uses community diversity in assessing water quality. The absence of pollution sensitive benthic macroinvertebrate groups (ephemeroptera, plecoptera, and trichoptera) and dominance of pollution-tolerant groups (oligochaetes or chironomids), is indicative of pollution. Overall, low richness of benthic macroinvertebrates may indicate impairment. However, naturally low nutrient levels in pristine headwaters may be the cause of low productivity and few benthic macroinvertebrate species exist in these conditions. Pollutant stressors tend to cause slime and filamentous algae productivity and/or fewer fish species and more tolerant species than expected (Plafkin et al., 1989). The judgment of impairment, based on these indicators should be made by an experienced biologist. Common Organisms used for Biomonitoring Benthic macroinvertebrates Advantages: Benthic macroinvertebrates are found in most aquatic habitats. There are a large number of species, and different stresses produce different macroinvertebrate communities. Small order streams often do not support fish but do support extensive macroinvertebrate communities. Macroinvertebrates generally have limited mobility. Thus they are indicators of localized environmental conditions. Since benthic macroinvertebrates retain (bioaccumulate) toxic substances, chemical analysis will allow detection in them where levels are undetectable in the water resource. A biologist experienced in macroinvertebrate identification will, be able to determine relatively quickly whether the environment has been degraded by identifying changes in the benthic community structure of the water resource. Benthic macroinvertebrates are small enough to be easily collected and identified. Sampling of macroinvertebrates under a rapid assessment protocol is easy, requires few people and minimal equipment, and does not adversely affect other organisms. Macroinvertebrates are the primary food source for recreationally and commercially important fish. An impact on macroinvertebrates impacts the food web and
73
Monitoring issues
designated uses of the water resource. State water quality agencies tend to collect macroinvertebrate data. Disadvantages: Benthic macroinvertebrates do not respond to all impacts. Seasonal variations may prevent comparisons of samples taken in different seasons. Drifting may bring benthic macroinvertebrates into waters in which they would not normally occur. Knowledge of drifting behaviour of certain species can alleviate this disadvantage. Certain groups are difficult to identify to the species level. Example invertebrate indicators of specific impairment types: Nutrient enrichment - increased ratio of aquatic worms (oligochaetes) to aquatic insects - increased ratio of midges (chironomids) to other aquatic insects - increase of herbivorous mayflies (ephemeropterans) and midges. Low dissolved oxygen - increased ratio of aquatic worms to aquatic insects increased ratio of midges to other aquatic insects. Contamination by heavy metals - increased ratio of aquatic worms to aquatic insects - increased ratio of midges to other aquatic insects - increased abundance of water bugs and water beetles - increased ratio of predators to herbivores and detrivores Sedimentation - decrease in mayflies and midges Low pH - loss of snails, clams, mussels, daphnids, mayflies, midges Temperature - Releases of heated effluents tend to reduce community richness Fish http://www.wildlife.utah.gov/, http://www.ens-newswire.com/ Advantages: Fish are good indicators of long-term effects (several years) and habitat conditions. Fish communities represent a variety of trophic levels; toxic substances tend to biomagnify, and thus fish community structure reflects community health. Fish are consumed by humans. Fish are relatively easy to collect and identify. Environmental requirements, life history information and distribution are well known for most species. Certain fish species such as salmon, trout, perch and sculpins, are less tolerant of pollution than others. Bottom dwellers are more tolerant of organic pollution since they are adapted to lower oxygen levels. Predatory species that use sight to hunt, such as pike, are sensitive to turbid conditions. Extensive fish kills are indicative of severe oxygen depletion caused by organic pollution, oil slicks, or severe toxic pollution, including toxic bacteria or plankton. Erratic behaviour, such as swimming close to the surface, slow movements, swimming in circles, and gasping for oxygen, are indicative of water contamination or severe oxygen depletion. Disadvantages: Motility and migration cause difficulty in pinpointing a pollutant as the cause of abnormalities in individuals or a population. Monitoring only certain fish species will miss changes in the benthic community or in other species in the community that over time will affect the fish species. Fish are not as sensitive as their food (macroinvertebrates) to pollution and monitoring of fish may not reflect severe changes in the invertebrate community. An assessment of fish alone will not ensure "ecosystem health." Example indicator fish species by impairment type: Oxygen depletion : Darter species salmonids Sculpin species benthic insectivores Sedimentation : Darter species salmonids Sculpin species benthic insectivores
74
Monitoring issues
Degradation of pools and vegetative cover: Sunfish species (centrarchids) Minnow species (cyprinids) salmonids Physical and chemical degradation of the water resource (long lived species) : suckers (catostomids) adult trout minnows catfish tolerant species (source: Plafkin et al., 1989)
Algae Algal growth is dependent on sunlight and nutrient concentrations. An abundance of algae is indicative of nutrient pollution. Algae are sensitive to some pollutants at levels which may not visibly affect other organisms in the short term or may affect other communities at higher concentrations. Advantages: Algae have very short life cycles and rapid reproduction. This can also be a disadvantage. Algae tend to be most directly affected by physical and chemical environmental factors. Sampling is easy and inexpensive, requires few people and minimally impacts other organisms. Standard methods exist.
Table 7 summarises parameters for bioecological monitoring and table 8 presents a short selection of European Union-funded work dedicated to the assessment of water quality with biological monitoring tools;
SAMPLING PROCEDURES Results from ecological monitoring are, as any other measurements, crucially dependent on the sampling protocol used to collect samples of invertebrates, algae, or fish. The experience and knowledge of the person undertaking the sampling are also very important for the comparability of results. Some ISO/CEN standard protocols for sampling fish, algae and invertebrates may be found in appendices. However, tools and softwares summarised in Table 8 require adequate sampling to obtain valid results or to be able to compare results to reference sites used in the softwares. One of the aims of the STAR project (Table 8) is to develop and provide sampling protocols to be used in conjunction with tools quoted in Table 8. Sampling protocols are available on the STAR project website (http://www.eustar.at/frameset.htm) for: - AQEM - Non-diatom benthic algae - Benthic diatoms - RIVPACS - UK invertebrate sampling - Biological monitoring under Polish conditions - PERLA - Field assessment of Macrophyte - STARFISH - The EBBEOSWA method - The Swedish invertebrate method These protocols are being continuously updated until the end of the STAR project.
75
Monitoring issues
Table 7. Biomonitoring "Rapid Assessment"
Parameter
Macroinvertebrates and Fish Number of macroinvertebrate taxa (e.g. family, genus) at site Number of EPT benthic macroinvertebrate taxa (ephemoptera, plecoptera, and trichoptera) to species level if possible Number of aquatic worms, midges, and/or snails Niche Occupant Forms Counts are of number of forms, not individuals Number of native fish species; benthic species (sucker species); darter species; pool species (sunfish species); long-lived species; tolerant species; intolerant species Evenness (Abundance) Number of individuals Ratio of ephemoptera, plecoptera, and trichoptera (EPT) (benthic macroinvertebrate) species to chironomids (midges) Ratio of individuals in numerically dominant taxa to total number of individuals Proportion of tolerant fish species of total number collected
Rationale for parameter selection

Taxa richness tends to decline as water quality declines These orders tend to be sensitive to pollutants Abundance of such groups indicates nutrient enrichment, low dissolved oxygen, and heavy metal contamination Number of niche occupant forms declines as water quality declines Determines level of degradation
Issues
Difficulty in identification results in underestimation. Richness measures counts at the level of the order or family may ignore the range of pollution tolerance across the family, genus, or even species level. Species level keys only available for 1/2 of taxa. Presence/absence of taxa is a measure as well Measure is most useful if you can see a change over time. Based on taxa that a novice biologist can discern. Faster. May count different life stage of same taxon as different taxa and therefore overcount. Knowledge of water body composition prior to pollutant makes measure most accurate. Introduction or stocking of species may cause a misrepresentation of actual stream integrity.
Pollutants may cause numbers or biomass to increase (for example, nutrients) or decrease (for example, pesticide). Chironomids (midges) are considered more pollutiontolerant. In particular, chironomids respond to nutrient enrichment and eutrophic conditions. EPT taxa are more sensitive to heavy metals Domination by few species or families indicates stress or conditions which preferentially support particular taxa such as nutrient enrichment, low dissolved oxygen, and toxic contaminants Domination by few species or families indicates stress or conditions which preferentially support particular taxa such as nutrient enrichment, low dissolved oxygen, and toxic contaminants
Competition and predation cause population changes as well. Simple counts of individuals will miss more subtle indications of stress such as physical condition or physiological changes. At the species level of chironimids, a range of pollution tolerances exists. Habitat can influence abundance. Mean size of kick screen must be small enough to ensure chironimids are captured Unstressed habitats may have few taxa.
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Monitoring issues
Proportion of fish with disease/deformities, etc Functional Feeding Group Ratio of shredders to total. Collect samples from leaves or other coarse particulate organic matter (CPOM). Ratio of scrapers to collector feeders High levels of toxic compounds may generate physical abnormalities.
Shredders and their microbial food are sensitive to toxic substances and habitat modification
Ratio of specialists to generalists Proportion omnivorous, insectivores, carnivorous fish
These groups indicate availability of food resources. Collector-feeder dominance indicates organic enrichment. Decline of filtering collectors is indicative of toxic contaminants, as toxicants bind to their food particles Specialists are restricted to specific food sources; generalists use a broader range of food sources Assumes there would be more omnivorous fish as environment deteriorates; as the invertebrate community is reduced, insectivores decrease; top carnivores will bioaccumulate pollutants so their presence is indicative of high integrity
Identifications must be accurate. Counting the same taxon of a different age group is a problem. Seasonality influences data; easily processed litter such as maples and birch generally have high shredder content in the winter; whereas oak, beech, pine litter have high shredder content in the summer. Some scrapers are pollution-tolerant. If toxic compounds are present in the organic matter, this measure may not be clearcut. Identifications must be accurate. Assumes that generalists are more pollution-tolerant and become numerically dominant. Difficult to identify whether and organism is definitely one or the other Score habitat using Plafkin system.
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Monitoring issues
Table 8 : Selection of tools for water quality evaluation/classification based on community structure and diversity
ID
Biological species
Description / Tool
Standardisation of river classification: Framework method for calibrating biological surveys against ecological quality classifications to be developed for the WFD Integrated assessment systems for streams using benthic macro-invertebrates:
Type of waters
Coordinator addresses/Website
Michael Furse (CEH Dorset) Winfrith Technology Centre, Winfrith Newburgh, Dorchester DT2 8ZD, Dorset, U.K. http://www.eu-star.at/frameset.htm Daniel Hering Institute of Ecology - Dept. of Hydrobiology University of Essen Universitaetsstr. 5 45117 Essen Germany http://www.aqem.de/start.htm Stefan Schmutz Institute of hydrobiology and aquatic ecosystem management Dept. Water-Atmosphere-Environment BOKU- University of Natural Resources and Applied Life Sciences, Vienna, Austria http://fame.boku.ac.at/ Sovan Lek CESAC (Centre decologie des systemes aquatiques continentaux) Universite Paul Sabatier 118, route de Narbonne 31062 Toulouse cedex, France http://aquaeco.ups-tlse.fr/index2.htm Prof. EW Taylor School of biosciences, The University of Birmingham, Edgbaston, Birmingham - B15 2TT, U.K. http://www.biosciences.bham.ac.uk/labs/taylor/CITYFIS H.htm CEH Dorset http://dorset.ceh.ac.uk/River_Ecology/River_Communiti es/Rivpacs_2003/rivpacs_introduction.htm http://perla.vuv.cz/
STAR project
Rivers
AQEM
Benthic invertebrates AQEM assessment software 2.3 available for download (Apr 2004) Fish-based Assessment Method for the Ecological status of European rivers Plans for a software
Rivers
FAME
Fish
Rivers
PAEQANN
Algae (diatoms) Benthic invertebrates And fish
Predicting Aquatic Ecosystem Quality using Artificial Neural Networks: Impact of Environmental characteristics on the Structure of Aquatic Communities (Algae, Benthic and Fish Fauna) PAEQANN software available for download Modelling the Ecological Quality of Urban Rivers: Ecotoxicological Factors Limiting Restoration of Fish Populations Stream invertebrate-based assessment system RIVPACS III+ (release 2.2) available for purchase (1000+VAT) Water quality prediction and assessment system using river macro invertebrates (based on the same
Rivers
CITYFISH
Fish
Heavily modified water bodies
RIVPACS PERLA
Benthic invertebrates Invertebrates
Freshwaters Freshwaters
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Monitoring issues
system to RIVPACS) PERLA and HOBENT available for download Water quality assessment using macro-invertebrates ECOPROF Macro invertebrates ECOPROF (version 2.5) software available for download Australian River assessment system AUSRIVAS 1.1beta3 software available for download ECOFRAME Macrophyte Phytoplankton Invertebrates Integrated assessment tools to gauge local functional status in river ecosystems Freshwaters Shallow lakes http://www.ecoprof.at/ http://enterprise.canberra.edu.au/Databases/AusRivAS. nsf/WebContents/?OpenView&ExpandView&Count=50 http//www.target-eu.org
AusRivAs
Macro invertebrates
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Monitoring issues
2.2.3 - Status assessment by biological diversity

The principal components of freshwater biological diversity Aquatic organisms may be classified in a number of different ways. For the purposes of assessment the two most important approaches are by systematics (that is by taxonomic group) and by ecological zonation, the latter being chiefly a reflection of the size of the organism and the position it occupies within the freshwater ecosystem. These two approaches should be regarded as complementary. The former is necessary for the identification and monitoring of species, these being the most important individual components of biological diversity. The latter is necessary for an understanding of the ecological integrity of ecosystems. It is also important methodologically: survey and sampling techniques generally concentrate on one particular ecological zone which typically contains representatives of a number of different taxonomic groups. Table 9 sets out the major freshwater groups taxonomically. Table 10 discusses the major ecological zones of inland waters.
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Monitoring issues
Table 9. Major freshwater groups (taxonomically organised)
General features
VIRUSES Microscopic; can reproduce only within the cells of other organisms, but can disperse and persist without host. BACTERIA Microscopic; can be numerically very abundant, e.g. 1,000,000 per cm3, but less so than in soils. Recycle organic and inorganic substances. Most derive energy from inorganic chemical sources, or from organic materials. FUNGI Microscopic. Recycle organic substances; responsible for decay of dead material; tend to follow bacteria in decomposition processes. Able to break down cellulose plant cell walls and chitinous insect exoskeletons. ALGAE Microscopic and macroscopic; include variety of unicellular and colonial photosynthetic organisms. All lack leaves and vascular tissues of higher plants. Green Algae (Chlorophyta) and Red Algae (Rhodophyta) include freshwater species; Stoneworts (Charophyta) mostly freshwater. PLANTS Photosynthetic organisms; mostly higher plants that possess leaves and vascular tissues. Mosses, quillworts, ferns important in some habitats. Some free-floating surface species (e.g. Water Fern Salvinia, Duckweed Lemna); most are rooted forms restricted to water margins. INVERTEBRATES: PROTOZOANS Microscopic mobile single-celled organisms. Tend to be widely distributed through passive dispersal of resting stages. Attached and free-living forms; many are filter-feeders.
Significance in freshwaters
Cause disease in many aquatic organisms, and associated with water-borne disease in humans (e.g. hepatitis).
Responsible for decay of dead material. Present on all submerged detritus where a food source for aquatic invertebrates. Many cause disease in aquatic organisms and humans.
Present on all submerged detritus where a food source for aquatic invertebrates. Some cause disease in aquatic organisms and humans.
Responsible for most primary production (growth in biomass) in most aquatic ecosystems. Free-floating phytoplankton main producers in lakes and slow reaches of rivers; attached forms important in shallow parts of lakes and streams.
Provide a substrate for other organisms and food for many. Trees are ecologically important in providing shade and organic debris (leaves, fruit), structural elements (fallen trunks and branches) that enhance vertebrate diversity, in promoting bank stabilisation, and in restricting or modulating flood waters. Found in virtually all freshwater habitats. Most abundant in waters rich in organic matter, bacteria or algae. Feed on detritus, or consume other microscopic organisms; many are parasitic on algae or vertebrates.
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Monitoring issues
INVERTEBRATES: ROTIFERS Near-microscopic organisms; widely distributed; mostly attached filter-feeders, some predatory forms. INVERTEBRATES: FLATWORMS Mobile bottom-living predatory flatworms. Poorly known. INVERTEBRATES: NEMATODES Microscopic or near-microscopic roundworms. INVERTEBRATES: ANNELID WORMS Two main groups in freshwaters; oligochaetes and leeches. INVERTEBRATES: MOLLUSCS Two main groups in freshwaters; Bivalvia (mussels etc) and Gastropoda (snails, etc). Very rich in species; tend to form local endemic species. INVERTEBRATES: CRUSTACEANS A very large Class of animals with a jointed exoskeleton often hardened with calcium carbonate. INVERTEBRATES: INSECTS By far the largest Class of organisms known. Jointed exoskeleton. The great majority of insects are terrestrial. VERTEBRATES: FISHES More than half of all vertebrate species are fishes. These are comprised of four main groups: hagfishes (marine), lampreys (freshwater or ascend rivers to spawn), sharks and rays (almost entirely marine, ray-finned 'typical' fishes (>8,500 species in freshwaters, or 40% of all fishes). VERTEBRATES: AMPHIBIANS Frogs, toads, newts, salamanders, caecilians. Require freshwater habitats. Larvae of most species need water for development. Some frogs, salamanders and caecilians are entirely aquatic; generally in streams, small rivers and pools. Larvae are typically herbivorous grazers, adults are predatory. Fishes are the dominant organisms in terms of biomass, feeding ecology and significance to humans, in virtually all aquatic habitats including freshwaters. Certain water systems, particularly in the tropics, are extremely rich in species. Many species are restricted to single lakes or river basins. They are the basis of important fisheries in inland waters in tropical and temperate zones. In rivers and streams, grazing and predatory aquatic insects (especially larval stages of flying adults) dominate intermediate levels in food webs (between the microscopic producers, mainly algae, and fishes). Also important in lake communities. Fly larvae are numerically dominant in some situations (e.g. in Arctic streams or low-oxygen lake beds), and are vectors of human diseases (e.g. malaria, river blindness). Include larger bottom-living species such as shrimps, crayfish and crabs of lake margins, streams and estuaries. Also larger plankton: filter-feeding Cladocera and filter-feeding or predatory Copepoda. Snails are mobile grazers or predators; bivalves are attached bottom-living filter-feeders. Both groups have speciated profusely in certain freshwater systems. The larvae of bivalves are parasitic on fishes. Because of the feeding mode, bivalves can help maintain water quality but tend to be susceptible to pollution. Oligochaetes are bottom-living worms that graze on sediments; leeches are mainly parasitic on vertebrate animals. May be parasitic, herbivorous or predatory. Typically inhabit bottom sediments. Poorly known; may be more diverse than recognised. Important in plankton communities in lakes and may dominate animal plankton in rivers.
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Monitoring issues
VERTEBRATES: REPTILES Turtles, crocodiles, lizards, snakes. All crocodilians and many turtles inhabit freshwaters but nest on land. Many lizards and snakes occur along water margins; a few snakes are highly aquatic. VERTEBRATES: BIRDS Many birds, including waders and herons, are closely associated with wetlands and water margins. Relatively few, including divers, grebes and ducks, are restricted to river and lake systems. VERTEBRATES: MAMMALS Relatively few groups are strictly aquatic (e.g. river dolphins, platypus), several species are largely aquatic but emerge onto water margins (e.g. otters, desmans, otter shrews, water voles, water oppossum, hippopotamus). Top predators, and grazers Top predators Because of their large size, crocodiles can play an important role in aquatic systems, by nutrient enrichment and shaping habitat structure. They, as well as freshwater turtles and snakes are all predators or scavengers
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Monitoring issues
Table 10. Major divisions of freshwater ecosystems Plankton phytoplankton Small, generally microscopic, suspendend organisms which float passively or swim weakly. Phytoplankton almost entirely algae; zooplankton from a range of groups, especially protozoa.
Pelagic zone (open water) Nekton Neuston
zooplankton Larger actively swimming organisms within the open water or pelagic zone. Mostly fishes Organisms which inhabit the surface layer of water, including floating plants and surfacedwelling invertebrates Component of neuston comprising large floating assemblages of plants blown about by wind (e.g. water hyacinth Eichhornia). Large algae attached to rocks and higher plants usually in the littoral zone Higher plants rooted in or anchored to the substrate, usually in littoral zone. Those which protrude above the water surface are termed emergents Very small, usually microscopic, attached community of algae, bacteria, fungi, protozoans and attached metazoans. Animals which live on the bottom Animals which burrow beneath the bottom Organisms which live within submerged vegetation
Pleuston Littoral (shallow water and shoreline) and benthic (bottom) zones Attached macro-algae Aquatic macrophytes Aufwuchs Benthos epibenthic fauna Infauna
Epiflora
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Monitoring issues
2.2.4 - Biomarkers
Several definitions have been given for the term biomarker, which is generally used in a broad sense to include almost any measurement reflecting an interaction between a biological system and a potential hazard, which may be chemical, physical or biological (WHO, 1993). 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 (Peakall, 1994). Van Gastel and Van Brummelen (1994) redefined the terms biomarker, bioindicator and ecological indicator, linking them to different levels of biological organization. According to the NRC (1987), WHO (1993), biomarkers can be subdivided into three classes: - biomarkers of exposure: covering the detection and measurement of an exogenous substance 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; - 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; - biomarkers of susceptibility: indicating the inherent or acquired ability of an organism to respond to the challenge of exposure to a specific xenobiotic substance, including genetic factors and changes in receptors which alter the susceptibility of an organism to that exposure. Although fundamental research and development for field application are still necessary, biomarkers are considered as powerful tools of detection of pollutants in aquatic systems. The table presents most of biomarkers used for the control of water quality including several examples of application. Table 11 presents some examples of biomarkers using aquatic organisms. A more complete table should be available in the article of Ron van der Oost (2003) in the review of Environmental Toxicology and Pharmacology. In these case, the more studied compounds are PAHs and PCBs. Some of these biomarkers are commercially available. Molecular biomarkers, based on genetic and cellular perturbation are currently being developped. They represent very most promising tools as they will allow the very early detection of an ecosystem perturbation caused by the presence of xenobiotics.
85
Monitoring issues
Table 11. Biomarkers
Parameters
ORGANIC POLLUTANTS PAHs, PCBs, PCDDs PCDFs
Method
Type Of Water
Status
Biomarkers type
organisms
Name
Ref
Enzyme activity CYP1A Protein CYP1A mRNA
Fresh and marine water Field study North Sea Lake
Laboratory test
Cytochrome P450 system A induction Constitutes a suitable biomarker for exposure to organic pollutants in fish or mollusc Phase I metabolism
Fishes Mollucs Crustaceans

fishes Carp Cyprinus carpio Dab Limanda limanda Rainbow trout Roach Rutilus rutilus EROD Flounder Platichthys flesus Eel Anguilla anguilla Red mullet Mullus barbatus sea bass Dicentrarchus labrax Roach Rutilus rutilus
1, 2
PAHs, PCBs BKME HCBs OC
Spectrophotometric, fluorometric method
River Field study Mediterranean Sea Mediterranean Sea Mediterranean Sea Lake (Holland)
France AFNOR NF T 90-385
3, 4, 5, 6, 7, 8
Radiometric technique measuring of total metabolite of BaP

PAHs
Molluscs
Mediterranean Sea Mediterranean Sea North Sea Lake Finland Mussel Mussel Mytilus galloprovincialis
BPO
5
Molluscs, fishes
Mussel Mytilus galloprovincialis Comber Serranus cabrilla
Fluorometric method
Unbleached kraft pulp-mill effluent
BPH
1
Cod, haddock, whiting

Rainbow trout (encaged)
86
Monitoring issues PAHs, PCBs, PCDDs PCDFs

BKME PAHs PAHs PCBs ELISA, Western-blotting histochemical techniques Field study fishes Perch Perca fluviatilis Salmon Salmo Salar Catfish Xenobiotic metabolism Phase II 7 CYP1A Protein 2
Measurement of CYP1A mRNA

Enzyme activity
River Fresh and marine water Mediterranean Sea Mediterranean Sea
PAHs, PCBs, PCDDs PCDFs Petroleum hydrocarbons and/or polychlorinated biphenyls (PCBs). PCBs, pesticides
Fish Mollucs Crustaceans sea bass Dicentrarchus labrax

Mussels Mytilus galloprovincialis GST 4 9
Spectrophotometr y
Kit (http://www.cayman chem.com/
Laboratory test
glutathione Stransferase
induction UDP-GT (Urindine DiPhosphoGlucuronsy Transferase)
(transplanted) Eel Anguilla anguiila
Xenobiotics
(PAHs, PCBs, pulp mill.)
Colorimetric method
Field study
10, 11
Non specific pollutants (organic pollutants, heavy metals)
Kits of measurement (http://www.oxisre search.com/) Enzymatic reaction + UV spectrophotometry Enzymatic reaction + colorimetric method
Reaction with thiobarbituric acid to form a coloured adduct HPLC + UV
Fresh and marine water
Laboratory test
Oxidant stress
Molluscs, fishes
12 -
Pesticides
Field study
Mussels Unio tumidus
CAT Catalase Induction GPOX glutathione peroxidase GRED glutathione reductase Lipid peroxidation
13
Non specific pollutants

oxidant chemical stress Cu, Hg
Field study
Mussels, fishes
MDA induction
13, 14
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Monitoring issues
Immunochemical method Molluscs, fishes Mussel Mytilus galloprovincialis, oyster Crassostrea sp., crab Carcinus maenas, mullet mugil cephalus Mussels, fishes Mussels Mytilus galloprovincialis, Fishes sparus aurata, dab limanda limanda, English sole, parophrys vetulus
PAHs, PCBs
Field study
SOD SuperOxyde Dismutase
15
PAHs, PCBs Urban and industrial pollution
HPLC/Electroche mical detector 32 P-postlabeling HPLC/fluoescence Immunoassays (adducts specific antibodies) electrophoresis
Field study
8-oxodGuo
16, 17, 18, 19, 20
PCBs, PAHs PCBs
Fresh and marine water Field study Laboratory test Genotoxic parameters
Fishes English sole Winter flounder Molluscs, fishes Fish

Laboratory test Bio transformation products Red mullet Mullus barbatus
DNA adducts 1 Comet assay PAH metabolites in bile

7 ,24 17, 21, 22, 23
PAHs
Field study Fresh and marine water
PAHs
LC-fluorescence GC/MS Fluorescence
Coastal area of Mediterranean Sea Field study
Sea comber Serranus cabrilla

Flounder Platichthys flesus Cod Gadnus morhua Eel Anguilla anguilla English sole 7 14
hydrocarbons pesticides Hydrocarbons (OP) carbamate pesticide (OP) carbamate pesticide pesticides, heavy metals, domestic waste and phytotoxins
Field study
Dot- western blot Reaction acethylthiocholine hydrolysis + VIS spectrophotometry Radiometric and imunnochemical techniques
Coastal French waters Fresh and marine water Mediterranean Sea Lagoon (Tunisia)
Laboratory test Laboratory test
Gastropod M. turbinata Mussel M. Galloprovincialis Mussels Mytilus edulis

Neurotoxic parameter
MXR AchE (inhibition)
14 25 14 4 26
Fish, invertebrates
sea bass Dicentrarchus labrax Clams Ruditapes decussatus Mussels Mytilus galloprovincialis
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Monitoring issues chromatography,

Atlantic coast north European water Mediterranean Dab Limanda limanda red mullet Mullus barbatus Comber Serranus Cabrilla
(OP) carbamate pesticide
Estuarine waters undetermined components of complex mixtures of pollutants (combustion hydrocarbons and natural wood leachate) PAHs WWTP PCBs Xenoestrogens Alkylphenols, synthetic steroids, organochlorine pesticides, plastic products (bisphenol A, phthalates) xenoestrogens Estrogenic chemicals Non-DDT pesticides, PCBs, PAHs, heavy metals PAHs, PCBs sewage effluent Endocrine disruptors chemicals Endocrine disruptors chemicals tributyltin
Mussel Mytilus galloprovincialis and edulis Oyster Crassostrea gigas

trout Salmo trutta flounder Pleuronectes americanus Mussel Mytilus edulis
River, Ocean
27
Field study
14
VTG
Fresh and marine water Reproductive endocrine parameters fishes 7, 28, 29, 31, 30
Increase RIA ELISA Western blot

freshwater Laboratory test
Trout , carp
Rainbow trout Oncorhynchus mykiss Atlantic salmon Salmo salar Atlantic cod Gadus morhua Female flounder (Pleuronectes americanus) Female flounder Platichtys flesus flounder Platichtys flesus Swordfish Xiphias gladius Laboratory test Laboratory test
32 http://www. bequalm.or g/biomarke rs.htm 33
Field study Field study Marine water Mediterranean Sea
induction
33 33 34
ELISA Western blot Observation
Mediterranean Sea Field study
Fish
Swordfish Xiphias gladius Gastropod molluscs
ZRP (zona radiate proteins) Imposex
34 35
89
Endocrine disruptors chemicals Non specific pollutants (organic pollutants, metals) PAHs, PCBs, metals Control water quality
Observation of gonads Automated image analysis
Review Fresh and marine water Mediterranean coast Estuarine coastal waters
fishes
Molluscs Fishes Mussels Mytilus galloprovincialis Mussels Mytilus galloprovincialis
Monitoring issues Histopathology

36
Laboratory test
Lysosomal alterations
lysosomal enlargement, reduction of stability of lysosomal membrane
12, 35, 14 35 37
HEAVY METALS Heavy metals (Zn, Cd, Cu) Cd, Cu, Hg Cd, Cu metals Cu, Cd Cd Heavy metals (Zn, Cd, Cu) Cd, Cu, Zn Zn Cd Non-specific pollutants : PAHs, PCBs, some pesticides ,heavy metals and others stressors (T, UV) Fresh and marine water
Molluscs, fish Mussel Mytilus edulis Mussel Mytilus galloprovincialis Zebra mussels Crabs
Stress proteins, metallothioneins multixenobiotic resistance (MXR) Flounder Platichthys flesus
5, 35 38 35
Metals substitution South coast methods Portugal RIA, ELISA River ARNm EstLaboratory Field study test quantification Differential pulse Estuarine water Estuarine water polarography (UK) Chromatography
Gironde Estuary River Canada River Sweden
MTs
induction
39 40 41 42 43 1 1
oyster Crassostrea gigas Rainbow trout Perch Fish, molluscs, crustaceans Heat shock protein (HSP)
Electrophoretic separation of metabolically labelled proteins Western blooting technique
Fresh and marine water
Laboratory test
12, 44, 45, 40
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Monitoring issues
2.2.5 - Direct toxicity measures (e.g. endocrine damage) (wide range some validated, some still experimental)
Biological techniques and sensors are useful analytical tools for environmental monitoring, because they provide rapid and cost-effective results. Moreover, the new technologies allow to make portable equipments, capable of real-time measurements, or remote devices. On the other hand, biological techniques as bioassays and generic biosensors provide responses about the possible biological effects in the receptor environment. The increasing number of potentially harmful pollutants in the environment calls for faster and more cost-effective analytical techniques to be used in extensive monitoring programs. A lot of work is undertaken at various research institutes. Table 25 in appendix 2 relates these scientific developments. Tables 12 summarises the main commercially available bioassays and biosensors that may be used to monitor biochemical oxygen demand (BOD), general toxicity, cyto- and genotoxicity and levels of organic and inorganic chemicals in water. Table 13 presents other means for direct toxicity measurements. The first one is the use of whole organism bioassays, generally based on spot samples collected in the field (e.g. 48hr-acute toxicity test with Daphnia magna or pulex). The second type, biological early warning systems (BEWS) is also based on the use of whole organisms but this time within on-line or continuous measurement systems, or for insitu deployment. These BEWS based on fish, daphnia, mussels, or other invertebrates are generally fast-response biological systems, relying on organism's behavioural response to changes in toxicity of the water. The reaction to trace metals, pesticides and other organics is used to trigger an alarm and may also trigger a sampler (e.g. on-line GC/MS).
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Monitoring issues
Table 12. Bioassays/biosensors
Variable measured*
Parameter
Method
Type of water
Type of device (reference)
Costs ()
Model
precisio n of the measure ment
Calibration Range
MONITORING OF BOD AND TOXICITY

O2 0.03 - 100% (in air) 0.04 - 35 mg L-1 (in water) T -5 to 70 C PH 4 - 9 pH units BOD 1-2000 mg/L
O2 ,T, pH, BOD CO2 , Humidity And dissolved. Hydrocarbons
Fibre optic chemical sensors based on luminescence
Surface/gro und water, atmosphere
Commercial
OPTOSEN system
Universidad Complutense de Madrid
O2 : 0.02 mg/L T:0.1 C pH: 0.05 pH BOD: 0.5 mg/L
BOD
BOD
Waste Water Treatment On line BOD Microbial Plants, Biosensor, respirometry Drinking water, Industrial estates On line BOD Microbial Water Biosensor, respirometry On line BOD Microbial Biosensor Water
On line
Commercial (www.biosensores.com)
BOD-TOX
Biosensores SL
3-200mg/L
<3%
Commercial (www.stip.de) Commercial (www.kelma.com/catalog.ht m)
BOD, toxicity
5 - 100000 mg/L 0 - 500 RODTOX2000 University of Ghent / 000mgBOD/l (KELMA) Kelma , 0 - 100 % TOXICITY BIOX 1010
Isco GmbH, GroUmstadt,
3% reproducibility
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Monitoring issues
Biodegradation rate, natural attenuation
Biodegradation rate sensor (continuous measurement of CO2)
Ground Water
Conti nuou s
Prototype [1, 2]
Bordeaux 3 university
Detection levels Degradation of 1 mg/L/day
Genotoxicity
Bioassay SOS-LUXTest is based on the Soils, measurement of the sediment, DNA damagesurface dependent induction of groundwat the bacterial SOS er system
Labo rator y 3-8 hour s
Prototype [3, 4, 5, 6]
comparable to the VITOTOX SOS-LUX-LACInstitute of test and FLUOROAerospace Medicine other SOSToxicity-test Radiation Biology dependent genotoxic assays Comparable to other LAC-FLUORO Institute of plasmid SOSAerospace Medicine dependent pGFPuv Radiation Biology genotoxic assays
LAC-FLUORO plasmid Labo pGFP uv were rator Soils, established to recognise sediment, y Genotoxicity and record in parallel test surface Cytotoxicity the genotoxic and/or groundwat 3-8 cytotoxic activity of hour er substances or radiation s On field Optical fibre covered Soils, Conti Genotoxicity and sensitive luminescent sediment, nuou surface s On-field-Detection bacteria (Escherichia of heavy metals coli MC1061) groundmea immobilised water sure ment yeast cellular biosensor used for the simultaneous detection of both genotoxicity Water (damage to genetic samples material) and more general cellular toxicity (cytotoxicity).
Prototype [3, 6]
Prototype [7, 8, 9]
Ben-Gurion University of the Negev
down to 2g/L
Genotoxicity Cytotoxicity
Field test
Commercial (www.gentronix.co.uk) [10, 11, 12]
GreenScreen Environmental Monitoring Gentronix Limited & Yeast University of Environmental Manchester Toxicity Indicator (YETY) cell density reader
Good vs. pure chemicals but less stable vv. Complex whole effluents
93
Monitoring issues
Genotoxicity
Umu-test Bacterial genotoxicity assay
Water samples
2-3 days
Commercial [13, 14]
High sensitivity to genotoxins standardized and validated by Berlin University of German DIN Technology (DIN 38 415 T3) and on the international level by ISO (ISO/DIS 13829, 2000 Loats Associates, Inc. 201
Genotoxicity
LAI's Automated Comet Assay Analysis System (LACAAS) Electrochemical DNA Wastewat Biosensors and er Acetylcholine sensors On field dete ction 2min
www.loats.com/comet.html
Genotoxicity / Toxicity /toxic aromatic amines
Prototype [15, 16]
Universit degli Study di Firenze
0.05 - 5 microM
Waste toxic effects that Water contaminants have on Treatment the microbial Labo Plants, metabolism of a rator Toxicity Drinking continuous biological y water, reference system Industrial estates Conti nuou surface, s Toxicity/herbicides/ Optical whole-cell groundwat mod heavy metals, biosensor using microer e solvents algae aerosols mea sure ment
Commercial (www.biosensores.com)
POLITOX
Biosensores SL
High
Prototype [17, 18, 19, 20]
Ecole Nationale Suprieure des Mines de St Etienne
0.1nM
Standard deviations with 10 membranes were 1.9% in the flow mode and 3.2% with the drop deposition technique.
94
Monitoring issues
Toxicity
Portable toxicity testing system specifically for solids based on bioluminescent bacteria
Solid matrix
Prototype [21, 22]
100 g/L for benzene, 50 g/L for Cybersense phenol, Biosystems Limited 20mg/L copper, 125mg/L for PAH Assays rejected if COV exceeds 10%
Luminescence based Soil, whole cell toxicity Mixture of commercial and sediment, labor sensors prototype Bacteria, fungi (yeast water, food, atory [23, 24, 25, 26, 27] wastes and multi-cellular), algae, nematodes etc. recombinant Fresh bioluminescent water, Prototype Toxicity/ TBT, DBT Escherichia coli strain marine [28, 29] harboring the luxAB water, genes of Vibrio harveyi sediment Water and CellSense Lab soil Commercial Amperometric whole cell 30 Toxicity [30, 31, 32] bacterial biosensor min Toxicity: acutely toxic risk chemicals-metals and organics Optical whole-cell Surface biosensor using micro- and ground algae designed for -water, toxicity assessment aerosols Water samples Bioluminescence and soil inhibition assay and sediments extracts. Prototype [18, 19, 20]
Remedios Ltd
University of Aberdeen
CBAC : capteur bactrien pour University of Nantes lanalyse et le contrle
8%
CellSense
Euroclone Ltd
Screening
Low concentration levels are obtained with herbicides (0.1 nM for diuron).
Toxicity
Ecole Nationale Suprieure des Mines de St Etienne
Toxicity
Lab 1530 min
Commercial [33, 34, 35, 36, 37]
ToxAlert 10, ToxAlert 100
Merck
High
Screening
ORGANIC CONTAMINANTS
volatile HC Membrane interface probe soil, sediment, groundwat er Commercial MIP/CPT Fugro Milieu Consult 100g/L
95
Monitoring issues
mineral oil product, PAH unsaturated HC PAHs BTEX, CHC, mineral oil
Fluorescence
Fluorometry system
soil, sediment, groundwat er groundwat er
Commercial [38] Prototype [39, 40, 41]
ROST
Fugro Milieu Consult
screening technique 1g/L
sensor system Institute of Hydraulic 1 Engineering VEGAS sensor system Institute of Hydraulic 2 Engineering VEGAS sensor system Institute of Hydraulic 3 Engineering VEGAS
Sensor for detecting liquid phase groundwat cont Prototype er contaminants based on optical fibres mercury, PAH, Acoustic sensor: Metal Soils, Prototype BTEX, Chlorinated oxide sensors and groundwate [42, 43] HC quartz oscillators r Volatile organic compounds (VOC) Commercial IR-PID-Portable gas In and other toxic Soil, air (http://www.georentals.co.u analyser situ gases LNAPLs, k/ecoprobe5.htm) DNAPLs, PAHs MTBE Immunoassay test kit Water Water automated Prototype Prototype Free, total, Electrochemical sensor combined chlorine
100mg/L 30.000mg/L
Ecoprobe 5
RS DYNAMICS Ltd.
20 g/L
DIACLONE Cranfield University
50-5000 g/L
Dissolved hydrocarbons
Optical fibre chemical sensor
Surface/grou nd water, atmosphere
Commercial (http://www.interlab.es/opto sen/optosen1.htm)
OPTOSEN
Down to 0.002 mg/L Cl CO2: 0.1 - 30% (in air) Humidity CO2: 1% INTERLAB, 1 - 100% RH Humidity: S.A.UNIVERSIDAD (at 30 C) 0.3% COMPLUTENSE Hydrocarbons Hydrocarbon DE MADRID 5 1500 mg/L (in s: 5% water) Sensor Tech Ltd down to the range of g/L
POPs Small Organic Water Pollutants: Herbicides, Fungicides, Insecticides, and Endocrine Disrupting Compounds
Potentiometric Biosensor based on screen-printed electrodes
soil, oil and water
Prototype
immunosensor coupled surface with detection via Total and Internal Reflection groundwat Fluorescence (TIRF) er sources
Prototype [44, 45, 46]
RIANA
University of Tuebingen
<0.1 g/L typically possible depending on the analyte of interest
96
Monitoring issues
Small organic water pollutants: herbicides, fungicides, Automated Water insecticides, Analyzer Computer surface endocrine Supported and disrupting immunosensor coupled compounds, groundwat with detection via Total er sources antibiotics, Internal Reflection suspected Fluorescence (TIRF). carcinogens, and industrial wastes/chemical markers Using a bipotentiostat configuration, the sensor monitors the conductance of a bilayer PCBs, PAHs, lipid membrane, which metals, phenols incorporates ligandgated channel proteins specific for the target analyte Flow injection system Phenols based on Glucose deshydrogenase Flow injection system based on cellobiose Phenols deshydrogenase Amperometric biosensor Phenols using GDH modified waters thin-film electrode surface and Amperometric mediator- groundwat Phenols modified enzyme sensor er and wastewat er
On line
Prototype [47, 48, 49] T7
AWACSS
University of Tuebingen
Typically <0.1 g/L
Prototype
Coventry University
Prototype
Lund University
Prototype Prototype [50, 51]
Lund University Potsdam Univ, BST Berlin UFZ Centre for Environmental Research Environmental Biotechnology Centre
Prototype
2 g/L
97
Monitoring issues
Phenol
Catechol, polyphenols, flavanol
Tirosinase based amperometric sensors for an FIA system (TRACE Analysis system GmbH) Electrochemical biosensor using either plant tissue material
water
FIA
Prototype/ Commercial [52, 53] Prototype [54, 55, 56]
TRACE Biotech AG Universidad de (Braunschweig, Alcal de Henares, Germany) University of Ulster Perpignan 12% University : reproducibilit Laboratory BIOMEM y Cranfield University
Screening
brewing industry On field
down 2.5 M
Pesticides / organo Portable amperometric water, fruit phosphorus biosensor system juice Isoproturon Amperometric immunosensor water and food
Prototype [57, 58] Prototype
range of g/L
METALS AND INORGANIC SPECIES

NO2 Heavy metals: mercury, organosoil, mercury Luminescence based sediment , compounds, biotest water, arsenic (both III effluent and V, speciation), cadmium, lead, copper. Cr, Mn, Fe, Co, Ni, Urease biosensor based Water, Cu, Zn, As, Se, Pb, on the amperometric extracted Hg, Rb, Sr, Zr, Mo, analysis of NADH with soils or Ag, Cd, Sn, Sb, screen-printed sediments Ba, K, Sc, Ti, V electrodes Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Pb, Pulse neutron based water, soil Hg, Rb, Sr, Zr, Mo, sensor samples Ag, Cd, Sn, Sb, Ba, K, Sc, Ti, V. Prototype Coventry University
Commercial [59, 60, 61, 62]
Aboatox Oy
Lab, on field
Prototype [63, 64]
Cranfield University
In situ
Commercial [65, 66, 67]
Bohrlochmessungen -Dr
98
Monitoring issues
Cr, Mn, Fe, Co, Ni, soils, Cu, Zn, As, Se, Pb, Dispersive X-Ray ores, air Hg, Rb, Sr, Zr, Mo, Fluorescence (EDXRF) and water Ag, Cd, Sn, Sb, Ba, filters K, Sc, Ti, V. Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Pb, water and Hg, Rb, Sr, Zr, Mo, Electrochemical system soils Ag, Cd, Sn, Sb,Ba, extract K, Sc, Ti, V.
Commercial [68, 69]
NITON Xli and XLt 700Series Energy Dispersive XNiton Europe GmbH Ray Fluorescence (EDXRF) analysers Heavy Metal Analyser HEMA 2002
lab
Prototype
NMRC, Ireland
Lead
Flow injection analysis and a potentiometric sensor
Prototype
QUAMET
Universitat Autnoma de Bellaterra, Barcelona. Grup de sensors I Biosensors
surface and Electrochemical batch Lab, Toxic Trace metals injection analysis sensor groundwat field er, system effluent anoxic fresh and anoxic/oxi Trace elements Voltammetric probe c sea metals waters, sediments interface fresh, sea In Voltammetric In situ waters situ, Profiling System (VIP Trace elements surface auto system) based on geland mate metals integrated microsensor groundwat d, array er cont
Prototype [70, 71, 72]
Instituto Pedro Nunes
Prototype [73, 74]
University of Neuchatel
Commercial [75, 76]
99
Monitoring issues
Trace elements metals
Compact portable Voltammetric In-line fresh, sea Analyzer for on-Field waters monitoring (VIA-Fieldsystem). Voltammetric flowthrough micro cells Fresh and sea waters
On site
Prototype [77] Prototype for C and Au microelectrodes commercial for Ir [73, 74]
Trace elements metals
Bioassay based on the E coli CM1569 is a soils, Arsenite (AsO2-) derivative of E. coli sediment, and arsenate DH10B containing surface (AsO4) pC202 and the groundwat ANTHOS LUCY1 er luminometer Bioassay based on the R. eutropha AE2440, a soils, derivative of R. eutropha sediment, CH34, containing Chromate surface pMOL1531 and the groundwat ANTHOS LUCY1 er luminometer Bioassay based on R. metallidurans AE1239 is soils, a derivative of R. sediment, Copper (Cu2+) metallidurans AE866 surface containing only pMOL90 groundwat and the ANTHOS er LUCY1 luminometer Bioassay based on R. metallidurans AE2515, a soils, derivative of R. sediment, Nickel (Ni2+) and metallidurans CH34 surface Cobalt (Co2+) containing pMOL1150 groundwat (20.8kb), and the er ANTHOS LUCY 1 luminometer
Prototype [78, 79]
Vlaamse Instelling voor technologisch onderzoek (Vito)
Prototype [80, 81]
Prototype [79]
Prototype [81] T8
100
Monitoring issues
Bioassay based on R. eutropha AE2450 is a derivative of R. eutropha CH34 containing Lead (Pb2+) pMOL1539 (19.1 kb) and the ANTHOS LUCY 1 luminometer Bioassay based on R. eutropha AE1101 is the result of a biparental mating between R. Thallium (Tl+) oxalatica A5.3 (rifampicine resistant mutant of A5) and A. eutropha strain AE1050 Zinc (Zn2+), and Bioassay based on R. some effects on metallidurans AE1433 is Cadmium (Cd2+) a derivative of R. and lead (Pb2+) metallidurans CH34 containing pMOL30 Sensor system based on ISFET based sensors
Prototype
Prototype
Prototype
Vlaamse Instelling voor technologisch onderzoek (Vito) Consejo Superior de Investigaciones Cientficas Institute of Microelectronics (IMB-CNM)/
pH, Ca2+, K+, NO3
Prototype
101
Monitoring issues
102
Monitoring issues
2.2.6 - Biologiocal early warning systems/Whole organism bioassays

Whole organism bioassays have been used for many years to test the acute toxicity of aqueous samples or extracts from soils and sediment. While most of them provide useful data on the short-term toxicity of water samples, they fail to provide information on longer term toxicity. Therefore, for long-term toxicity of water, ecological monitoring may reveal more useful. In some cases such as the use of the Microtox test, a large amount of data is available for many chemicals, which may be helpful to interpret results from toxicity studies. While setting-up and keeping cultures alive is costly and laborious, it is, nowadays, possible to obtain kits that are relatively simple to set-up for conducting toxicity tests. The remaining drawback is their labbased implementation that still requires the spot sample to be collected in the field and brought back to the laboratory for analysis. An improvement on these standard bioassays using whole organisms is their introduction into on-line continuous system or for in-situ deployment. In the past 20 years, a number of systems based on the behavioural response of biological whole organism to changes in water quality have been developed. Systems are generally based on the acute toxicity of chemicals or mixture of chemicals present in water. The behaviour of the organism whether it is a mussel, fish, daphnia, 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 detected it, a transducer, is then transformed into an representative electrical signal. These devices are particularly useful for water quality monitoring at drinking water, aquaculture intakes for example or for continuous monitoring of industrial waste waters. The following table (Table 13) presents a list of these technologies 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 stimuli (i.e. change in swimming behaviour of fish or daphnia, 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 these systems may not only be able to detect chemical toxicants but also microbiological pathogens. The three on-line biosensors for general toxicity/BOD using respirometry listed in Table 12, are also a form of biological early warning systems and could also be present in this table.
103
Monitoring issues
Table 13. Biological early warning system commercially available or in development Biological organism used in assay
Freshwater fish
System ID
Stimuli
Applications/ Additional Availability data
Contact detail
AquaTox Control
Ability to swim against current
BehavioQuant
Fish
Video analysis system: Fish swimming behaviour
Commercially available
Kerren Umwelttechnik, Ing (Olaf) Hollstein, Postfach 100640, Helmho 26, D - 4060 Viersen, GER Tel: +49-2162 9393 Fax: +49-2162 33514 Bundesanstalt fr Gewss BFG, Section Ecotox.; Dr. E. (Elke) Blbaum-Gro Postfach 309, Kaiserin Au Anlage 15-17, D - 56003 KOBLENZ, GERMANY Email: bluebaumgronau@koblenz.bfg.bund Tel: +49-261.1306 5105 Fax: +49-261.1306 5302 8/16 bivalves options, possibly for additional sensors (pH, DO)
Electric pulse monitor MosselMonitor
Dynamic Daphnia Test, Daphnia Test
Freshwater fish only Freshwater mussel: Dreissena polymorpha Unio pictorum Marine mussel: Mytilus edulis Water flea
Lab-version Valve movement response On-line and insitu Commercially available
Delta Consult B.V. Postbu 4420 AC Kapelle, The Netherlands Tel: +31 113 36 21 00, Fax: +31 113 36 21 99 E-mail: Jan de Maat
Daphnia activity and swimming behaviour
Kerren Umwelttechnik, Ing (Olaf) Hollstein, Postfach 100640, Helmho 26, D - 4060 Viersen, GER Tel: +49-2162.9393, Fax: +49-2162.33514 Samples collected every 30min
DF-Algentest, Flu0x40measurement system
Algae (Chlamydomonas species)
Oxygen production and consumption / Chlorophyll measurement using fluorescence
Semi-continuous measurements
Dr. Volkmar Gerhardt Universitt RegensburgI fr Angewandte und Experimentelle PhysikUniversittsstrae 3193053 Regensburg Tel.(0941) 943 2141
Multi-species freshwater biomonitor
Prototype
Dr. A. Almut Gerhardt, An der Aa 5, D - 49477 IBBENBUEREN, GERMAN Email: limco.int@t-online.d Tel: +49-5451.970 390 Fax: +49-5451.970 390
An assessment of the cageculture turbidostat as an alternative algal bioassay(1998)
cage culture turbidostat
Algae
Algal growth rate monitoring
Prototype
104
Monitoring issues
Water Res., Vol. 32 (4), pp 11621168 N. Clarkson,et al
Aws automated digital sensor: BD5 SEM Truitosem CIFEC Truitel ToxAlarm, Toxiguard:
Young trout (fingerlings of 3)
CIFEC, 12 bis rue du Cdt 92200 Neuilly/Seine, Fran Tel: 33 (0)1 4640 4949, Fax: 33 (0)1 4640 0087, Email: info@cifec.fr.
Algae and bacteria
Respirometry: Algal/bacterial O2 prod/consumption
Solyom, P. (1977) Industrial experiences with TOXIGUARD, a toxicity monitoring system. Prog. Wat. Technol. 9 (5/6), 193-198.
Bull. Environ. Contam. Toxicol. 2001 66: pp 392 -399. ASTM (1995) Standard guide for ventilatory behavioral toxicology testing of freshwater fish. Designation E 1768 -95. p8.
USACEHR Fish Biomonitoring system
bluegill (Lepomis macrochirus)
Fish ventilatory rate, depth, and cough frequency and body movement patterns
USACEHR 568 Doughten Drive Fort Detrick, MD 21702-50 http://usacehr.detrick.army aeam/Methods/Fish_Bio/d
Rhine-Danube paradigm Combined fish & daphnia Toximeter
Dynamic daphnia test and mossel monitor Young living zebrafish and daphnia
Speed and swimming observations (altitude, circular movements, turns), growth and death Speed and swimming observations (altitude, circular movements, turns), growth and death Photosynthetic activity Oxygen consumption and transition to anaerobic metabolism
Fish toximeter
Zebrafish (Danio rerio)
BBE - Moldaenke GmbH; (Detlev) Lohse; Wildrosenweg 3, D - 2411 KRONSHAGEN, GERMAN E: DLohse@bbe-moldaen www.bbe-moldaenke.de T: +49-431.380 400 F: +49-431.380 40 10 BBE Moldaenke GmbH
Algae toximeter Trondheim early warning system
Algae Blue mussel (10)
Commercially available Prototype?
BBE Moldaenke GmbH
SINTEF Applied Chemistry N-7465 TRONDHEIM Tel: (+47) 73 59 28 73 Fax: (+47) 73 59 69 95
105
Monitoring issues
Research in Europe: During the last three decades numerous test methods have been developed to assess the effects of chemicals pollutants on the environment. In this summary, the most relevant biological tools developed under the European Commissions 4th and 5 th Framework Research Technology and Development Programs (1994-1998 (FP4) and 1998-2002 (FP5)), with special attention on sensors and biosensors achievements are compiled. Another list of sensors and biosensors available for water quality monitoring may be found on the Sensor for Water Interest Groups website (SWIG): http://www.swig.org.uk/Section%20A%20(research%20projects)%20master.pdf Under these EU programs over 300 projects have been carried out within the Environment and Climate program. Table 24 (appendix 3) presents the more relevant projects. It is important to highlight certain concerted actions: Biosensor for Evaluation of the performance of Waste Water Treatment Works (BIOSET)(http://www.cranfield.ac.uk/biotech/bioset/) and, Sensors for Monitoring Water Pollution from Contaminated Land, Landfills and Sediment (SENSPOL) (http://www.cranfield.ac.uk/biotech/senspol/), which are networks of excellence that have been organizing various annual workshops on different areas of biosensors for environmental monitoring in order to stimulate research in that topic in Europe. On table 24 (appendix 3) are summarised sensors, biosensors and biological bioassays developed under the EU Framework research programs and, on table 25 (appendix 3) the main achievements (in appendix).
106
Monitoring issues
2.3 - Chemical assessment techniques

Table 14 presents chemical methods for the measurement of PAHs and heavy metals from water samples. Chemical sampling of polar, non-polar organic pollutants as well as for inorganic contaminants such as metals has generally relied on spot or grab sample collection. In other words, it provides a picture of chemical contamination of a body of water only at the time of sampling. In these cases, 1-2 L water samples are collected and brought back to the laboratory for analysis. Despite high costs (field collection and laboratory work), this method is generally easy to implement. The main drawback of this standard sampling technique is that it fails to give a long-term picture of the chemical contamination of a water body. It may easily miss higher or lower concentration events. 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 15, 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. Table 16 reviews chemical analytical methods that are available for the quantitation of organic and inorganic pollutants, depending on their physico-chemical properties. References are made to related existing standard methods, total and running costs, and robustness. The following table (17) reviews all currently available immunoassay test kits available for a wide range of organic pollutants such as PAHs, pesticides, PCBs.
107
Monitoring issues
Table 14. Currently available chemical analytical methods to measure Heavy metals and PAHs
Calibration Range
Maintenance Frequency (Days)
Precision of the measurement
Parameter
Method
Type of water
Sampling time (min)
Costs
Model
Response
Cycle duration
HEAVY METALS Heavy Metal

(Pb, Cu, Zn, Cd, Cr3, Cr6, Ni) 30min for 6 metals Cd:1-100g/L Pb.Cu.Cr6.Ni :5-500g/L Zn:101000g/L Cr3:20020000g/L 10-1000g/L (for Cu. Zn. Cr(VI)) 5400g/L (Pb) 0.5-200g/L (Cd) 0.01100mg/L
Membranes: Polarography
All
15
HEAVY METALS ANALYSER
ELTA
1g/L
Heavy metals
Membranes: Polarography
All
ML 9000
ENVIRONNEMENT SA
<10%
Mercury PAHs
Optical: Photometry: UV Spectrometry - Cold Steam Method
All
MERCURY ANALYSER PA-1
MARTEC
Optical: Fluorometry
All
BACKSCAT
AQUAMS
0-50/0-1600 g/L chrysene
108
Maintenance duration (min)
Variable measured*
Monitoring issues
Membranes: Fusible
ECOSTACK
AQUAMS
Detection of a thickness of layer of 0.5 mm 0,1 g/L 0-500 mg/L naphthalene equivalent 0-1000 mg/L reproducibility 0-10000 g/L : 3 g/L, (phenol detection limit: equivalent) 3 g/L +/- 10% 0-30 mg/L
Optical: Fluorometry 254/360 nm Optical: Fluorometry
All All
FLUO HPA ANALYSER SERIES 1000 FL 200
AQUAMS AWA INSTRUMENTS
Optical: Fluorometry
All
DATALINK ENVIRONNEMENT SA EQUIPEMENTS SCIENTIFIQUES SA HORIBA FRANCE ISMA ISMA MARTEC MARTEC NEREIDES
Optical: Photometry: IR Optical: Fluorometry Optical: Photometry: NDIR Optical : Light intensity reflection Optical : Light intensity reflection Optical: Light dispersion Optical: Fluorometry Membranes: Fusible membrane dissolving Optical: Photometry: IR absorption at 3420 nm (Total Hydrocarbon ) 3300 nm (Aromatic Hydrocarbon) SE, R, IE SE, R SE, IE SE, R, IE SE, R, IE SE, R, IE SE, R, IE 4s to 2 min
HC 9010 HYDROSENSE 9410 OCMA 25 ODL 12 / DHC 102 OF - 10 ANALYSER MULTIFONCTIO NS OMD7 SPILL-SENTRY OILSPY
0-10 / 0-500 1 mg/L mg/L Repeatability : 0-10 0 0-20 +/- 3 % PE mg/L
0-200 mg/L 5 m
SE, R
DHIR
SERES
3% of the range or 0,3 mg/L
0-10 mg/L 0-30 mg/L
Keys: Method: S = Spot sampling, O = Continuous monitoring, T = Test kits, P = Passive sampling Types of waters: T = Treated water, R = Raw waters, SE = Sewage Effluent, IE = Industrial Effluent, L = leachate
109
Monitoring issues
Table 15. Non-biological sampling methods available for monitoring environmental substances
Robustness*
Method
Classes of substance measured*
Typical detection limit
Sampling period
Costs
SPMD Solvent filled dialysis membranes Ceramic dosimeter Adsorption dosimeter POCIS Portsmouth passive sampler Gore-Sorber Gaiasafe passive sampler MESCO DGT SPME
P P P P P P P P P P S,P
N N P, N, M N, P P P,N,M N P,N,M N M N,P
D D D D D D D unknown D D D
ng/L ng/L g/L mg/L ng/L ng/L g/L Unknown ng/L ng/L ng/L
8 5 10 5 8 8 unknown unknown 4 6 4
up to 1 month weeks Weeks - months months weeks weeks weeks
U.S. patents #5098573 and # 5395426
EUR 50
1, 2 3, 4, 5
German patent DE 198 30 413 A1
U.S. Patent #6478961 Euro 112
8, 9 10, 11, 12 13 14
UK Patent No. GB 2 353 860.
weeks weeks minutes
German Patent DE 100 42 073 Patents WO95/05591 and GB2295229
15 16 17, 22, 25
U.S. patent #5691206, European patent #523092
110
References
6 7
Variable measured*
Sampling
Monitoring issues
Ecoscope Solvent filled polyethylene membranes Silicone passive sampler PISCES Stir bar sorptive extraction (SBSE) MESI
P P P P S O
N,P,M N N N N,P N,P
D D D D D D
ng/L ng/L ng/L ng/L ng/L g/L
6 8 9 unknown
weeks weeks weeks weeks
18 19, 20 21 24 26, 27, 28 23
*Keys:
Classes of substance measured: N = Non-polar organic, P = Polar organic, M = Metals Sampling: S = Spot sampling, O = Continuous monitoring, T = Test kits, E = Sensors, P = Passive sampling, Variable measured T = Total present D = Dissolved only Robustness: expressed on a scale 0-10 (0 and 10 are the least and most robust respectively)
111
Monitoring issues
Table 16. Laboratory/field chemical analytical methods reference/cer tified reference materials available
Technique
Reference Relevant to Parameters standard methods
Status*
Cost
Running cost/annum (euro)
Suitable for Robustness regulatory use (yes/no)
GC-ECD
Molecules that have at least one halogen atom
Dioxins
L, F
yes
60000
2000 - 3000
Yes
GC-MS
requires isotopic dilution with HRMS
Dioxins
L, F
yes
From 130000 to 350000 From 150000 to 180000
3000 - 12000
Yes
LC-MS Atomic fluorescence spectrometry Cold Vapour-AAS
Dioxins
yes
3000 - 12000
Yes
Hg
EN 13506
L, F
yes
Yes
Hg
EN 1483
L, F
yes
Yes
CV-AAS with Amalgamation
Hg
EN 12338
L, F
yes
Yes
112
Monitoring issues
ET-AAS
Most metals
EN ISO 5961,ISO DIS 15586, DIN 38406, US EPA 7421 ISO 8288
L, F
yes
35000- 60000
Yes
flame AAS GC GC or HeadspaceGC
Most metals
L, F L, F L, F
yes yes yes
15000
3000
6 6 6
Yes Yes
Organophosphorus DIN EN 12918, compounds NF T 90-250 Highly volatile halogenated EN ISO 10301 hydrocarbons Organochlorine insecticides, PCBs EN ISO 6468, US EPA 8081 and chlorobenzenes Organohalide pesticides and commercial US EPA 505 polychlorinated biphenyl (PCB) Phenols Chlorophenols PAH ISO 8165-2 EN 12673 US EPA 8100 ISO WD 22032, ISO DIS 18856, US EPA 8270, ISO CD 18857-1, ISO/AWI 23161, XP X33-012 ISO/DIS 17353
GC/ECD
L, F
yes
Yes
GC/ECD (MS for conf.) GC/ECD after Derivatisation GC/ECD/MS after Derivatisation GC/FID
L, F
yes
Yes
L, F L, F
yes yes yes
6 6 8
Yes Yes Yes
GC/MS
L, F
yes
Yes
GC/MS - FPD AES
yes
113
Monitoring issues
GC/MS or GC/ECD or GC/NPD Headspace-GC/FID HPLC/Fluo
Phosphorylated and halogenated EN ISO 10695 compounds Benzene and DIN 38407-9, related compounds ISO 11423-1 PAH ISO 17993, DIN 38414-23
L, F L L, F
yes yes yes
6 6 8
Yes Yes Yes
HPLC/UV
Parameters that have or form a EN ISO 11369, chromophore with a XP X33-012 selective reagent
L, F,H
yes
From 2000 - 20000
300 - 3000
Yes
ICP-AES ICP-MS Purge/Trap + Thermal Desorption TLC, AMDTechnique Voltammetry
Most metals Most metals
EN ISO 11885 ISO/DIS 17294-2 Draft ISO 15680 ISO 11370 2000
L L L, F L, F L, F
yes yes yes yes yes
60000 -100000 100000-200000
9 7
Yes Yes
8 15000 2
Yes No
Reducible metals
DIN 38406-16
*Keys:
Status : L = laboratory-based measurement, F = field measurement; Robustness: expressed as %.
114
Monitoring issues
Table 17. Immunoassay test kits
Variable measured*
Parameter
Method
Type of water
Type of device (reference)
Costs
Mode
precisio n of the measure ment
Calibration Range
Acetochlor and other acetanilides
Polyclonal antibodies attached to magnetic particle
Incubation time 45 min water, food, Read soil absorbanc e at 450nm water
100 tests per kit
A (100 tests)
Acetochlor ELISA kit
Abraxis LLC (USA), Biosense biosense
0.1 g/L
0.10 to 2.5 g/L (quantitative, semiquantitative and qualitative)
Alachlor ELISA field or lab testing method 50 samples at one time Alachlor RaPID Assay Aldicarb RaPID Assay
Randox Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
Alachlor
Aldicarb
50 min Soil, food or Read water absorbanc samples e at 450nm Read Antibody coated absorbanc Water paramagnetic particles e at 450nm Antibody coated magnetic particle.
0.1 g/L
0.05 to 5.0 g/L
30/100 test per kit
Alkyl Ethoxylates C10-C12
Read Monoclonal antibodies Surface and 96 tests may be absorbanc attached to surfaces of waste performed at any one e at microtitre plate wells waters time 450nm Read Monoclonal antibodies Surface and absorbanc 96 tests at any one attached to surfaces of waste time e at microtitre plate wells waters 450nm
Alkylphenols
Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Developed by Japan EnviroChemicals, A per kit Takeda AE Ltd., licenced by (96 EIA kit Takeda Chem. Ind. tests) biosense distribution Developed by Japan A per kit Takeda AP- EnviroChemicals, (96 EIA kit Ltd., licenced by tests) Takeda Chem. Ind.
Low g/L
0.25 to 100 g/L
g/L
20 to 1000 g/L
Low g/L
5 to 500 g/L
115
Monitoring issues
Monoclonal antibodies attached to surfaces of the tube Alkylphenols Ethoxilates Monoclonal antibodies attached to surfaces of microtitre plate wells
Water
Read absorbanc e at 450nm
20 test kit (tubes)
Water
96 test kit
Arsenic 50 min soil, food or water Read samples absorbanc e at 450nm 50 min Read Water, soil absorbanc e at 450nm 60 minassay US EPA approved Method 4670 for drinking water
biosense distribution Developed by Japan EnviroChemicals, A per kit Takeda Ltd., licenced by (20 APE-EIA kit Takeda Chem. Ind. tubes) biosense distribution Developed by Japan EnviroChemicals, A per kit Takeda Ltd., licenced by (96 APE-EIA kit Takeda Chem. Ind. tests) biosense distribution Baoding Way Chen Sodium Food Industrial Co. Diacetate LTD. Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
g/L
20 to 1000 g/L
g/L
20 to 1000 g/L
Antibody coated magnetic particle.
Rapid field or lab testing method
Atrazine Rapid Assay
0.1 g/L
0.04 to 5.0 g/L
Antibody coated magnetic particle. Atrazine and related triazines
Rapid field or lab testing method Up to 43 samples Rapid field or lab testing method
HS Atrazine Rapid Assay
15 ng/L
15 to 1000 ng/L
Competitive-type ELISA Water and using polyclonal food antibodies immobilised products on microplates Mix enzyme conjugate with sample then addition of the colour solution Competitive-type ELISA using polyclonal antibodies immobilised in tubes
Transia Plate Triazines
Diffchamb AB
0.02g/L
<50 min Water, Read The kit, a 96-well sediment, absorbanc microplate and ready soil, fish e at to use reagents plasma 450nm water and food products 15 minassay
A per kit
Atrazine ELISA kit
Abraxis LLC (USA), biosense
ng/L
0.03 to 3 g/L
Transia Tube Triazines
Diffchamb AB
0.1g/L
116
Monitoring issues
Latex particle/membrane immunoassay Benzene Compounds Antibody coated magnetic particle.
15 minSoil, water assay time 60 minassay time Read Water, soil absorbanc e at 450nm urine, serum, tissue, milk, feed
Up to 4 samples simultaneously
US EPA SW 846 4030 / CAL EPA US EPA SW 846 4030 / CAL EPA
D-Tech BTEX Test
D-Tech / Strategic Diagnostics
2.5mg/L
2.5 to 35 mg/L (soil) 0.6 to 10 mg/L (water)
100/30 test kits available Rapid field or lab testing method
BTEX Rapid Assay
Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
20g/L
0.9 to 30mg/L (soil) 0.02 to 3.0mg/L (water) as total BTEX
Benzodiazepines
Benzodiazep ine ELISA Kit
TECNA S.r.l
Monoclonal antibodies attached to surfaces of the microtitre plate or tubes Bisphenol A Monoclonal antibodies attached to surfaces of the microtitre plate
Water
Readings 96 tests at any one of time absorbanc 20 tests at any one e at time 450nm Readings of 96 tests at any one absorbanc time e at 450nm
A per kit Developed by Japan (96 EnviroChemicals, tests) A Takeda BPA Ltd., licenced by per kit EIA kit Takeda Chem. Ind. (20 biosense distribution tubes Takeda A per kit supersensiti (96 ve tests) BPA EIA kit Developed by Japan EnviroChemicals, Ltd., licenced by Takeda Chem. Ind. biosense distribution
g/L
5 to 500 g/L
Water
ng/L
0.05 to 10.0g/L
Carbendazim/ Benomyl
Antibody coated paramagnetic particles
Readings of water, soil absorbanc e at 450nm
100 test kit
USDA AMS
Benomyl/Car Ohmicron Environmental bendazim Diagnostics, Inc./ RaPID Strategic Diagnostics Assay Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
g/L
0.10 to 5.0 g/L
Carbaryl
water
Read 30/100 test per kit for absorbanc up to 50 samples e at Rapid field or lab 450nm testing method
Carbaryl RaPID Assay
0.25 g/L
0.25 to 5.00 g/L
Carbofuran
Read 30/100 test per kit for absorbanc up to 50 samples water, soil e at Rapid field or lab 450nm testing method
Carbofuran RaPID Assay
0.25g/L
0.25 to 5.00 g/L
117
Monitoring issues
Carazolol
urine, muscle Read absorbanc water, soil e at 450nm AOAC Official Method 28.1.45
Ridascreen Carazolol
r-Biopharm GmbH
Captan
Captan RaPID Assay
Carbon Dioxide
food
Carbon Dioxide Assay
Sigma Chemical Corp
Chlorine (Organic)
Colorimetric titration
6, 12 or 48 tests per kit Water, Rapid test to antifreeze <10minand oil/water assay time determine chlorinated solvents in water and mixture waste waters 60min-test 30/100 test per kit for Read up to 50 samples water, soil absorbanc Rapid field or lab e at testing method 450nm 60min-test Read absorbanc e at 450nm 100 test kit (50 samples) Rapid field or lab testing method
Hydroclor-Q
Dexsil Corp
200 to 4000mg/L
Chlorothalonil
Chlorothanil Rapid Assay
Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
0.07 g/L
0.07 to 5.00 g/L
Chloropyrifos
water
Chloropyrifo s Rapid Assay
0.1 g/L
0.22 to 3.0 g/L
Cyanazine
60 mintest 30/100 test per kit for up to 50 samples Read water, soil absorbanc Rapid field or lab testing method e at 450nm
Ohmicron Environmental Cyanazine Diagnostics, Inc./ Rapid Assay Strategic Diagnostics
0.04g/L
0.04 to 3.0 g/L
118
Monitoring issues
Cyclodienes (dieldrin, endosulfan)
Mix enzyme conjugate with sample then addition of the colour solution
<2 hours Read water, soil, The kit, a 96-well sediments, absorbanc microtitre plate and e at fish plasma ready to use reagents 450nm
A per kit Cyclodienes Abraxis LLC (USA), (96 ELISA kit biosense tests)
0.25 to 25 g/L
Antibody coated Cyclodienes (BTO) paramagnetic particles
water
DT/DDE/DDD
Mix enzyme conjugate food, water, with sample then soil, addition of the colour sediments, solution fish plasma Polyclonal antiserum attached to magnetic particles Antibody coated paramagnetic particles Monoclonal antibodies immobilised at the surface of microtitre plate wells or to tube surfaces Polyclonal antibodies attached to magnetic particles food, water, soil, sediments
Diuron and related phenylurea herbicides
2,4-D
water, soil
Total Estrogens
Water
Glyphosate
Water, soil
water Isoproturon Polyclonal antibodies attached to wells on plates
60 min100 test kit (50 test samples) Cyclodienes Read Rapid Assay absorbanc Rapid field or lab testing method e at 450nm < 2 hours The kit, a 96-well A per kit Read DDT- ELISA microtitre plate and (96 kit absorbanc ready to use reagents tests) e at 450nm Assay time The kit, a 96-well A per kit of 1 hour, Diuronmicrotitre plate and (96 Reading at ELISA Kit ready to use reagents tests) 450nm 60min test EPA SW30/100test kit for up 2,4-D Rapid Read 846 to 50 samples tested Assay absorbanc Method Rapid field testing e at 450nm #4015 A per kit The kit, a 96-well (96 Takeda microtitre plate or 20 Read tests) supersensitiv absorbanc tubes and ready to e A per kit e at 450nm use reagents (20 ES EIA kit tubes) Assay time of 1 hour A per Glyphosate 120 tests per kit 120 HS ELISA Read absorbanc tests kit, 120T e at 450nm Isoproturon ELISA Read 8strips x 12wells per absorbanc kit e at 450nm + reagents. EnviroGurad Isoproturon plate kit
0.15 to 7.5 mg/L (soil) 0.6 to 26.6 g/L (water)
g/L
1.25 to 75.0 g/L 0.03 to 3.0 g/L (quantitative, semiquantitative or qualitative) 0.7 to 50 g/L (water) 0.15 to 7.5 mg/L (soil)
Abraxis LLC (USA), biosense Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Developed by Japan EnviroChemicals, Ltd., licenced by Takeda Chem. Ind. biosense distribution
ng/L
1g/L
0.1g/L
0.1 to 3.0 g/L
1.0 g/L
1.0 to 25.0 g/L (quantitative, semiquantitative or qualitative test)
Randox Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
0.02 g/L
0.05 to 0.5 g/L
119
Monitoring issues
Monoclonal antibodies Surface and Read attached to microplate waste absorbanc surfaces waters e at 450nm Linear Alkylbenzene Sulfonate (LAS) Monoclonal antibodies attached to tubes Surface and Read waste absorbanc waters e at 450nm
96 tests
A per kit Takeda (96 test) LAS-EIA kit
20 tests
A per kit Takeda (20 LAS-EIA kit tubes)
Metholmyl
water
Read 30/100test kit for up absorbanc to 50 samples tested e at 450nm Rapid field testing
Methomyl Rapid Assay
Antibody coated paramagnetic particles Metalochlor
50min-test 30/100test kit for up Read to 50 samples tested Water, soil absorbanc Rapid field testing e at 450nm Total incubation Polyclonal antibodies Water, food, <60 min 100 tests per kit attached to magnetic soil Read particles absorbanc e at 450nm Water Read absorbanc e at 450nm
Metalochlor Rapid Assay
Developed by Japan EnviroChemicals, Ltd., licenced by Takeda Chem. Ind. biosense distribution Developed by Japan EnviroChemicals, Ltd., licenced by Takeda Chem. Ind. biosense distribution Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
20g/L
20 to 1000g/L
20g/L
20 to 1000g/L
0.45 g/L
0.45 to 15.0g/L
0.01g/L
0.05 to 5.0 g/L
A per kit Metalochlor (100 ELISA Kit tests)
Abraxis LLC (USA) biosense
0.25 to 5.0 g/L (quantitative, semiquantitative or qualitative)
Metribuzin
Metribuzin Rapid Assay Mutatox Genotoxicity Test 6-12 samples depending on the assay US EPA SW 846
Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Microbiotics Corp
Mutagens
water, waste water Water, milk, fruits and Luceferase/enzyme vegetables, 20 min-test luminescence assay tissue, honey, grains Antibody coated Read water soil paramagnetic particles absorbanc
Organophosphate pesticides and carbamite pesticides Paraquat
CideLite
Charm Sciences, Inc.
0.1 - 50 g/L
Paraquat RaPID
Ohmicron Environmental
120
Monitoring issues
e at 450nm Petroleum (aliphatic and aromatic hydrocarbons) Turbimetric Soil, water developme nt
Meth 9074
Assay
Diagnostics, Inc./ Strategic Diagnostics Dexsil Corp 15mg/L for Most HC Gasoline: 1000mg/L 0.5mg/L (soil) 50 g/L (water) 15 to 2500 mg/L
Packs of 10 or 40 US EPA tests SW 846 Rapid and fieldMeth 4020 portable equipment Up to 4 samples per 30min-test hour, up to 8 samples US EPA Coated-tube Water and Read SW 846 at any one time immunoassay soil absorbanc 48 tubes per kit Meth 4030 e at 450nm Rapid field testing 10 min-test 10, 20 tests per pack, US EPA Fixed or cases of 80 test Soil/transfor SW-846 endpoint kits mer oil Method colorimetri Rapid and field9079 c titration portable equipment 5 min-test Packs of 6/12 kits or Fixed Soil, cases of 48 endpoint surfaces Rapid and fieldPCB colorimetri portable equipment (polychlorobenzene c titration ) Water, soil 10 min-test and ion specific Rapid and fieldtransformer electrode portable Analiser oil 60min-test 100/30 test kit for up Antibody coated Read to 50 samples tested US EPA soil, water paramagnetic particles absorbanc Rapid field testing e at 450nm Soil and Polyclonal antibodies ground, well, A per kit Reading at attached to magnetic surface or 100 tests (100 45nm particles tests) effluent waters 30min-test 48 tubes per kit (up to US EPA & PAHs (polycyclic Coated-tube Read 10 samples at any SW-846 aromatic Water, soil immunoassay absorbanc one time) Method hydrocarbons) e at 450nm Rapid field testing 4035
Petroflag TPH
EnSys PCB Test
0.5 to 500 mg/L (soil)
Chlor-N-Oil
Dexsil Corp
Action levels : 20, 50, 100, 500mg/L
Chlor-N-Soil
Dexsil Corp
Action level : 50mg/L
L2000 PCBChloride
Dexsil Corp Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics
Soil: 2-2000 mg/L Water: 10 g/L -2000 mg/L 0.5 g/L 0.5 to 10 mg/L (soil) 0.5 to 10 g/L (water)
PCB Rapid Assay
PCB ELISA kit
biosense
EnSys PAH Test
1mg/L (soil) 15 g/L (water)
Total PAH in soil : 1 to 1000mg/L
121
Monitoring issues
60 min-test Read CAL EPA 100/30 test kit for up soil, water absorbanc & US EPA to 50 samples tested e at 450nm Meth 4035 Rapid field testing 60 min-test Read CAL EPA 100/30 test kit for up soil, water absorbanc & US EPA to 50 samples tested e at 450nm Meth 4035 Rapid field testing
PAHs RaPID Assay
Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics Ohmicron Environmental Diagnostics, Inc./ Strategic Diagnostics D-Tech / Strategic Diagnostics
0.93 g/L
Carcinogenic PAHs RaPID Assay
0.04 g/L
0.2 to 5.0mg/L (soil) 0.93 to 66.5 g/L (water) As phenanthrene 10 to 500 g/L (soil) as benzo[a]pyrene 0.04 to 10.0 g/L (water) As benzo[a]pyrene 0.5 to mg/L 50mg/L (soil) 5 to 500 g/L (water) 0.1 to 10.0mg/L (soil) 0.06 to 10 g/L (water) 0.8 to 100.0g/L
30min-test 48 tubes per kit (up to Read 10 samples at any Water, soil absorbanc one time) e at 450nm Rapid field testing Pentachlorophenol 60 min-test Read Antibody coated 100/30 test kit for up water, wine absorbanc paramagnetic particles to 50 samples tested e at 450nm Rapid field testing Coated-tube immunoassay Procymidone Promazine, Acetopromazine, Triflupromazine, Chloepromazine, Propionylpromazine RDX, HMX and related explosives TCE Latex particles/membrane immunoassay Read 100 test kit for up to Antibody coated Water, wine, absorbanc 50 samples tested paramagnetic particles soil e at 450nm Rapid field testing
EnSys PCP soil Test
0.5mg/L (soil) 5 g/L (water) 0.06 g/L
Pentachloro Ohmicron Environmental phenol Diagnostics, Inc./ RaPID Strategic Diagnostics Assay Ohmicron Procymidone Environmental RaPID Diagnostics, Inc./ Assay Strategic Diagnostics Promazine ELISA Kit
0.8 g/L
Urine
TECNA S.r.l.
Water, soil
CAL & US 20min-test 4 samples at a time EPA SW Read absorbanc Rapid field testing 846 Meth 4051 e at 450nm
D-tech RDX Test
0.5mg/L 5 g/L
0.5 to 5.0 mg/L (soil) 5 to 60 g/L (water)
Soil, water Soil, water
TNT
Latex particles/membrane immunoassay
Water, soil
20min-test CAL & US Read 4 samples at a time EPA SW absorbanc Rapid field testing 846 Meth e at 450nm 4050
2,4,5-TP (Silvex)
Water, soil
D-Tech TCE D-Tech / Strategic Diagnostics / PCE Test RIDASCREE r-Biopharm GmbH N TNT Ohmicron Environmental D TECH Assay Diagnostics, Inc./ Strategic Diagnostics Silvex, 2,4,5Jacobs Engineering TP
0.5mg/L 5 g/L
0.5 to 5.0 mg/L (soil) 5 to 60 g/L (water)
122
Monitoring issues
Water
Silvex Rapid Assay
Water Water Water Triazines Competitive-type ELISA Water and using polyclonal food antibodies immobilised products on microplates Competitive-type ELISA Water and using polyclonal food antibodies immobilised products in tubes Antibody coated paramagnetic particles water 60 minassay Up to 43 samples Rapid field or lab testing method
Triazine Randox ELISA ELIZA System for Reidel-de Haen AG Triazine RIDASCREE r-Biopharm GmbH N Triazine Transia Plate Triazines Transia Tube Triazines Triclopyr Rapid Assay Diffchamb AB 0.02g/L
15 minassay Read 100/30 tests kit for up absorbanc to 50 samples tested e at 450nm Rapid field testing
Diffchamb AB
0.1g/L
Triclopyr
Ohmicron Environmental 0.003 g/L Diagnostics, Inc./ Strategic Diagnostics
0.03 to 3.00 g/L
Vitellogenin
Zebrafish vitellogenin Carp vitellogenin
Vitellogenin
Vitellogenin
Rainbow Trout (Oncorhynch us mykiss) Vitellogenin
OECD Guideline no. 204 or 215
Zebrafish vitellogenin EIA kit Carp/fathead minnow vitell Biosense ogenin Laboratories AS, EIA kit Thormhlensgt. 55, Quantitative N-5008 Bergen, Rainbow Norway Trout (Oncorhynch us mykiss) Vitellogenin (Vtg) EIA
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Legislation and Standards
3. LEGISLATION AND STANDARDS

In appendix 4, several tables are available and concern: - Published and Draft ISO Water and Effluent Standards (tables 28 and 29 ) - Published and Draft CEN Water and Effluent Standards (table 30) - Published and Draft SCA Water and Effluent Standards (table 31 ) - Standard methods for Inorganic species and metals (table 32) - EPA methods for inorganic species and metals (table 33) - EPA methods for ground or wastewater (table 34) - EPA standard immunoassays (table 35)
3.1 - Introduction and background

Legislation and standard methods of sampling and analysis across the EC is a complex area. There are both national standard methods and international standard methods (CEN/ISO/USEPA etc). For this study only the CEN/ISO and Standing Committee of Analysts (SCA) and a few other national standards will be considered. This report is mainly aimed at water and effluent samples, although many of the comments and recommendations will also apply to other types of samples (e.g. leachates; soils; sediments and sludges). The objective is to be able to demonstrate equivalency of regulatory analysis results across the EC. It has recently estimated by Alejandro Herrero, Director, EU Joint Research Centre, Geel that 30% of regulation involves measurement. Without fit for purpose measurement, the objectives of the regulation will not be achieved. This report will not cover sampling other than recommending that all samples for regulatory analysis should be taken by an organization accredited to ISO 17025 [1] for sampling all relevant sample types. In order to achieve the objectives of this directive across the EC it is essential that all regulatory analysis related to this directive is fit for purpose and meets common minimum agreed performance criteria. It is important to be able to demonstrate equivalency of results across all laboratories and countries.
3.2 - Standard Methods

Section 1.3.6 of Annex V of the WFD discusses standards for monitoring of quality elements. It states: Methods used for the monitoring of type parameters shall confirm to the international standards listed below or such other national or international standards which will ensure the provision of data of equivalent scientific quality and compatibility. For standards applicable to physico-chemical parameters, it goes on to state: Any relevant CEN/ISO standards. In the authors opinion it is a totally mistaken assumption that if a laboratory uses an ISO/CEN standard method then the result produced must be fit for purpose. Many ISO/CEN methods have little associated method performance data. The data that is given is mainly precision data and gives little, if any, indication of the effects of bias from variations in sample matrix or longer term between batch variation for individual or a range of laboratories. The results from many EC-based proficiency schemes for waters indicate that some laboratories have problems consistently obtaining fit for purpose results even when using ISO/CEN standard methods.
124
Another problem with many ISO/CEN (and other international standard) methods that involve a final measurement stage involving complex instrumentation such as ICPOES; ICP-MS; ETA-AAS; EC-MS, HLPC-MS etc. usually simply state follow the manufacturers instructions for the final measurement stage. Unfortunately, most manufacturers do not provide definitive instructions for fit for purpose environmental analysis. Thus laboratories reporting results using a given ISO/CEN method could be using significantly different measurement conditions for the final measurement stage. A more pro-active approach is needed to ensure fit for purpose analysis results (see 3.3). Example from the UK In the UK, there are two national bodies producing standard methods for waters and soils, these are British Standards (which is mirrored in most other European countries) and the Standing Committee of Analysts (SCA) which produce the commonly referred to Blue Books or Methods for the Examination of Water and Associated Materials (MEWAM). The SCA is part of the Environment Agency of England and Wales. The main difference between the two organisations is that British Standards tends to publish ISO and CEN standards and a few of its own standards whilst SCA being less formal has the ability to publish methods more rapidly. It also tends to involve more organisations in the preparation stage, consequently methods tend to be more pragmatic and more reflect methods used routinely by industry for environmental analysis. The validation data in many of the SCA methods [3] tend to be more comprehensive than British Standard (and ISO/CEN methods). The SCA methods also tend to have more background information than ISO and CEN standards. There are a number of SCA guideline methods explaining the principle of major techniques (e.g. atomic absorption, ultraviolet-visible spectrophotometry, HPLC, multielement methods of analysis). It can be seen that there is a very large number (>500) of standard methods available to carry out analysis of waters and effluents. Unfortunately not many of these methods have been comprehensively validated across a number of different countries using the same validation protocol and the same set of samples. Some have only minimal validation data.
3.3 - Prescribed standards versus prescribed performance characteristics

There are two main approaches to obtaining fit for purpose regulatory results. - The use of prescribed international standard methods. - The use of any fit for purpose non-empirical method, with full standardised method validation to meet minimum method performance criteria: (i) Precision (ii) Trueness (bias) (iii) Limit of detection 125
For empirical methods, (e.g. leaching tests, AOX, EOX, ecotoxicological methods) where the method protocol defines the result, a prescribed method has to be used. However, the final measurement stage of many empirical methods (e.g. determination of metals or organic parameters in leachates) can be carried out by any validated method. For microbiological parameters, see 3.5 The approach of specifying minimum method performance criteria rather than prescribed national or international standard methods is strongly endorsed by UK laboratories. It can take up to 3 10 years to upgrade or replace an ISO or CEN international standard method after a significant method improvement or a new technique has been reported. The method minimum performance criteria are prescribed instead. Three examples of this are the 1998 Drinking Water Directive [4] and related Water Quality Regulations [5]; the specification for Waste Water Monitoring for Urban Wastewater Treatment Implementation [6] and the recent Environment Agency monitoring certification scheme (MCERTS) [7] for the chemical testing of soils. Any regulations involving environmental analysis should clearly define fit for purpose performance criteria for analysis methods used to demonstrate compliance with the regulations. One area where a rigidly prescribed method has significantly improved the precision and accuracy of analysis is for Cryptosporidium analysis. The Cryptosporidium regulations [8] which have evolved with the collaboration of the UK water industry and the DWI have radically improved this very complex analysis. Laboratories can introduce an alternative method, but must carry out a very large amount of method validation work covering all types of water to be tested and demonstrate that the new version is equivalent or better than the officially prescribed method and then obtain formal approval from the DWI before employing it. The problems of this complex analysis are outlined in a recent conference publication [9]. Recently, ISO has shown a more pragmatic approach to standardisation. The new recently published COD standard [10] allows the use of validated test kits. In fact the non-test kit version of the method was only tested by 2 out of the 44 laboratories that took part in the method validation trials. Four different manufacturers test kits were tested and all gave fit for purpose results. Users of the standard can use any manufacturers COD test kit as long as they validate it following advice given in the standard. ISO has also recently published a guidance document for the use of ICP-MS [11]. This 45 page document provides an up to date reference pragmatic reference book for using the ICP-MS technique. It should be used in conjunction with the associated formal ICP-MS standard [12]. A prime example of how long it can take to produce an ISO standard and also the fitness of purpose of the associated performance data is the soil cyanide method [13]. The work on this commenced in 1986 and it was finally published in 2003. In the authors opinion, the performance data is unfit for purpose (Table 18). It is likely to be withdrawn shortly! 126
Table 18. Example of some of the performance data in soil cyanide method (data from
ISO 11262 Easily Liberatable Cyanide in Soils by Manual Distillation)
Soil N
1 2 3
No of labs
78 9 20
Mean (mg/kg DS)

4.7 71 133
Relative reproducibility standard deviation (%)

92.0 79.0 29.0
95% low (mg/kg DS)

0 0 56
95% high (mg/kg DS)

13 183 210
Other examples of some of the performance data
Soil No
No of labs
Mean (mg/kg DS)
95% low (mg/kg DS)
95% high (mg/kg DS)
1 2 3
89 10 20
107 2039 4062
30.0 40.0 22.1
43 408 2267
171 3670 5857
Similarly the results from the graphite furnace-atomic absorption in waters standard quotes some unfit for purpose data (Table 19). It can be seen that the within laboratory precision was good, but the between laboratory agreement was poor indicating very significant bias. This is depicted in the figure 2. Table 19. Graphite Furnace Atomic Absorption (GF-AAS) Performance (Data From EN ISO 15586:2003 Water quality - Determination of trace elements using atomic absorption spectrometry with graphite furnace (ISO 15586:2003))
Element No of labs Mean (g/L)
8.74 68.6 7.8 68.2 27.7

25.2 17.8 17.2 15.0 40.7
Relative repeatability standard deviation (%)

7.4 3.6 8.5 2.8 3.0
As As Pb Pb Tl
19 21 32 32 5
127
Lab 4 Lab 1 XXX XXXX XX XXX XXXX XX XXX XXXX XX
Lab 2
XXX XXXXX X Lab 3
Figure 3. Depiction of the Results from the table above; Labs 1, 2 & 3 have obtained the wrong answer very precisely!!! Table 20 shows how a system using prescribed performance characteristics with labs using various fully validated methods can obtain fit for purpose results. Table 20. Leap Scheme Potable Water Results
Element
No of labs
Mean
Standard deviation (%)
95% low
95% high
Pb Mn Alkalinity
21 20 18
24.7 g/L 14.8 g/L 203 mg/L
8.5 6.1 2.9
20.5 g/L 13.0 g/L 191 mg/L
28.9 g/L 16.6 g/L 215 mg/L
These results are from a number of different methods for each test and show the benefit of a well regulated prescribed performance approach
Finally, method requirements are: - Fit for purpose - Very robust - Simple as possible - Not prone to interference effects - Automatable - Cost-effective
128
3.4 - ISO17025 Accreditation

The fit for purpose non-empirical method approach has been widely adopted in the UK for environmental analysis. All laboratories in England and Wales carrying out regulatory drinking water analysis are accredited to ISO 17025 [1] and in addition have to meet the Drinking Water Testing Specification (DWTS) [14]. These two stringent requirements with comprehensive regulatory audits should ensure that the laboratories are using accepted analysis procedures and employing an adequate number of trained and qualified staff. It should also ensure that suitable quality assurance/quality control procedures are adopted and maintained. The DWI audits and proficiency scheme data indicate that for this type of analysis that this type of regulatory regime works well. For all regulatory analysis it is important that a laboratory should be accredited to ISO 17025 with all relevant tests on the accreditation schedule. This should be mandatory for any laboratory carrying out regulatory analysis. It is also important to ensure that consistent ISO 17025 accreditation both within and between countries occurs when this standard is applied. In the authors experience, there are variations in the interpretation of ISO17025 requirements between countries and even between assessors within a given country. This consistency issue needs to be addressed to ensure that there is a level playing field across Europe.
3.5 - Validation of analysis methods

The analysis methods that need to be considered can be divided into four groups: Chemical, Microbiological, Ecological (Effects on biota), Radioactivity. There is a need for a common validation protocol for assessing standard methods or in-house non-standard non-empirical methods across Europe. Carefully defined method validation protocols (typically involving 11 batches with clear pass fail criteria) assists both laboratories and their customers assess whether a method is fit for the intended purpose. It is important that the analytical method should be subjected to testing of its trueness, precision and limit of detection, including spiking recovery and resilience against possible interferences [3]. In the UK the design of tests and calculation of performance characteristics for most environmental regulatory analysis is in accordance or consistent with the guidance given in A Manual of Analytical Quality Control for the Water Industry(NS30) [3]. For most parameters the specification for the performance characteristics is determined as follows: - Estimate the within-laboratory total standard deviation of individual analytical results for blanks, standard solutions, samples and spiked samples on at least 11 separate days in duplicate.
129
- The trueness (bias) for standard solutions, mean spiking recovery and standard deviation of spiking recovery should also be determined. - The range of the standard solutions tested should include the regulatory prescribed concentration or value wherever possible, but in all cases the whole calibrated range of the method must be covered subject to allowance for ensuring that all measurements fall within the calibrated range. This implies that a minimum of two different standard solutions must be included in the performance tests. - All estimates of standard deviation used to estimate limit of detection or precision, or used in significance tests must have at least 10 degrees of freedom. - The samples, and spiked sample(s) selected for use should represent all the type or types of water or effluent normally analysed. It should include a worst case matrix. The same bulk sample(s) should be used throughout the tests. Samples should be spiked immediately before analysis for each batch. The spiking standard should either be known to be stable for the period of the tests or be freshly prepared as for standard solutions. For each parameter the analysis must satisfy the prescribed method performance characteristics: trueness (bias), precision limit of detection. Table 21 shows these characteristics for some compounds. This Table is derived from Statutory Instrument 2000 No. 3184, The Water Supply (Water Quality) Regulations 2000 and is based upon CD98/83/EC 3rd Nov 1998 on the quality of water intended for human consumption. For easily determined parameters, (such as toxic metals, nutrients, COD, TOC, etc.) the trueness (bias) should be less than 10%; the precision (RSD) less than 5% and the limit of detection better than 10% of the prescribed (regulatory) value for the relevant parameter. For ultra trace complex organic analysis more lax prescribed characteristics are normally applied. Table 21: Parameters in relation to which Methods of Analysis must satisfy Prescribed Characteristics Trueness % of prescribed concentration or value or specification
10 10 25 10 25 25 10 25 10 10 10 10
Parameters
Precision (RSD) % Limit of detection % of prescribed of prescribed concentration or concentration or value or value or specification specification
5 5 12.5 5 12.5 12.5 5 12.5 5 5 5 5 10 10 25 10 25 25 10 25 10 10 10 10
Aluminium Ammonium Antimony Arsenic Benzene Benzo(a)pyrene Boron Bromate Cadmium Chloride Chromium Colour
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Conductivity Copper Cyanide (i) 1,2-dichloroethane Fluoride Iron Lead Manganese Mercury Nickel Nitrate Nitrite Pesticides and related products (ii) Polycyclic aromatic hydrocarbons (iii) Selenium Sodium Sulphate Tetrachloroethene (iv) Tetrachloromethane Trichloroethene (iv) Trihalomethanes: Turbidity (v) Turbidity (vi) 10 10 10 25 10 10 10 10 20 10 10 10 25 25 10 10 10 25 20 25 25 10 25 5 5 5 12.5 5 5 5 5 5 5 5 5 12.5 12.5 5 5 5 12.5 10 12.5 12.5 5 12.5 10 10 10 10 10 10 10 10 20 10 10 10 25 25 10 10 10 10 20 10 10 10 25
Notes: (i) The method of analysis should determine total cyanide in all forms. (ii) The performance characteristics apply to each individual pesticide and will depend on the pesticide concerned. (iii) The performance characteristics apply to the individual substances specified at 25% of the parametric value in Part I of Table B in Schedule 1. (iv) The performance characteristics apply to the individual substances specified at 50% of the parametric value in Part I of Table B in Schedule 1. (v) The performance characteristics apply to the prescribed value of 4 NTU. (vi) The performance characteristics apply to the specification of 1 NTU for water leaving treatment works.
There are two types of analytical measurements, firstly total parameters and secondly empirical parameters. For total parameter (i.e. total lead) the analytical result should be independent of the method employed (e.g. electrothermal atomization, atomic absorption, (ETA-AAS) or induction coupled plasma mass spectrometry (ICP-MS)). An empirical method is defined as a method where the method protocol defines the result, (e.g. leaching tests, AOX, EOX, etc.). Thus, a well-defined, validated protocol is then essential in order to obtain consistent results across the EC. Microbiological and ecological methods are also empirical as the method protocol defines the result. Thus for these tests a prescribed gold standard method is essential. However, this on its own, without minimum performance targets is insufficient to obtain fit for purpose results. Unlike chemical substances, microbiological species can exist in states from almost non-viable to fully viable and the percentage recovery is very dependent upon the resuscitation protocol employed. For all empirical methods suitable stable reference standards that can be used for QC purposes are considered essential. Without these there is likely to be a wide variability in results between laboratories. Some disturbing
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variations between laboratories in environmental microbiological proficiency scheme results for a range of bacteria have been reported [15]. Although microbiological methods are empirical, it does not mean that other methods cannot be employed in place of the gold standard method. However, the proposed new method must be shown to give equivalent or better method performance data than the gold standard method. There is an ISO standard on how this should be achieved. (EN ISO 17994:2004 Water quality - Criteria for establishing equivalence between microbiological methods). Most water chemical and radiological methods are total methods where the result should be independent of the fit for purpose method employed.
3.6 - Legislation requirements environmental analysis.
for
carrying
out
regulatory
In order to ensure that this analysis is fit for purpose the following legislation requirements are recommended : (ISO17025 accreditation should be required for all relevant parameters) - Full method validation data for all measurements with a minimum of 10 degrees of freedom to a single agreed protocol should be required for all methods using a single agreed protocol for all chemical measurements. Suitable protocols also need to be developed for microbiological and ecotoxicological parameters. - Prescribed minimum method performance characteristics for each regulatory parameter: - Limit of detection, - Precision, - Trueness (bias). Prescribed empirical methods (see also 3.5.8), but for total methods just rely on prescribed method performance characteristics. Many ISO/CEN standards involving complex instrumentation (e.g. ICP-MS, ICP-OES, GC-MS or HRLC-MS) simply state follow the manufacturers instructions. Unfortunately, manufacturers do not provide these instructions. Laboratories can then claim that their results must be fit for purpose because the followed the ISO/CEN standard. This issue needs to be addressed. Minimum quality control criteria are needed (min 5% samples should be appropriate QC samples and minimum 5% blanks). Regulatory parameter approved proficiency schemes and enforced participation. Approved reference materials for QC have to be used wherever possible.
3.7 - Quality Assurance / Quality Control Issues

Quality assurance considerations could easily fill a textbook. The most important consideration is confidence in the analysing laboratory. There should be good liaison
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between the client and the laboratory. The quality assurance procedures of the laboratory as outlined in its Quality Manual should be examined by the client. The basic definition of any quality system is : a) Write what is to be done b) Then do what is written c) Finally write what was done The most important criterion is that all individual results can subsequently be fully audited to examine the raw data, determine the analyst and his/her training status, the instrumentation used, the method employed; and that no transcription or calculation errors have occurred. The client should agree with the laboratory the turnaround time, the time the samples are retained by the laboratory after the analysis is completed and an acceptable reporting format for the results. Achieving promised turnaround and other agreed service standards is crucial to most customers. A late result is often of reduced or even of no value to the customer. All laboratories carrying out environmental analysis should participate in at least one proficiency-testing scheme on a regular basis (at least monthly). It is crucial that all proficiency scheme failures are thoroughly audited, investigated and documented by the laboratory. This will help to avoid future similar errors. Clients should audit the proficiency test result of their laboratories. A significant number of failures for any given parameter are a cause for concern. However, judging laboratories in a league table on proficiency results is to be discouraged, as it will tend to lead to the situation where proficiency samples are treated as special samples. This completely defeats the whole purpose of proficiency testing. The EC should be persuaded to fund a blind chemical and microbiological proficiency trial over a period of a year for a snapshot of laboratories in the EC carrying out regulatory environmental analysis. This will then give information on fitness for purpose of regulatory analytical results across the EC. This should then be repeated on a threeyear basis. Some potential areas for sampling and analysis errors are listed: Sample collection Sample handling Transportation to laboratory Sample receipt Logging-in Storage at laboratory Selection of fit for purpose method Sample pre-treatment Actual sample analysis Data entry/transfer to LIMS Data manipulation Data reporting
Measurement Uncertainty It is important to appreciate that all analytical results have an associated measurement uncertainty. This is an estimate attached to a measurement, which characterises the range of values within which the true value is asserted to lie. This uncertainty has two main components, random uncertainty and systematic 133
uncertainty (bias). It is relatively easy to calculate random uncertainty, it is much more difficult to calculate bias uncertainty especially for complex samples (e.g. contaminated soils, unknown wastes, variable strength saline samples; samples containing high levels of dissolved solids etc.). ISO17025 [1] now requires laboratories to assess the uncertainty of their results. This is normally expressed as a 95% percentile. Hence, as an example, a cadmium result of 4.5 g/L with a 95% uncertainty (confidence limit) of 0.8 g/L would then be reported as 4.5 0.8 g/L. For a regulatory limit of 100 g/L with a maximum permitted total error of 20%, the grey area where there is some (5%) uncertainty of pass or fail is relatively wide (80 to 120 g/L). When interpreting results it is important to appreciate that all results have an uncertainty and that the reported 95% confidence limits only typically apply to 95% of samples (Figure 3).
Fail 120 Probable Failure Concentration (arbitrary units) 100 Prescribed Concentration
The grey area
Probable Pass 80 Pass

Figure 4. Result Confidence Limits for Most Potable Water Parameters
Valid Analytical Measurement (VAM) Principles The UK Laboratory of the Government Chemist (LGC) has proposed six basic principles known as the VAM principles. These are: 1 Analytical measurements should be made to satisfy an agreed requirement. 2 Analytical measurements should be made using methods and equipment which have been tested to ensure that they are fit for purpose. 3 Staff making analytical measurements should be both qualified and competent to undertake the task. 4 There should be a regular independent assessment of the technical performance of a laboratory. 5 Analytical measurements made in one location should be consistent with those elsewhere 6 Organisations making analytical measurements should have well defined quality control and quality assurance procedures. 134
These six principles are common sense and represent the basis of good laboratory practice. Three additional principles strongly advocated by the author are: 1 The routine workload for each analyst should not be above that to ensure production of fit for purpose results 2 Senior analysts should understand the basic significance of the results that they approve and how they are likely be interpreted and used by the client 3 Senior analysts should be formally trained in method development techniques. With laboratory automation and high sample throughputs and minimisation of operating costs there has been a general de-skilling of laboratory staff over the last 25 years. Also nowadays many laboratory routine personnel have little knowledge of water treatment processes and the significance of the results that they produce. The Royal Society of Chemistry-Water Science Forum is actively trying to ensure that senior staff in laboratories are suitably experienced (e.g. Chartered chemist or biologist) especially those responsible for approving analytical results.
3.8 - Need for low-cost reference materials

Reference materials (RM) are widely used for the calibration of equipment and the validation of measurement procedures, e.g. in chemical analysis or materials testing. The measurand needs to be clearly defined and the property values need to be, where possible, traceable to the SI units of measurement, or to other internationally agreed references such as the values carried by certified reference material. Users of reference materials require reliable information concerning the RM property values, preferably in the form of a certificate. The user and accreditation bodies will also require that a competent body has produced the RM Where appropriate; the technical competence of the producer will have been assessed and recognised by a competent third party. The internationally recognized technical guide available for the assessment of RMs and their production is ISO Guide 34, which makes normative reference to ISO/IEC 17025 and includes ILAC G12 in the bibliography. There is no international consensus about the accreditation of RM producers. In Europe, the accreditation of RM producers is not used, but the laboratory of a RM producer is accredited usually as a calibration laboratory without reference to the extra requirements of ISO Guide 34 for homogeneity, stability, etc. In the Asia-Pacific region and the United States, RM producers are accredited with ISO Guide 34 usually used as the requirements document. Thus there is a need to obtain EC wide agreement about the accreditation of reference material suppliers. In the authors opinion the availability of low cost reference materials is key to obtaining fit for purpose results across the EC. This includes waters; effluents; soils; sludges; leachates and sediments
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The problem with water samples is the large volumes required which increase costs and also the stability of many trace or ultra trace species in water samples. Rather than supply full volume samples (which for trace organics can require over one litre per test), sealed glass ampoules containing a concentrate (10-20ml) should be considered. These would contain the main matrix components of natural waters (e.g. Ca, Mg, Na, K, HCO3, Cl, SO4, NO3 humic/fulvic acid etc.) as well as the relevant determinands. (For non-polar highly insoluble organic parameters, a separate glass vial with 1-2 ml of a methanol or acetylnitrile concentrate could be used). These type of reference materials are available in the US. ( A range of water matrices could be covered (e.g. soft, moderately hard, hard and saline waters as well as low and high humic/fulvic acid content).
3.9 - Potential Screening Methods

A significant amount of analysis will be required to assess the state of natural waters in the EC. Low cost screening tests will be required to assist in indicating where there may be water quality problems. It is considered more effective to carry out a large number of fit for purpose screening tests than a much smaller number of comprehensive targeted analysis suites covering all potential pollutants. Table 22 indicates some suitable screening tests. Some of these tests have been developed for water contamination incidents (including chemical, biological, radiological and nuclear (CBRN) incidents, where the aim is to try and demonstrate the absence of contaminants and can be considered as trying to prove a negative) Table 22. Potential Screening Tests considered relevant to the WFD TEST
CHEMICAL Ammonia Androgen screening test Ca, Mg, Na, K, S, P Cholinesterase inhibition screening test COD Colour Dioxin screening test Dissolved organic carbon (DOC) Electrical conductivity Estrogen screening test GC-MS screen ICP-MS toxic metal screen Nitrate Nitrite On-line diode array UV monitoring pH Nutrient ICP-OES Responds to low levels of OPs and carbamates As per ISO 15705:2002 Water quality -- Determination of the chemical oxygen demand index (ST-COD) -- Small-scale sealedtube method For details of these tests [16]
COMMENT
A rapid 15 min test using 100ml sample has been developed that will detect down to 1 g/l of relevant substances. Should easily detect down to 1g/L virtually all toxic metals Nutrient This can monitor for nitrate, DOC, SS, turbidity. Any substance with an aromatic ring present at concentration above ~ 0.1 mg/L. [17, 18]
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Phosphate Suspended solids (SS) Targeted parameter 55 tests Thyroid active substances screening test Turbidity UV-Scan (Diode array for speed) MICROBIOLOGICAL Clostridia spp Coloforms Cryptosporidium E.coli Enterococci Giardia Viruses ECOTOXOLOGICAL METHODS Daphnia magna Microtox Nitrification inhibition Phytotoxicity tests Algae Seed germination Thamnocephalus platyurus RADIOLOGICAL METHODS Rapid gross Alpha and Beta screen 100 ml sample and 30 min counting time Sensitive to a wide range of toxic substances [18, 20] Sensitive to a wide range of toxic substances Not very sensitive, but good database of response to a wide range of chemicals Sensitive to a wide range of toxic substances Expensive. On a proven risk basis only. Nutrient On a risk assessment basis. Responds to brominated fire retardants 230 400 nm 30 50 mm path length (for nitrate 200 230nm; 2 10 mm path length)
Recently a range of receptor mediated chemically activated luciferase reporter gene bioassays have been developed for a range of substances [16]. Separate tests are available for dioxins; estrogens; androgens; progestins; glucocorticoids; retinoids and inflammatory response. Most of these tests can detect down to the femtogram (10-15 g) level. In many instances more sensitive than high resolution GC-MS. The other advantage of these tests is that as they use the appropriate receptor to detect the sought substances, a holistic result of the total effect of the sample on the given receptor is obtained. For instance the dioxin test will also respond to co-planar PCBs some of which are almost as toxic as 2,3,7,8-TCDD. Weakly biologically active dioxins will only be loosely bound whilst strongly active dioxins such as 2,3,7,8-TCDD will be strongly bound and lead to a higher response. The UK Water Industry Research Limited (UKWIR) recently undertook a project comparing BDS estrogens responsive ER CALUX bioassay versus the yeast estrogen screen (YES) for measuring estrogenicity in sewage sludge and soils. The results of the blind study showed that for 17 estradiol spiked liquid and solid phase of activated sludge, BDS ER CALUX bioassay measured the level to within 2 7% of the spike values. This test can also be applied to waters and effluents [16] The above test was shown to be superior to the Yeast Oestrogen Screening Test (YES screen) which reported levels 400 600% away from the spikes. The report "Toxicology: Endocrine Disrupters - Waste Waters and Sludge TX/04" Ref:(04/TX/04/8) is available from UKWIR via their website at www.ukwir.org The use of diode array UV scanning has been shown to have considerable potential for detecting low levels of substances containing an aromatic ring (down to 20 -100 137
g/L) [18]. This technique can also for continuous simultaneous monitoring of DOC; COD; turbidity; nitrate and suspended solids using a low cost dedicated low power (12 Watts) on-line monitor [17]. A range of low cost rapid robust screening tests have been developed in the UK in relation to handling emergency contamination incidents [18]. Some of these could be relevant for monitoring purposes with respect to the WFD. A proficiency testing scheme for emergency pollution incidents has also been set up [19]. Screening waters using the Thamnocephalus platyurus dormant organism test [18, 20], for example, is a useful method for screening waters for a wide range of toxins. Some typical EC50 values are given in the table 23 Table 23. Test Comparison E(L)C50 (mg L-1) of bioscreening method for some parameters Chemical
Arsenic (III) Cyanide Rat poison Paraquat Thallium
Eclox
26 0.07 >1000 73 113
Microtox
0.3 3.5 507 20 450
Thamnotoxkit F
1.3 0.3 0.4 0.6 0.2
3.10 - Recommendations
1) All regulatory analysis should be carried out by ISO 17025 accredited laboratories. All relevant tests being reported should be on the accreditation schedule of the laboratory. 2) Minimum performance standards should specify for all regulatory analysis especially with respect to any compliance limit. These performance standards should include precision, trueness (bias) and required method detection limit. 3) All methods used for regulatory analysis should be validated according to an agreed defined protocol. This validation should be repeated at least every five years or whenever the method is modified or subject to significant changes. 4) All method validation data should be open to inspection by the regulatory and /or ISO17025 accreditation body. This data should include some worst case matrices. This should then ultimately allow a direct comparison of the routine performance of all laboratories across the EC to be made. 5) An EC-wide proficiency scheme should be set up to assess the equivalency of results of regulatory water analysis. This should have a minimum of 10 distributions per annum. Participation would be compulsory for all laboratories carrying out regulatory analysis. Existing proficiency schemes should be asked to tender for running this proposed EC-wide scheme. An annual meeting open to all scheme
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subscribers should be held to allow feedback and assist in the continuous improvement process. 6) A blind proficiency scheme should be given serious consideration (see 3.7.6).
7) More low-cost reference (QC) materials should be developed for a wide range of relevant determinands. 8) There is a need to obtain EC wide agreement about the accreditation of reference material suppliers. 9) Ensure suitably qualified staff is responsible for overseeing and approving regulatory chemical and microbiological analytical results. 10) Consider providing guideline best practice documents for non-empirical complex analysis methods (such as ICP-OES, ICP-MS, ETA-AAS, GC-MS and HPLC-MS) and recommended minimum method performance criteria. Produce conventional standards for all empirical parameters, where the method defines the result. 11) Ensure that all published international standards are validated by at least ten laboratories from at least three countries to an agreed protocol [21]. This should include trueness (bias) testing using typical worst case matrices.
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Appendix 1
APPENDIX 1
Table 24. Main uses of the priority compounds
Compound
EPA code
Use
Priority Pollutants - Volatile Organics

Acrylonitrile K011; K014; U009 K048; K049; K051; K052; K060; K083; K085; K087; K103; K104; K105; K141; K142; K143; K144; K145; K147; K151; U019; Herbicide
Benzene
Medicinal chemistry, dyes, artificial leather, linoleum, oil cloth, varnishes, lacquers; solvent for waxes, resins, oils use as solvent is now discouraged used for printing & lithography, paint, rubber, dry cleaning, adhesives & coatings, detergents extraction and rectification; preparation and use of inks in the graphic arts industries; as a thinner for paints; as a degreasing agent, chemical intermediate for ethylbenzene, cumene, cyclohexane, nitrobenzene, maleic anhydride, chlorobenzenes, detergent alkylate, anthraquinone, benzene hexachloride, benzene sulfonic acid, biphenyl, hydroquinone, & resorcinol /benzol for pesticide uses has been cancelled. It was in use alone or in formulations for screwworm control on animals. it was an ingredient of some early grain fumigants in the tire industry (McMichael et al, 1975), & in shoe factories (Aksoy et al, 1974), benzene is used extensively. used primarily as a raw material in the synthesis of styrene (polystyrene plastics and synthetic rubber), phenol (phenolic resins), cyclohexane (nylon), aniline, maleic anhydride (polyester resins), alkylbenzenes (detergents), chlorobenzenes, and other products used in the production of drugs, dyes, insecticides, and plastics
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Appendix 1 D018 Bromodichlorometh ane Fire retardant, solvent, intermediate in synthesis of other compounds Fire-extinguisher fluid ingredient, heavy liquid for mineral and salt separations; laboratory use Used for synthesis of pharmaceuticals; used in shipbuilding, aircraft, & aerospace industries ingredient in fire-resistant chemicals & gauge fluid chem intermed for organic synthesis; solvent for waxes, greases, & oils; reagent for graphite ore fractionation. Medication: sedative Medication: antitussive Medication: antiseptic Used as a heavy liquid floatation agent in mineral separation, sedimentary petrographical surveys, and purification of materials such as quartz; Used as an industrial solvent in liquid-solvent extractions, in nuclear magnetic resonance studies In ionization chambers, degreasing wool, extracting oils from nuts, seeds, & flowers. Fumigant used to treat soil, grain & other commodities; methylating agent. Has been used as a refrigerant and fire extinguisher. Used for insect and rodent control in space and commodity fumigations; for preplant soil fumigation (only with chloropicrin) to control nematodes, insects, weed seeds & fungi. Used in food sterilization for pest control in fruits, vegetables, dairy products, nuts, and grain; as solvent in aniline dyes. As methylating agent, especially for prepn of antipyrine & other pharmaceuticals. The first recorded use of methyl bromide occurred in the last part of the 19th century: it was used as a medicinal agent to destroy malignant tissue and as an anaesthetic in dentistry. Used as a fungicide, nematicide, herbicide (unspecified), herbicide (terrestrial), and an insecticide and miticide against nematodes and weeds (preemergence) through soil fumigation treatment for fumigation of storage areas (feed/food-full) and domestic dwellings (indoor). For control of termites in structures. Organic synthesis; extraction solvent for vegetable oils Recovery of tin in tin plating waste in formulation of petrol additives in refrigerants; metal degreasing; prodn of semiconductors used to reduce fire hazard in combinations with either carbon disulfide or ethylene dichloride intended as grain fumigants. These mixtures are not approved for fumigation of dry beans, peanuts or peas. Former uses solvent for rubber cement; cleaning agent for machinery and electrical equipment; in synthesis of nylon-7 and other organic chlorination processes. Use in polymer technology as reaction medium, catalyst; in organic synthesis for chlorination of organic compounds; in soap perfumery and insecticides. Industrial solvent for cable and semiconductor manufacture. Metal recovery and catalyst regeneration. Chem int for fluorocarbons, esp fluorocarbons 11 & 12 chem int for pesticides & hexachloroethane chem int for tetrabromomethane & pyrosulfuryl chloride metal degreasing solvent (former use) carbon tetrachloride may have small commercial uses as chain transfer agent for making bromotrifluoroethylene polymers and as a catalyst preparation for the commercial isomerisation of n-butane to isobutane; also it is used in plasma etching gases for etching aluminium in integrated circuits as solvent for oils, fats, lacquers, varnishes, rubber waxes, resins; grain fumigant. Pharmaceutical aid (solvent). Formerly used as dry cleaning agent and fire extinguisher. Formerly as antihelmintic (nematodes). Solvent for paints sometimes used in dry-cleaning chem int for phenol, o- & p-chloronitrobenzene, DDT, & aniline used in MFR of insecticides & as int in MFR of dyestuffs solvent carrier for methylene diisocyanate. Used as a fibre swelling agent and dye carrier in textile processing, a tar and grease remover in cleaning and degreasing operations, a solvent in surface coating and surface coating removers. Used as a solvent in the manufacture of adhesives, paints, polishes, waxes, diisocyanates, pharmaceuticals, and natural rubber
Bromoform
U225
Bromomethane
K117; K131; K132; K136; U029; K118
Carbon tetrachloride
K021; K073; K150; K151; U211; D019
Chlorobenzene
K019; K085; K105; K149; U037; D021
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Appendix 1 Chemical intermediate refrigerant, solvent, alkylating agent, starting point in the mfr of tetraethyl lead medication and vet in synthesis of ethyl compounds organic synthesis; solvent for phosphorus, sulfur, fats, oils, resins, and waxes; insecticides Use in organic synthesis of perchloroethane, esters, and Grignard reagents. Use in manufacture of dyes and drugs, use as a propellant in aerosols. Use in manufacture of perfumes Used in the manufacture of anaesthetics, sedatives and cellulose ethers. Copolymer of 95% ethyl acrylate with 5% 2chloroethyl vinyl ether /has been used to produce acrylic elastomer
Chloroethane 2-Chloroethyl vinyl ether
K018
U042 K009; K010; K019; K021; K029; K073; K117; K136; K149; K150; K151; U044; D022 K018; K149; K150; U045
Chloroform
General solvent for adhesives & pesticides as solvent for fats, oils, rubbers, alkaloids, waxes, gutta-percha, resins; as cleansing agent; in fire extinguishers to lower freezing temp of carbon tetrachloride; in the rubber industry registered for use in use as insecticidal fumigant on stored barley, corn, oats, popcorn, rice, rye, sorghum & wheat srp: formerly registered chem int for fluorocarbon 22 (chlorodifluoromethane) extraction & purification solvent - eg, for penicillin mildewcide for tobacco seedlings dry cleaning agent chem int for dyes & pesticides polymer chain transfer agent chem int for tribromomethane medication: general anaesthetic (former use) component of cough syrups, toothpastes (former use) component of linaments & toothache cmpd (former use)
Chloromethane
Dibromochlorometh ane
1,2Dichlorobenzene
K030; K042; K085; K105; U070
Medication: local anaesthetic As aerosol propellant (former use) foaming agent in plastics industry; in stainless steel industry in MFR of tetramethyl lead, methyl cellulose, fumigants, synthetic rubber; also as a methylating agent, propellant, and herbicide fluid for thermometric & thermostatic extracting equipment for oils, fats and resins chem int (unisolated) for methylene chloride & chloroform, chem int for methylarsonate herbicides, quaternary ammonium chlorides, methyl mercaptan; solvent & diluent in prodn of butyl rubber. Methyl chloride is primarily used to produce silicone resins and rubbers. Methyl chloride is used to terminate the polymerization of bakelite polysulfone. This controls the molecular weight of the polymer and contributes to thermal stability Timber products processing Blowing agent for some polystyrene foams. As a refrigerant Dibromochloromethane is used as a chemical intermediate in the manufacture of fire extinguishing agents, aerosol propellants, refrigerants, and pesticides Solvent for waxes, gums, resins, tars, rubbers, oils, asphalts, insecticide for termites & locust borers removing sulfur from illuminating gas; as intermed in mfr of dyes; as heat transfer medium as degreasing agent for metals, leather, wool; as ingredient of metal polishes indust odour control Herbicide, insecticide, and soil fumigant as solvent mixt used to remove lead & carbonaceous deposits from engine parts; as component of rust-proofing mixt as a magnetic coil coolant; in woodpreserving cmpd chem intermed for making agric chem; emulsifiable form recommended for deodorizing garbage & sewage org synth esp of pesticides & solvent in chem processes Used as a process solvent in the manufacture of toluene diisocyanate. Ortho-dichlorobenzene is used as a solvent in the following applications: motor-oil additive formulations; paints; formulations for removing paints; firearm cleaners; dissolution of pitch on papermaking felts; a carrier for wood preservatives and repellents; and upper cylinder lubricants Hydrolysis of 1,2-dichlorobenzene with KOH and NaOH gives ortho-chlorophenol an intermediate for dyestuffs and initiator for higher chlorinated phenols Manufacture of 3,4-dichloroaniline, solvent for oxides
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Appendix 1 of non-ferrous metals
1,3Dichlorobenzene
K085; K096; U071
Fumigant & insecticide /reacted with potassium hydroxide or sodium hydroxide to produce chlorophenols; used in the preparation of arylene sulfide polymers in the pps polymerization process Insecticidal fumigant; popular for domestic use against clothes moths germicide; MFR of 2,5-dichloroaniline; dyes; used in pharmacy p-Dichlorobenzene is sometimes used as a deodorant for garbage and restrooms, as well as an insecticide for control of fruit borers and ants. May be applied to tobacco seed beds for blue mold control; for the control of peach tree borer; and mildew and mold on leather and fabrics. Gallery injections with 6 insecticides and 3 fumigants were tested for comparative effectiveness in controlling Prionoxystus robiniae (Peck), and Paranthrene simulans (Grote). The three fumigants (carbon disulfide, Serafume, and paradichlorobenzene) provided complete control. The gallery injection technique was deemed feasible for use against borers in high-value trees. Gallery injection has advantages over bark sprays because it can give satisfactory control of borers already established in galleries and limits chemical application to a few galleries instead of entire trees or stands of trees. It is used as an additive in resin-bonded abrasive wheels to provide a more open structure, and vaporizes during the curing operation leaving pores and wider grain spacing. Hydrolysis of 1,4-dichlorobenzene with cupric salts and hydroxylamine gives the para-chlorophenols. Nitration of p-dichlorobenzene to yield 1,4-dichloro-2-nitrobenzene intermediate for dyestuff/. The reaction of p-dichlorobenzene with sodium sulfide in a polar organic solvent to produce poly(phenylene sulfide) An engineering plastic used for surface coatings and model resins/. Para-dichlorobenzene may have had minor use as an extreme-pressure lubricant. Applications include use as an intermediate in organic synthesis and as on animal repellant. Use in pig stalls as an odor control agent Leak-detecting agent; freezing of foods by direct contact; srp: former use chilling of cocktail glasses to prepare frozen tissue sections In manufacture of aerosols for cosmetics, pharmaceuticals, insecticides, paints, adhesives, and cleaners SRP: Former use/. Use in manufacture of and extensive use as a refrigerant in home and commercial applications. Used as a blowing agent for cellular polymers, a solvent or diluent in fumigants for food sterilization, in paints and varnish removers, and in polymerization processes. Used as a foaming agent in fire extinguishing aerosols, for surfactants. Used in water purification, copper and aluminum purification, petroleum recovery, and in manufacture of glass bottles. Used in regulating devices for leak detection, in thermal expansion valves, used in manufacture of materials for electrical applications as insulators and generator windings. Used in organic synthesis of Freons and a polymerization catalyst, used as a working fluid for heat pumps and in hydraulic fluids. In various "skin freezes" by aerosol application, as propellant for antibiotic powders, mastitis formulations, etc, & for admixture to other gases such as ethylene oxide to make them non-flammable. Used in refrigeration systems. Mechanical vapour compression systems use fluorocarbons for refrigeration & air conditioning & account for majority of refrigeration capability in us. Fluorocarbons are used as refrigerants in home appliances, mobile air conditioning units, retail food refrigeration systems & chillers. Fluorocarbons
1,4Dichlorobenzene
K019; K030; K042; K085; K149; K150; U072; D027
Dichlorodifluorometh ane
U075
143
Appendix 1 As a solvent for plastics, oils and fats; cleaning agent; degreaser; in rubber cementing; as a fumigant and insecticide spray; in fabric spreading; in fire extinguishing; medication: formerly used as an anaesthetic. Chem int for 1,1,1-trichloroethane, a solvent. Extractant for heat-sensitive substances. Used in the manufacture of high vacuum rubber. Thermal cracking of 1,1dichloroethane produces vinyl chloride at 400-500 deg c and about 1500 psi. Coupling agent in antiknock gasoline; in paint, varnish & paint removers; in ore flotation. Manufacture of acetyl cellulose, tobacco extract. In paint, varnish and finish removers; soaps & scouring compounds; wetting and penetrating agents; ore flotation; lead scavenger in antiknock gasoline; prodn of vinyl chloride, trichloroethylene, vinyldiene chloride & trichloroethane. Fumigant for grain, upholstery & carpets; registered for agric use in the use for postharvest fumigation of grain & for use in orchards, agric premises and mushroom houses. In leather cleaning, rubber goods fabrication, drum filling, and metal cleaning industries. In degreaser compounds, rubber cement, and acrylic adhesives. Catalyst in production of hexachlorophene. Solvent for processing pharmaceutical products. Chem int for tetrachloroethylene. Manufacture of ethylenediamine, succinonitrile, glycol ethers & esters. Chem int for ethyleneimine. Chem int for polysulfide elastomers. Manufacture of ethylene glycol, diaminoethylene, polyvinyl chloride, nylon, viscose rayon, styrene-butadiene rubber, and various plastics; solvent for resins, asphalt, bitumen, rubber; used as pickling agent and a dry clean agent; in photography, & cosmetics. Used as co-monomer, primarily with vinyl chloride. In adhesives; component of synthetic fibres. In the synthesis of the refrigerant 142b, 1-chloro-1,1-difluoroethane, is synthesized from 1,1-difluoroethane, vinylidene chloride & 1,1,1trichloroethane. A monomeric intermediate in the production of plastics, particularly the saran types. Co-monomer, esp for food packaging & coating resins. Comonomer for modacrylic fibres; unisolated chemical intermediate for 1,1,1-trichloroethane. Chemical intermediate in production of chloracetyl chloride. Solvent & chemical intermediate. Solvent (as isomeric mixt) for perfumes, dyes, & lacquers. Solvent (as mixt) for thermoplastics, fats, & phenols. Solvent (as mixt) for camphor & natural rubber. Chem int (as isomeric mixt) for chlorinated cmpd. Agent in retarding fermentation. Used as a solvent for waxes, resins, and acetylcellulose. It is also used in the extraction of rubber, as a refrigerant, in the manufacture of pharmaceuticals and artificial pearls and in the extraction of oils and fats from fish and meat. 1,2-dichloroethylene cis- & trans-isomers of 1,2-dichloroethylene have had use as solvents & chem intermediates. Neither of isomers has developed wide industrial usage in the us partly because of their flammability. Cis and trans isomers Used as a solvent for waxes, resins and acetylcellulose. It is also used in the extraction of rubber, as a refrigerant, in the manufacture of pharmaceuticals and artificial pearls and in the extraction of oils and fats from fish and meat. 1,2Dichloroethylene Livestock (in dd mixt); solvent in plastics, resins, & metals indust, int in rubber processing oil & fat solvent; in dry cleaning fluids; in degreasing, in insecticidal fumigant mixtures. Intermediate for perchloroethylene & carbon tetrachloride; lead scavenger for antiknock fluids; solvents for waxes, gums; solvent mixtures for cellulose esters & ethers; scouring cmpd; spotting agent; metal degreasing agents; soil fumigant for nematodes Used primarily in soil fumigants or as component of soil fumigant mixtures; small amt as chem intermediate. Used as an insecticide and fumigant Used primarily in soil fumigants for nematodes or as component of soil fumigant mixtures for nematodes/; small amt as chem intermediate. Trans-1,3-dichloropropene is used as a chemical intermediate and corrosion inhibition agent.
1,1-Dichloroethane
K028; U076
1,2-Dichloroethane
K019; K020; K029; U077; D028
1,1-Dichloroethene
K029; U078; D029
cis-1,2Dichloroethene
trans-1,2Dichloroethene 1,2-Dichloropropane cis-1,3Dichloropropene trans-1,3Dichloropropene
U079 K017; U083 U084
144
Appendix 1 K048; K049; K051; K052; K086 Used in the production of synthetic rubber as a solvent or diluent, a component of automotive and aviation fuels; mfr of cellulose acetate Ethylbenzene is mainly used as a precursor to styrene. Solvent-eg, for alkyd surface coatings, chem int for diethylbenzene & acetophenone, for ethyl anthraquinone, for ethylbenzene sulfonic acids (o-, m- & p-), for propylene oxide & alpha-methylbenzyl alcohol, unrecovered component of gasoline Solvent for cellulose acetate; medication: anaesthetic (inhalation) paint removers; vapour degreasing solvent for metals & plastics solvent & cleaning agent in the chem processing indust blowing & cleaning agent in urethane foam indust in chemical processing & as carrier solvent insecticides & herbicides; as a post-harvest fumigant for strawberries, as grain fumigant, & in combination with ethylene for degreening citrus fruits solvent for plastic film, adhesives, protective coatings; cleaning solvent for circuit boards & stripper solvent for photoresists in pharmaceutical industry as a process solvent in prodn of steroids, antibiotics & vitamins & solvent for tablet coatings decaffeinating coffee; extraction of heat-sensitive substances such as cocoa, edible fats, spices & beer hops refrigerant; in oil dewaxing; as dye & perfume intermediate; as carrier solvent in textile industry component of fire extinguishing cmpd chem int for bromochloromethane & other chemicals In furniture processing In pour molding of dental material, the 50:50 mixture of dichloromethane and methylmethacrylate cold curing monomer is used to treat the acrylic teeth to improve the bonding Ingredient in nonflammable removers, strippers, & cements; used in aerosol formulations; in solid phase peptide synthesis; solvent for resins Low temp heat transfer medium Nonflammable solvent for fats, oils, waxes, resins, cellulose acetate, copal, phosphorus, sulfur, rubber; solvent in certain types of friedel-crafts reactions, phthalic anhydride condensations; in mfr of paints, varnish, rust removers; in soil sterilization and weed killer, insecticide formulations; in determination of theobromine in cacao; as immersion fluid in crystallography; in the biological laboratory to produce pathological changes in gi tract, liver & kidneys. Intermediate in mfr of trichloroethylene & other chlorinated hydrocarbons having two carbon atoms. For cleansing & degreasing metals; paint removers, lacquers, photographic film; alcohol denaturant . Chem int for trichloroethylene & tetrachloroethylene; chem int for 1,2- & 1,1dichloroethylene; solvent eg, for polyesters & extractions; moth-proofing agent for textiles. Use in manufacture of cyanogen chloride, polymers, and tetrachloro-alkylphenol; use as a solvent in preparation of adhesives. Bleach manufacturing used in cement, lacquers; in manufacture of artificial silk, and artificial pearls. Recently, it has also been used in the estimation of water content in tobacco and many drugs, and as a solvent for chromium chloride impregnation of furs. Used in the textile industry for dry-cleaning & for processing & finishing; used in both cold cleaning & vapour degreasing of metals; it is used as a chem intermediate in the synthesis of fluorocarbon 113, 114, 115, & 116; it is used as a heat-exchange fluid scouring, sizing & desizing agent in textile manufacture component of aerosol laundry-treatment products solvent, eg, for silicones insulating fluid & cooling gas in electric transformers In typewriter correction fluids (eg, Liquid Paper, Wite-Out, Snopake, etc) MEDICATION VET: use in small animals as a ruminant anthelmintic (vermifuge) has been largely replaced by drugs that are less toxic & easier to admin Formerly used, but no longer approved, in mixtures with grain protectants and certain liquid grain fumigants In manufacture benzoic acid, benzaldehyde, explosives, dyes, and many other organic compounds; as a solvent for paints, lacquers, gums, resins, in the extraction of various principles from plants; as gasoline additive. Diluent for photogravure inks in fabric & paper coating, mfr artificial leather Used in cements, solvents, spot removers, cosmetics, antifreezes, and inks. Asphalt and naphtha constituent. Detergent manufacture. Mfg caprolactam, saccharin, medicines, and perfumes; diluent and thinner in nitrocellulose lacquers, adhesive solvent in plastic toys and model airplanes. Fuel blending DENATURANT The
Ethylbenzene
Methylene chloride
U080, F001or F002
1,1,2,2Tetrachloroethane
U208; U209
Tetrachloroethene
K043; U210; D039
Toluene
K022; U220
145
Appendix 1 largest chemical use for toluene is the production of benzene and urethane via hydrodealkylation
1,1,1Trichloroethane
U226
1,1,2Trichloroethane
U227
Trichloroethene
U228; D040
Trichlorofluorometha ne
U121
Solvent for natural & synthetic resins, oils, waxes, tar & alkaloids dry cleaning agent in cold type metal cleaning, cleaning plastic moulds formerly used with ethylene gas for degreening citrus fruits & postharvest fumigation of strawberries Solvent for various insecticides Former use spotting fluid in textile processing; chem int for org chems (eg, vinylidene chloride); solvent for adhesives & coatings; coolant & lubricant in metal cutting oils; extraction solvent; component of inks & drain cleaners; solvent for photoresist polymers; solvent in textile dyeing. In aerosols, in which it acts both as a vapour pressure depressant and as a solvent and carrier for many of the active ingredients used in aerosols. Vapour degreasing Solvent for cleaning precision instruments; metal degreasing, pesticide, textile processing Used in adhesives, production of teflon tubing, in lacquer, and coating formulations. Intermediate in the production of vinylidine chloride, as a solvent and component of adhesives. Solvent-eg, for chlorinated rubbers & polyesters solvent for fats, oils, waxes, resins, other products; organic synthesis In degreasing, in dry cleaning; in mfg org chem & pharmaceuticals in gas purification, as a solvent of sulfur & phosphorus refrigerant & heat exchange liquid; diluent in paints & adhesives; textile processing; aerospace operations (flushing liquid oxygen) cleaning solvent, esp in vapour degreasing chain terminator in prodn of polyvinyl chloride swelling agent in disperse dyeing of polyesters agent in removal of basting threads in textile processing chem int for 1,1,2,2-tetrachloroethyl sulfenyl chloride solvent in adhesives & paint-stripping formulations heat transfer medium-eg, in case hardening of metals solvent base for metal phosphatizing systems solvent in characterization test for asphalt entrainer for recovery of formic acid extraction solvent-eg, for caffeine Used as household cleaner; with trichloroethane it is used in most typewriter correction fluid. /SRP: Former use Used in wool-fabric scouring Extractant for spice oleoresins. Intermediate in the production of pentachloroethane. Carrier solvent for the active ingredients of insecticides, and fungicides. Medication (Vet): Inhalation anaesthetic. Former use Used in mfr of cleaning cmpd & in fire extinguishers Chemical intermediate, solvent blowing agent in prodn of polyurethane foams; refrigerant; degreasing agent Freon 11 is used in electric insulation since it has high electric strength, inhibits partial discharges, and tends to extinguish power arcs. Propellant in aerosols for insecticides, floor waxes, paint, cosmetics, and perfumes former use In production of polymeric resins. Dielectric fluid in bubble chambers and in wind tunnels. Sulfonation solvent in chemical synthesis. Used to propel bronchodilator sympathomimetic drugs or corticosteriods for the treatment of bronchial asthma /formerly in cosmetic aerosol products. In refrigeration machinery requiring refrigerant effective at negative pressures mechanical vapour compression systems use fluorocarbons for refrigeration & air conditioning & account for majority of refrigeration capability in us. Fluorocarbons are used as refrigerants in home appliances, mobile air conditioning units, retail food refrigeration systems & chillers. Fluorocarbons
146
Appendix 1 In plastic industry; as refrigerant; in organic syntheses. Monomer for poly(vinyl chloride) homopolymer. Comonomer-eg, with vinyl acetate or vinylidene chloride. Chem intermed for methyl chloroform & 1,1,1-trichloroethane. Chem intermed for other org chems-eg, chloroacetaldehyde. Monomer & comonomer for fibres-eg, vinyon & saran fibres. Oxidn inhibitor in ethylene oxide prodn. Refrigerant & extraction solvent (former use). Vinyl chloride is used in the manufacture of numerous products in building and construction, automotive industry, electrical wire insulation and cables, piping, industrial and household equipment, medical supplies, and is depended upon heavily by the rubber, paper, and glass industries. Adhesives for plastics vinyl chloride was formerly a component of aerosol propellants. Vinyl chloride and vinyl acetate copolymers are used extensively to produce vinyl asbestos floor tiles. Limited quantities of chloroethene were used in the united states as an aerosol propellant and as an ingredient of drug and cosmetic products. (former use) Raw material for production of benzoic acid; as solvent; manufacturing dyes & other organics; sterilizing catgut; production of phthalic anhydride, isophthalic & terephthalic acids & their dimethyl esters used in manufacture of polyester fibres; with canada balsam as oil-immersion in microscopy; cleaning agent in microscope technique Manufacture of resins, paints, varnishes, general solvent for adhesives in aviation gasoline; protective coatings; synthesis of org chemicals source of oxylene, m-xylene, p-xylene & ethylbenzene solvent-eg, for paints, coatings, adhesives & rubber back-blended into gasoline unrecovered component of gasoline Used in manufacture of quartz crystal oscillators, hydrogen peroxide, perfumes, insect repellants, epoxy resins, pharmaceuticals, and in the leather industry. /SRP: Used in histological laboratories. Used as a solvent in phenoxyalkanoic herbicides. (medication) Used in manufacture of pharmaceuticals . Used as an indirect food additive for use only as a component of adhesives. Used as an indirect food additive polymer for use as a basic component of single and repeated use food contact surfaces. Xylene is used as a solvent in polysulfide polymer-polyepoxide resins
Vinyl chloride
U043; D043
Xylenes (total)
U239
Priority Pollutants - Pesticides/PCBs

Aldrin Aroclor 1016 Polychlorinated byphenils Aroclor 1221 Polychlorinated byphenils Aroclor 1232 Aroclor 1242 Polychlorinated byphenils P004 Cyclodiene insecticide Although the production and sale was discontinued in late 1977, it is still present in capacitors now in use. Formerly used in gas-transmission turbine hydraulics, rubber plasticizers, adhesives, and electrical capacitors. Although the production and sale was discontinued in late 1977, it is still present in many of the capacitors now in use Aroclor was formerly used as hydraulic fluids, rubber plasticizer, and adhesives. Used in electrical capacitors, electrical transformers, vacuum pumps, and gas-transmission turbines. Formerly used as heat transfer fluid, hydraulic fluids, rubber plasticizer, and in carbonless paper, adhesives and wax extenders. Although the production and sale was discontinued in late 1977, it is still present in transformers and capacitors now in use. Formerly used in electrical transformers, gas transmission turbines, hydraulic fluids, adhesives, plasticizer rubber, heat transfer systems, wax extenders and carbonless reproducing paper.
147
Appendix 1 Aroclor 1248 Polychlorinated byphenils Aroclor 1254 Polychlorinated byphenils Aroclor 1260 Polychlorinated byphenils Atrazine alpha-BHC beta-BHC delta-BHC U129; D013 U129; D013 Former use in hydraulic fluids, vacuum pumps, rubber plasticizers, synthetic resins, and adhesives. Formerly used in hydraulic fluid, rubber plasticizers, synthetic resin plasticizers, adhesives, wax extenders, dedusting agents, inks, cutting oils, pesticide extenders, sealants and caulking compounds In routine screening program for in vitro assays, S-9 fractions are generally prepared from the livers of male rats which have been treated with nonspecific enzyme inducers such as phenobarbital or Arochlor 1254. Although the production and sales was discontinued in late 1977, it is still present in transformers now in use. In electrical capacitors, electrical transformers, vacuum pumps and gas-transmission turbines Formerly used in electrical transformers, hydraulic fluids, plasticizer in synthetic resins and dedusting agents. Although the production and sale was discontinued in late 1977, it is still present in many of the transformers and capacitors now in use Atrazine is a widely used selective herbicide for control of broadleaf & grassy weeds in corn, sorghum, rangeland, sugarcane, macadamia orchards, pineapple, & turf grass sod. It is used also in some areas for selective weed control in conifer reforestation & christmas tree plantation as well as for nonselective control of vegetation in chemical fallow. Atrazine also is used as a nonselective herbicide for vegetation control in noncrop land Component of benzene hexachloride, bhc-former insecticide /SRP, Former Use/: HCH is often used with DDT Hexachlorocyclohexane Formerly used in the USA as an insecticide. Benzene hexachloride Formerly used as an insecticide. Benzene Hexachloride Insecticide for field crops corn, wheat insecticide for ornamentals, pasture, & forage crops insecticide for forestry, timber protection, & livestock insecticide for soil & seed treatment & viticulture Medication (Human: pediculicide, scabicide; Vet: ectoparasiticide) Used in baits & seed treatments for rodent control. Application rates: Range from 0.25 to 2.25 ounces/100 lb of seed for seed treatment; 0.1 to 2.06 lb/acre for foliar and soil treatment; 0.8 to 1.5 oz/50,000 cubic feet of greenhouse; 0.006 to 0.11 lb/gallon for bark; 0.023 to 3% sprays, dips, and dusts for indoor and animal treatment; <0.01 lb/1000 square feet for animal premises; <4 lb/1000 square feet (14.64% solutions) for wood, and wooden structures; and 1% dust for human skin/clothing treatment (military use only). Medication: pediculicide, scabicide Medication (vet): ectoparasiticide Chlordane is a manufactured chemical that was used as a pesticide. Technical chlordane is not a single chemical, but is actually a mixture of pure chlordane mixed with many related chemicals. It doesn't occur naturally in the environment. It is a thick liquid whose colour ranges from colourless to amber. Chlordane has a mild, irritating smell. Some of its trade names are Octachlor and Velsicol 1068. Until 1983, chlordane was used as a pesticide on crops like corn and citrus and on home lawns and gardens. Because of concern about damage to the environment and harm to human health, the Environmental Protection Agency (EPA) banned all uses of chlordane in 1983 except to control termites. In 1988, EPA banned all uses.
gamma-HCH (Lindane)
D013; U129
Chlordane
148
Appendix 1 Broad spectrum insecticide used until 1974; EPA restricted its use to termite control by direct soil injection and non-food seed and plant treatment. Wool processing industry Dieldrin was used in tropical countries as a residual spray on the inside walls and ceilings of homes for the control of vectors of diseases, mainly malaria. /Dieldrin is used to control locusts and tropical disease vectors, such as Glossina species. Industrial uses include timber preservation, termite-proofing of plastic and rubber coverings of electrical and telecommunication cables, of plywood and building boards and as a termite barrier in building construction. Contact, stomach poison in certain crops. Control of public health insect pests, termites, locusts, and tropical disease vectors. TDE less effective against moths than ddt, but it is superior against some other insects (eg, tomato hornworms). Srp: former use in usa employed for controlling a number of pests on vegetables & tobacco. In medical entomology field tde is about equal to ddt against mosquito larvae but inferior against adults. Former use in usa no longer any registered uses in usa. In actions dated January 15, 1971 & July 7, 1972, the US EPA cancelled all uses of DDT products, except the following: 1) The US Public Health Services & other Health Service Officials for control of vector diseases; 2) The USDA or military for health quarantine; 3) In drugs, for controlling body lice (to be dispensed only by a physician); & 4) in the formulation for prescription drugs for controlling body lice DDT can be used for a few specialized emergency purposes, eg, to combat the tussock moth medication: pediculicide contact insecticide for variety of vegetables and crops srp: former use in usa ddt is a potent non-systemic stomach & contact insecticide of high persistence on solid surfaces & readily partitions into animal fats where it may accum. It has little activity against phytophagous mites & is phytotoxic to cucurbits & some varieties of barley. Srp: former use in usa use for control of malaria, typhus, & other insect-transmitted diseases srp: former use in usa control of some forest defoliators with ddt incl spruce budworm black headed budworm hemlock looper gypsy moth tent caterpillar douglas-fir tussock pine tussock moth pine butterfly elm spanworm sawflies srp: former use in usa one of chief uses was in medical entomology for controlling mosquito larvae & adults, flies, body lice, bedbugs, & fleas pests of livestock, farm crops, forest & shade trees, & stored products. /former use It is a non-systemic & persistent insecticide used mainly on field crops. It is non-phytotoxic @ insecticidal concn, but is suspected of /causing damage to maize. Srp: former use Insecticide used to control the army cutworm (Euxoa aoxiliaris), the pale western cutworm (Agrotis orthogonia), pine vole (Microtus pinetorium), meadow voles (Microtus species), and grasshoppers, but only when federal regulations are strictly followed. SRP: Former use INSECTICIDE FOR SMALL GRAINS, SUGARCANE, & APPLE ORCHARDS SRP: FORMER USE The only known use of endrin is as an insecticide, as an avicide, and as a rodenticide. Former use Endrin has been used mainly on field crops such as cotton and grains. It has also been used for grasshoppers in noncropland and to control voles and mice in orchards. SRP: Former use Control of a wide range of insects (particularly Lepidoptera) in cotton, maize, sugarcane, rice, cereals, ornamentals, and other crops. SRP: Former use Not commercially produced. Endosulfan is its precursor. Not commercially used but occurs as an impurity of endrin
Dieldrin
P037
4,4'-DDD 4,4'-DDE
U060
4,4'-DDT
U061
Endrin
P051; D012
Endosulfan sulfate Endrin aldehyde
149
Appendix 1 Insecticide, eg, for deciduous fruits, nuts, cotton, & vegetables; acaricide Insecticide used to control the Colorado potato beetle, flea beetle, cabbageworm, peach tree borer, and the tarnished plant bug. [R5] controls aphids, thrips, beetles, foliar feeding larvae, mites, borers, cutworms, bollworm, bugs, whiteflies, leafhoppers, & slugs on deciduous, citrus & small fruits, vegetables, forage crops, oil crops, fibre crops, grains, tobacco, coffee, tea, forest, ornamentals. Controls termites & tsetse fly. Foreign application ... For control of green leafhoppers, stem borers & whorl maggot in lowland rice, shootfly in sorghum, pod borers in legumes ... Insecticide, eg, for deciduous fruits, nuts, cotton, & vegetables; acaricide Insecticide used to control the Colorado potato beetle, flea beetle, cabbageworm, peach tree borer, and the tarnished plant bug. [R5] controls aphids, thrips, beetles, foliar feeding larvae, mites, borers, cutworms, bollworm, bugs, whiteflies, leafhoppers, & slugs on deciduous, citrus & small fruits, vegetables, forage crops, oil crops, fibre crops, grains, tobacco, coffee, tea, forest, ornamentals. Controls termites & tsetse fly. Foreign application ... For control of green leafhoppers, stem borers & whorl maggot in lowland rice, shootfly in sorghum, pod borers in legumes ... Insecticide used on deciduous fruits/nuts, 50%; insecticide used on vegetables, 50% (1982 Insecticide for control of cotton boll weevil former use insecticide for termite control (former use) insecticide for certain field crops-eg, corn (former use) insecticide for citrus crops (former use) insecticide for foliar & seed treatment (former use) insecticide for pest control operators (former use) insecticide for pineapples & cereal (former use) insecticide for vegetables & sugar beets (former use) insecticide for certain nut crops (former use) usually added to soil to control white grubs, root weevils, & wireworms to prevent girdling of seedlings by reproduction of weevils. Material is either sprayed on planted trees or trees are dipped in water emulsions of active cmpd prior to planting. Srp: former use in usa vet: as premise spray against flies, fleas, mosquitoes, & their larvae by use of residual sprays (0.125-0.5%). Srp: former use Formulation of pesticides supplied as an emulsifiable concentrate, wettable powder, dust or granular material; Used formerly as an insecticide in seed treatment, preplanting soil application, dipping tops of plants and roots for control of insects, flies and mosquitoes; Used formerly on household plots and on fruits; Used formerly in termite control (dispensed in caulking guns). The only commercial use of heptachlor products still permitted is for fire ant control in power transformers. Vet: as premise spray against flies, fleas, mosquitoes, & their larvae by use of residual sprays (0.125-0.5%). Srp: former use Not avail as commercial product in usa, & it is not normally present in commercial heptachlor srp: heptachlor epoxide is formed from heptachlor in the environment Ectoparasiticide an excellent replacement for ddt where application may constitute hazard to warm-blooded animals or susceptible plants. It is rarely phytotoxic, & injury is negligible even on ddt-susceptible crops such as cucurbits. It is approved in us for use on 78 agric crops (incl several types of seeds), with restrictions on use of treated seeds. For use as insecticide on beef cattle, dairy cattle, goats, sheep, & swine & for spray treatment of barns, grain bins, mushroom houses, & other agric premises . Methoxychlor has been utilized extensively for the control of biting flies in both northern and southern regions of Canada. 0.25-1.0% AS DIP; 0.5-1.0% as aerosol spray--cats, dogs, swine; 1.0-3.0% as aerosol spray--cattle; 1.0-5.0% in oil base for backrubbers--cattle; 2.0-5.0% dust bags--cattle horn flies 5.0-50.0% as spot treatment dusts on livestock; tablespoonful doses only of the 50% concn on cattle; up to 2.0% dusts on hamsters, mice, and rats; 2.0-5.0% as a premise SPRAY Insecticide effective against mosquito larvae and house-flies. A contact & stomach insecticide effective against a wide range of pests, but not aphids, in field & forage, fruit & vegetable crops.
Endosulfan-I
Endosulfan-II
Heptachlor
K097; P058; P059; D031
Heptachlor epoxide
Methoxychlor
U024; U247; D014
150
Appendix 1 It is a pre-emergence herbicide recommended for control of broad-leaved & grassy weeds deep-rooted crops such as artichokes, asparagus, berry crops, broad beans, citrus, coffee, forestry, hevea, hops, oil palms, olives, orchards (pome & stone fruits) ornamentals, sisal, sugarcane, tea, tree nurseries, turf, vineyards & noncrop area, major use is on maize; in the usa it is also used to control vegetation & algae in farm ponds, fish hatcheries, etc It is a non-systemic contact & stomach insecticide with some acaricidal action insecticide for cotton, peas, soybeans, peanut, corn, wheat & other small grains, eg, rice (former use), alfalfa, sorghum (former use), cattle, sheep, goats, swine, & horses (former use), fruits & nuts (former use), ornamentals, forage, & turf (former use), & certain agricultural premises (former use) As dip to control scabies on cattle & sheep; minor use: for armyworms, cutworms, & grasshoppers; for mealybug & pineapple gummosis moth control on pineapples & weevil control on bananas control of cassia obtusifolia in soybeans; used for control of animal ectoparasites Conditional and restricted use as an insecticide and as a miticide in foliar treatment of: cranberries, strawberries, apples, pears, quinces, nectarines, peaches, bananas, pineapple, eggplant, peppers, pimentos, tomatoes, broccoli, brussel sprouts, cabbage, cauliflower, collards, kale, kohlrabi, spinach, lettuce (head and leaf), parsnips, rutabagas, beans (lima, green and snap), corn (sweet), cowpeas, okra, alfalfa, barley, oats, rice, rye, wheat, celery, cotton, horseradish, peanuts, peas, sunflowers, soybeans, ornamental plants, birch, elm, hickory, maple oak, and noncrop areas. Also used in seed crop foliar treatment of clover and trefoil; in soil treatment of corn; in back rubber of beef cattle; in animal treatment of goats, sheep, beef cattle, and hogs; and aerial application and tank mixtures. Toxaphene 8 Emulsifiable Insecticide Conditional and restricted use as an insecticide and as a miticide in foliar treatment of small grains, corn, and cotton. Also used in aerial application. Rigo toxaphene 8, For use only under special emergency exemptions Restricted use as an insecticide and as a miticide in foliar treatment of barley, oats, rice, wheat, cotton, and soybeans and in aerial application. Unclassified use as an insecticide and as a miticide in manufacturing only. Conditional and unclassified uses as an insecticide and as a miticide in foliar treatment of cranberries, strawberries, grapefruit, kumquat, lemons, limes, oranges, tangelos, tangerines, apples, pears, eggplant, tomatoes, broccoli, brussel sprouts, cabbage, cauliflower, lettuce, spinach, carrots, onions, parsnips, rutabagas, beans (dry, lima, green), barley, rice, rye, celery, corn, cotton, soybeans, wheat, oak, and alfalfa (seed crop). Also used in aerial application. Conditional and restricted use as an insecticide and as a miticide in foliar treatment of bananas and pineapple; in animal treatment of sheep and beef cattle; and in aerial application. Used as an insecticide and as a miticide in foliar treatment of peanuts, soybeans, and cotton; also, used in aerial application and tank mixtures. Hercules Toxaphene 72% Emulsifiable Concentrate Used as an insecticide and as a miticide in foliar treartment of barley, oats, sunflowers, and wheat; also, used in aerial application. Red Top Toxaphene 8 Spray
Simazine
Toxaphene
K041; K098; P123; D015
Priority Pollutants - Semi-Volatile Organics
151
Appendix 1 Organic synthesis (dyes) chem int-eg, for higher chlorinated phenols (unisolated); component of disinfectant formulations (as chlorophenol); chem int for phenolic resins (possible use); solvent for polyester fibres (possible use) Intermediate in the manufacture of dyestuffs, higher chlorophenols, and preservatives. Catechol production ... Utilized in a process for extracting sulfur and nitrogen cmpd from coal. [R4] the ortho isomer ... Has shown excellent killing action within a few hr against various ascarid eggs & larvae on soil, brick, concrete, metal, & wood surfaces as a 1-5% emulsion. Soil sterilant Used as a disinfectant/bacteriocide/germicide for animal pathogenic bacteria (gram negative and gram positive vegetative) in or on: household premises, sickroom equipment, sickroom premises, swimming pool related surfaces, commercial premises, industrial premises, institutional premises, bathroom premises, urinals, water closets, and garbage containers. /Septi-Kleen/ [R2] Used as a disinfectant/bacteriocide/germicide for animal pathogenic bacteria on bathroom premises or in toilet bowls and urinals. /Pine-O Disinfectant/ [R2 External germicides; preservative for glues, gums, paints, inks, textile & leather goods medication: topical antiseptic; medication (vet): has been used as topical antiseptic Used as disinfectant medication (vet): in topical medicaments & in intrauterine lubricants as antiseptic & preservative (0.1-0.2% concn). Chlorocresol & chloracetamide are used in medications, glues, & cosmetics as preservatives. Used in injectable formulations as preservative. Chlorocresol (p-chlorometacresol) was formerly utilized as preservative & antifungal agent in eyedrops Fungicide In synthesis of antihelminthic bithionol sulfoxide chem int for herbicides such as 2,4-dichlorophenoxyacetate, bifenox & dichlorprop herbicides, 4-(2,4-dichlorophenoxy)butyrate herbicide 2,4-dcp is used as a feedstock for the manufacture of certain methyl cmpd used in mothproofing, antiseptics & seed disinfectants. 2,4-DCP is also reacted with benzene sulfonyl chloride to produce miticide or further chlorinated to pentachlorophenol, a wood preservative. Manufacture of pharmaceuticals, plastics, insecticides, fungicides, rubber chem, wetting agents, dyestuffs. Additives to lubricants and gasolines; in plasticizers. Commercial mixtures horticultural formulation for eradication of crown gall tumors. Used in phosphate esters, alkylated xylenols, antioxidants. Xylenol 100 in solvents, pharmaceuticals, insecticides and fungicides; plasticizers; rubber chemicals; wetting agents; additives to lubricants and gasolines; dyestuffs. Commercial mixtures Used in the production of high-viscosity phosphate esters, as a feedstock for hindered phenol antioxidant and specialty modified phenolic resin manufacture. Xylenol 410 Used as a disinfectant/bacteriocide/germicide, sanitizer, virucide and fungicide on hospital premises, hospital critical premises, human nursery premises, hospital patient premises, hospital noncritical premises, surgical instruments, hypodermic needles/syringes, dental instruments, hospital instruments, oral and inhalation equipment, diagnostic instruments/equipment, dental appliances, hospital critical equipment, dental equipment, hospital materials, human nursery equipment, hospital janitorial equipment, lockers, laundry (hospital), diapers (hospital), laundry equipment, bathroom premises, water closets, and hard, nonpourous surfaces. Bulk Lysol Brand Disinfectant Used as disinfectant/bacteriocide/germicide, fungicide and sanitizer against animal pathogenic bacteria (gram - and gram vegetative) and pseudomonas spp on household premises, household contents (nursery), sickroom premises, bathroom premises, toilet bowls, diaper pails, and garbage containers. Lysol Brand disinfectant Used as a bacteriostat against Agrobactrium tumefaciens (crown gall) on almonds (bark treatment, dormant application), walnuts (post-harvest application to
2-Chlorophenol
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2,4-Dimethylphenol
152
Appendix 1 non-stored commodity, dormant application), pears (bark treatment, dormant application), apricots (bark treatment dormant application), cherries (bark treatment, dormant application), peaches (bark treatment, dormant application), plums (bark treatment, dormant application), and prunes (bark treatment, dormant application, dormant application). Also used against Pseudomonas savastanoi (olive knot) on olives (bark treatment, dormant application). Bacticin Used as a microbicide/microbistat against Agrobacterium tumefaciens crown gall in bark treatment and dormant application of grapes, almonds, walnuts, apples, pears, apricots, cherries, peaches, plums, prunes, and ornamental plants. Gallex Used as an intrastate and insecticide and miticide against flies and their eggs in/on livestock buildings (open premise treatment), livestock loafing areas (open premise treatment), livestock manure, pets (open premise treatment), non-farm animal non-pet buildings (extrior treatment, non-farm animal/non-pet manure, homes (yards, outdoor), bakeries (outdoor-inedible), meat processing plants (outdoor-inedible) and land fill areas. Du Cor Concentrated fly Insecticide/ Used as an intrastate, insecticide/miticide, and fungicide on wood to control termites. Wood preservative; insecticide; as indicator; as reagent for detection of potassium & ammonium ions. Chem int for ci sulfur black 1, ci sulfur black 2, photochemicals & explosives; acid-base indicator; fungicide for protection of metal-cutting oil emulsions. Polymerization inhibitor in styrene production. 2,4-Dinitrophenol is used primarily as a chemical intermediate for the production of azo dyes. Use in manufacturing of photographic developers. /SRP: Former use Medication, as dieting aid. Used as a fungicide on railroad ties, wood poles/posts, wood pilings, and in wood pressure treatment to prevent wood rot/decay fungi. Used as an insecticide and miticide for domestic dwellings (outdoor) to control mosquitos Insecticide, fungicide, herbicide, defoliant. Former use in dyestuff industry. Former use contact herbicide for the control of broad-leaved weeds in cereals at less than 10 kg/ha and in emulsifiable concentrate formulations, for the pre-harvest desiccation of potatoes and leguminous seed crops. Former uses contact insecticide, toxic to eggs of certain insects, insecticidal uses limited, by phytotoxicity, to dormant sprays on tree fruits & raspberry. Fungicidal activity against overwintering venturia inaequalis on orchard floor, also against foreign fungi in mushroom houses (applied when houses are empty). Former use 4,6-Dinitro-o-cresol is used as a dormant spray insecticide, especially for fruit trees or on waste ground, to kill locusts and other insects. Former use at one time it was used medically as a weight-reducing agent similar to dinitrophenol. Former use Indicator in 2% alc soln; ph range 5 colourless, 7.0 yellow, but colour change is not sharp & cannot be used where carbon dioxide is present used in synthesis of dyestuff and other intermediates Intermediates for the production of pigments, rubber chemicals, lumber preservatives, photographic chemicals, and fungicide agents. Reagent for glucose As indicator in 0.1% alcohol soln; ph range: 5.6 colourless, 7.6 yellow fungicide chem intermediate for the insecticides methyl parathion & ethyl parathion, azo & sulfur dyes, n-acetyl-p-aminophenol; chem intermediate for leather preservatives as substrate for analysis of udp-glucuronyl transferase bactericide Leather treatment agent Has been recommended for use in the preservation of starches, dextrins, glues as a molluscicide to inhibit fermentation in
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
2-Nitrophenol
4-Nitrophenol Pentachlorophenol
153
Appendix 1 various materials registered homeowner uses incl maintenance of boats, trailers, station wagons, siding, fences, outdoor furniture & similar articles. There are a large number of registered industrial uses, such as construction of boats and buildings, mold control in petroleum drilling & prodn, & in treatment of cable coverings, canvas belting, nets, construction lumber & poles. Other uses incl incorporation in paints, pulp stock, in pulp & paper, cooling tower water, hardboard & particle board. Wood preservative (fungicide) chem int for sodium pentachlorophenate soil fumigant for termites herbicide for weeds & preharvest defoliant for seed crops srp: former use seed treating agent for beans herbicide for control of moss-eg, on lawns & roofs fungicide-eg, for use on prunes preservative-eg, for paints, leather, textiles & inks slimicide & algaecide in indust applications antibacterial agent in disinfectants & cleaners Used as a preharvest defoliant on selected crops SRP: Former use In various products, pentachlorophenol has been used as a herbicide, algacide, defoliant, wood preservative, germicide, fungicide, and molluscicide. As a wood preservative, it is commonly applied as a 0.1% solution in mineral spirits, NO 2 fuel oil, or kerosene. It is used in pressure treatment of lumber at 5% concentration. Weed killers contain higher concentrations. PCP is no longer available for over-the-counter sale in the USA. General disinfectant in soln or mixed with slaked lime, etc, for toilets, stables, cesspools, floors, drains, etc; mfr of colourless or light-coloured artificial resins, many medical & indust org cmpd & dyes; reagent in chem analysis /phenol is still std against which other antiseptics are compared phenol is bacteriostatic in concn of approx 0.2%, bactericidal above 1%, & fungicidal above 1.3% chem int for phenolic resins & bisphenol a chem int for caprolactam via cyclohexanone chem int for xylenols, esp 2,6-xylenol & cresols chem int for nonyl-, dodecyl-, & other alkylphenols chem int for adipic acid via cyclohexanol chem int for o-hydroxybenzoic acid chem int for plasticizers-eg, cresyl diphenyl phosphate chem int for 2,4-dichlorophenol & derivs chem int for pentachlorophenol & 2,4,6-trinitrophenol extractive solvent for petroleum refining chem int for medicinals-eg, phenolphthalein chem int for dyes-eg, azo dyes blocking agent for blocked isocyanate monomers preservative-eg, in pneumococcal polysaccharide vaccine analytical reagent-eg, for cholesterol peptizing agent in glue as Herbicide, defoliant srp: former uses preservative & disinfectant (as isomeric mixt); bactericide, germicide, & fungicide (as isomeric mixt); sanitizer (as isomeric mixt). /former use wood preservative, glue preservative, insecticide ingredient, bactericide and an antimildew treatment for textiles srp: former uses 2,4,6-trichlorophenol can also be used to prepare the following fungicides (although they are not believed to be produced commercially from 2,4,6-trichlorophenol): chloranil (2,3,5,6-tetra-chloro-1,4-benzoquinone), pentachlorophenol and 2,3,4,6-tetrachlorophenol. Srp: former uses antimicrobial agent srp:former use Dye intermediate; mfr plastics; insecticide; fungicide mfr pharmaceuticals Acenaphthylene is a component of crude oil, coal tar and a product of combustion which may be produced and released to the environment during natural fires Important source of dyestuffs (manufacture of alizarin dyes) chem intermed for dyes-eg, vat green 7 diluent for wood preservatives (anthracene oil) anthracene is used for manufacture of anthraquinone, an important raw material for the
Phenol
Acenaphthene Acenaphthylene Anthracene
154
Appendix 1 manufacture of fast dyes, and also in the production of synthetic fibres, plastics, and monocrystals. /used in the prepn of alizarin, phenanthrene, carbazole, anthraquinone; calico printing; as component of smoke screens; as scintillation counter crystals; organic semiconductor research Manufacture of dyes; as reagent for hydrogen peroxide in milk . Org synthesis; stain in microscopy; stiffening agent in rubber compounding mfr of plastic films; it reacts with ink erasers to give colored products & therefore has been used in security printing; lab agent for detection of hydrogen cyanide & sulfate, for quantitative determination of nicotine & as spray reagent for sugars Lignification measurement Benzidine is a chemical intermediate in the synthesis of direct black 4, 8; direct blue 2, 6; direct brown 1A, 2, 6, 31, 59, 74, 95, 154; direct green 1, 6, 8; direct orange 8; direct red 1, 28, 37; direct violet 1, 22; and acid red 85. Alcoholic benzidine & hydrogen peroxide were formerly used to verify tlc bands attributed to blood. The pattern of benz(a)anthracene (BA) release into air and water is quite general since it is a universal product of combustion of organic matter. Benzo(a)pyrene's (BaP) release to the environment is quite wide spread since it is an ubiquitous product of incomplete combustion Used extensively as a positive control in a variety of laboratory mutagenicity & carcinogenicity short-term tests. Research chemical not used commercially in usa Release of benzo(b)fluoranthene is most likely to result from the incomplete combustion of a variety of fuels including wood and fossil fuels. Plants may produce benzo(b)fluoranthene Benzo(ghi)perylene is a component of crude oil and a product of combustion which may be produced and released to the environment during natural fires Benzo(k)fluoranthene's (BkF) release into air and water is quite general since it is a ubiquitous product of incomplete combustion. RESEARCH CHEMICAL Used as flame retardant additives in polymers. Former use Organic intermediate plasticizer for pvc-based flooring products, polyvinyl acetate emulsion adhesives, other plastics, eg, ethyl cellulose, in coatings, eg, for automobiles Plasticizer for polyvinyl and cellulose resins Monochloronaphthalenes have been used for chemical resistant gage fluids and instrument seals, as heat exchange fluids, high boiling specialty solvents, color dispersions, as crank case additives to dissolve sludge and gums, and as ingredients in motor tune-up compounds.
Benzidine
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene Benzo(g,h,i)perylene Benzo(k)fluoranthene 4-Bromophenyl phenyl ether Butyl benzyl phthalate
2-Chloronaphthalene
155
Appendix 1 Dye int, pharmaceuticals, agricultural chemicals chem int for dyes, eg, vat red 32 chem int for azoic coupling agents 5 & 10 chem int for urea herbicides, eg, monuron chem int for pigments, eg, pigment green 10 Reacts with anhydrous hydrogen chloride and phosgene at 70-75 deg C in dioxane to produce p-chlorophenyl isocyanate, an intermediate used for the production of urea herbicides Organic synthesis research chemical Chrysene's release to the environment is quite wide spread since it is a ubiquitous product of incomplete combustion Solvent; intermediate for polysulfide rubber Solvent for waxes, gums, resins, tars, rubbers, oils, asphalts, insecticide for termites & locust borers removing sulfur from illuminating gas; as intermed in mfr of dyes; as heat transfer medium as degreasing agent for metals, leather, wool; as ingredient of metal polishes indust odor control Herbicide, insecticide, and soil fumigant as solvent mixt used to remove lead & carbonaceous deposits from engine parts; as component of rust-proofing mixt as a magnetic coil coolant; in woodpreserving cmpd chem intermed for making agric chem; emulsifiable form recommended for deodorizing garbage & sewage org synth esp of pesticides & solvent in chem processes Used as a process solvent in the manufacture of toluene diisocyanate. Ortho-dichlorobenzene is used as a solvent in the following applications: motor-oil additive formulations; paints; formulations for removing paints; firearm cleaners; dissolution of pitch on papermaking felts; a carrier for wood preservatives and repellents; and upper cylinder lubricants Hydrolysis of 1,2-dichlorobenzene with KOH and NaOH gives orthochlorophenol an intermediate for dyestuffs and initiator for higher chlorinated phenols Manufacture of 3,4-dichloroaniline, solvent for oxides of non-ferrous metals Chem intermed for benzidine, an intermed for dyes, in synthesis of phenylbutazone (antiarthritic drug) antisludging additive to motor oil, evaluated as agent for insecticidal and insecticidal synergistic activity, desuckering agent for tobacco plants, reductant in reclamation of rubber, component of experimental organometallic polymers, use in photochromic resin compositions, in polymerization reactions. In mfr of hydrogen peroxide Some hydroazobenzene derivatives are used as flame-retardant agents. Hydrazobenzene derivatives Fumigant & insecticide /reacted with potassium hydroxide or sodium hydroxide to produce chlorophenols; used in the preparation of arylene sulfide polymers in the pps polymerization process Insecticidal fumigant; popular for domestic use against clothes moths germicide; mfr of 2,5-dichloroaniline; dyes; used in pharmacy p-Dichlorobenzene is sometimes used as a deodorant for garbage and restrooms, as well as an insecticide for control of fruit borers and ants. May be applied to tobacco seed beds for blue mold control; for the control of peach tree borer; and mildew and mold on leather and fabrics. Gallery injections with 6 insecticides and 3 fumigants were tested for comparative effectiveness in controlling Prionoxystus robiniae (Peck), and Paranthrene simulans (Grote).
4-Chloroaniline
Chrysene Bis(2-Chloroethoxy)methane
1,2-Dichlorobenzene
1,2-Diphenylhydrazine
1,3-Dichlorobenzene
1,4-Dichlorobenzene
156
Appendix 1 Chem int for toluene-2,4-diamine, a toluenediisocyanate int; gelatinizing & waterproofing agent in explosives; chem int for dyes (former use) used by the munition industry as a modifier for smokeless powders. 2,4-Dinitrotoluene is used to prepare 2,4-toluenediisocyanate by catalysed hydrogenation followed by phosgenation. Used as an explosives intermediate, rubber chemical and plastics manufacture. Used as a plasticizer in moderate and high explosives. Chem int for toluene-2,6-diamine, a toluene diisocyanate int; gelatinizing & waterproofing agent in explosives Used in the synthesis of TNT, urethane polymers, flexible and rigid foams, surface coatings and dyes MFR azo dyes [r1] curing agent for isocyanate-containing polymers [r6] rubber & plastic compounding ingredient [r7] 3,3'dichlorobenzidine is used alone and in blends with 4,4'-methylenebis(2-chloroaniline) as a curing agent for liquid-castable polyurethane elastomers; in color test for /detection/ of gold [r8] 3,3'-Dichlorobenzidine base and salts are used as chemical intermediates to produce pigments that are produced commercially in the USA (Pigment Yellows 12, 13, 14, 17, 34, & 55). [R9] The yellow pigments derived from 3,3'-dichlorobenzidine and salts can be used as substitutes for the lead chromate pigments Dibenz(a,h)anthracene's (DBahA) release to the environment is quite general since it is a ubiquitous product of incomplete combustion Insect repellant for impregnation of clothing as manometer fluid solvent for chlorinated rubber plasticizer in nitrocellulose lacquers, elastomers, explosives, nail polish & solid rocket propellants; solvent for perfume oils; perfume fixative; in textile lubricating agent; in safety glass; in printing inks; resin solvent; paper coatings; in adhesives /an insect repellant, in general not as effective as dimethyl phthalate except to trombiculid mites. Widely used as plasticizer, since it is compatible with number of resins. It is one of most common plasticizers for nitrocellulose, ethylcellulose, & benzylcellulose. Gives long life to outside varnishes exposed to sun & weather. Plasticizer for polyvinyl acetate & polymethylmethacrylate. It enters into composition of leather varnishes & mixed lacquers Used as a plasticizer in plastics & rubber materials plasticizer for cellulose ester resins plasticizer for polystyrene resins plasticizer for vinyl resins
2,4-Dinitrotoluene
2,6-Dinitrotoluene
3,3'-Dichlorobenzidine
Dibenzo(a,h)anthracene
Di-n-butyl phthalate
Di-n-octyl phthalate Diethyl phthalate
Dimethyl phthalate
Solvent & plasticizer for cellulose acetate & cellulose acetate-butyrate compositions for making varnishes & clear white or slightly colored clear films which may be exposed to the sun in solid rocket propellants, lacquers, coating agents, safety glass, molding powders & perfumes since world war ii has been used effectively as a mosquito & insect repellant. It is a plasticizer for polyvinyl acetate & has a gelling action on polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetal, & polystyrene. It is compatible with acrylic resins & rubbers, improving their plasticity. Plasticizer for cellulose ester plastics dispersing medium, eg, dye carrier plasticizer in hair spray
157
Appendix 1 Fluoranthene Fluorene Constituent of coal tar & petroleum derived asphalt used as lining material to protect interior of steel & ductile-iron potable water pipes and storage tanks research chemical Chem int in numerous misc applications & in formation of polyradicals for resins /in resinous products, dyestuffs Derivatives of fluorene show activity as herbicides and growth regulators. In organic syntheses as a raw material for synthetic rubber; plasticizer for polyvinyl chloride; as a rubber peptizing agent in the manufacture of nitroso and styrene-type rubbers additive for pyrotechnic compositions for the military, porosity controller in manufacture of electrodes; intermediate in dye manufacture. A selective fungicide suggested for seed treatment of wheat against bunt (tilletia tritici) found effective for control of dwarf bunt. Attribute control to inhibitory action of vapor on spore germination. Fungicide for control of smut on grain, esp wheat chem intermediate. Eg, for dyes & hexafluorobenzene in organic syntheses as a raw material for synthetic rubber; plasticizer for polyvinyl chloride; as a rubber peptizing agent in the manufacture of nitroso and styrene-type rubbers additive for pyrotechnic compositions for the military, porosity controller in manufacture of electrodes; intermediate in dye manufacture. A selective fungicide suggested for seed treatment of wheat against bunt (tilletia tritici) found effective for control of dwarf bunt. Attribute control to inhibitory action of vapor on spore germination. Fungicide for control of smut on grain, esp wheat chem intermediate. Eg, for dyes & hexafluorobenzene Solvent for elastomers; heat-transfer liq; transformer & hydraulic fluid; wash liquor for removing c4 & higher hydrocarbons. Chem int for fluorinated lubricants, rubber compounds; fluid for gyroscopes Intermediate for many insecticides, polyester resins, and flame retardants. Intermediate for resins, dyes, pharmaceuticals. /Used to make shock proof plastics, acids, esters, ketones, and fluorocarbons Solvent; in explosives; as camphor substitute in celluloid component of screening smokes and component of extreme pressure lubricants; degassing agent in production of aluminum & magnesium metals Organic synthesis; retarding agent in fermentation Medication (Vet): Anthelmintic (flukicide) Former use Hexachloroethane is used in refining aluminium alloys. It is also used for removing impurities from molten metals, recovering metals from ores or smelting products and improving the quality of various metals and alloys. Hexachloroethane is contained in pyrotechnics. It inhibits the explosiveness of methane and the combustion of ammonium perchlorate. Smoke containing hexachloroethane is used to extinguish fires. Hexachloroethane has various applications as a polymer additive. It has flame proofing qualities, increases sensitivity to radiation crosslinking, and is used as a vulcanizing agent. Added to polymer fibres, it acts as a swelling agent and increases affinity for dyes. Moth repellant former use/; fire extinguishing fluids manufacture; laboratory chemical; military smoke candles and grenades; plasticizer for cellulose esters; insecticide and rubber process solvent; camphor substitute in nitrocellulose solvent; retardant in fermentation process Indeno(1,2,3-cd)pyrene (IP) is formed in most combustion or elevated temperature processes that involve compounds containing carbon and hydrogen
Hexachlorobenzene
Hexachlorobutadiene Hexachlorocyclopentadiene
Hexachloroethane
Indeno(1,2,3-cd)pyrene
158
Appendix 1 Solvent for lacquers & plastics solvent for many oils, fats, gums, resins, nitrocellulose, & vinyl-resin copolymers chem int for 3,3,5-trimethylcyclohexanol, & 3,5-xylenol; specialty solvent in pesticides; stoving lacquers solvent in acrylic, epoxy, polyester and silicone resin systems MFR OF phthalic & anthranilic acids, naphthols, naphthylamines, sulfonic acid, synthetic resins, celluloid, lampblack, smokeless powder, hydronaphthaleneS. Is used in the preparation of anthraquinone. Is used for the manufacturing of indigo. Is used in the formation of perylene via the intermolecular Scholl reaction. A high yielding (98%) process from the oxidn by microrganisms, has been developed in Japan for the production of salicylic acid from naphthalene. Chem int for phthalic anhydride chem int for 1-naphthyl-n-methylcarbamate insecticide chem int for beta-naphthol & synthetic tanning chems chem int for surfactants-eg, naphthalene sulfonates chem int for 1-naphthylamine (former use) mediciation (vet) externally, on livestock & poultry to control lice. Ingredient of some moth repellants and toilet bowl deodorants. Sulfonation of naphthalene with sulfuric acid produces mono-, di-, tri-, and tetranaphthalenesulfuric acids. Intestinal vermifuge and wood preservative. Former use Manufacture of aniline; solvent for cellulose ethers; modifying esterification of cellulose acetate; ingredient of metal polishes in soaps, shoe polishes, for refining lubricating oils, mfr of pyroxylin cmpd a preservative in spray paints, constituent of floor polishes, substitute for almond essence, & in perfume indust used to produce benzidine and metanilic acid as well as dinitrobenzene and dyes such as nigrosines and magenta used in the production of isocyanates, pesticides, rubber chemicals and pharmaceuticals (acetominophen) Industrial solvent, antioxidant; solvent in fibre & plastics industry; in lubricants, condensers to incr dielectric constant; has been used as nematocide; softener for copolymers. Former uses formerly in prodn of rocket fuels research chemical; chem int for 1,1-dimethylhydrazine (former use) Solvent, Rubber accelerator Inhibition of nitrification in soil, used as plasticizer for acrylonitrile polymers, used in active metal anode-electrolyte systems (high-energy batteries), in the preparation of thiocarbonyl fluoride polymers, in the plasticization of rubber. No evidence was found that NDMA is used at present, except for research purposes N-nitrosodiphenylamine is an effective radical scavenger, and can be used to stabilize monomers, polymers, and petroleum products. In rubber processing, its major use is believed to be as an anti-scorching agent, or vulcanization retarder, during rubber compounding chem int for n-phenyl-p-phenylenediamine, a rubber chem Used as a rubber accelerator. Used as a staining retarder for natural and synthetic rubbers. Used as a vulcanization retarder (0.5-1.0%) in a variety of rubbers and to make p-nitrosodiphenylamine. N-nitrosodiphenylamine, used as an additive in the rubber industry, was determined to be a powerful nitrosating agent, reacting with other amines present in the rubber to form n-nitrosamines which may be released to the air. Explosives; biological research research chemical Synthesis of drugs and phenanthrenequinone
Isophorone
Naphthalene
Nitrobenzene
n-Nitrosodimethylamine
N-Nitrosodiphenylamine
Phenanthrene
159
Appendix 1 Pyrene Biochemical research No known use Pyrene from coal-tar has been used as a starting material for the synthesis of benzo(a)pyrene. Solvent in chemical manufacturing, dyes & intermediates, dielectric fluid, synthetic transformer oils, lubricants, heat-transfer medium, insecticides. Former use: As a soil treatment for termite control. Used as a comonomer with p-Dichlorobenzene in the production of arylene sulfide polymers. /Used as a dye carrier , intermediate in the manufacture of herbicides and higher chlorinated benzenes, dielectric fluid, solvent, heat-transfer medium. Used in degreasing agents, septic tank and drain cleaners, wood preservatives, and abrasive formulations
1,2,4-Trichlorobenzene
160
Appendix 2
APPENDIX 2
Table 25. Scientific papers relating the development or use of immunoassays for organic pollutants
Analyte
Alachlor Aroclor 1248 Aroclor 1254 Amidochlor Atrazine Atrazine Atrazine Atrazine Atrazine Azinphos-methyl Bisphenol A
Type and Antibody

ELISA polyclonal ELISA polyclonal ELISA polyclonal ELISA ELISA monoclonal ELISA Polyclonal ELISA Polyclonal Flow inject immuno assay Fluorescent Immunoassay ELISA monoclonal ELISA monoclonal
LOD (g/L) and sample matrices

0.2 water 1.34 in water, soil and sediments Nr Nr 0.03 water and soil 0.009 water 0.011 fresh water 0.02 water 0.5 buffer 0.4 buffer 5.0
References
P.C.C Feng, S.R. Horton, C.R. Sharp, J. Agric. Food Chem., 40 (1992) 211 J.C. Johnson, J.M. Van Emon, Anal. Chem., 68 (1996) 162 J.P. Mapes K. D. McKenzie, T. N. Steward L. R. Mc. Clelland, W. B. Studabaker, W. B. Manning, S. B. Friedman, Bull. Environ. Contam. Toxicol, 50 (1993) 219 P.C.C Feng, S.R. Horton, C.R. Sharp, J. Agric. Food Chem., 40 (1992) 211 P. Schneider, B. D. Hammock, J. Agric. Food. Chem., 40 (1992) 525 J. Gascon, A Oubia, B. Ballesteros, D. Barcel, F. Camps, M-P. Marco, M.A. Gonzlez Martnez, S. Morais, R.Puchades A. Maqueira, Anal. Chim. Acta 347 (1997) 149 S. J. Huber, Chemosphere, 14 (1985) 1795 P.M. Krmer, B.A. Baumann, P.G. Stocks, Anal. Chim. Acta, 347 (1997) 187 J Feng, G Shan,l Maquieira,M E. Koivunen,B Guo, B D. Hammock, I M. Kennedy Anal. Chem. 75 (2003) 5282 J.V. Mercader, A. Montoya. J. Agric. Food Chem., 43 (1995) 2789 Y.Goda, A. Kobayashy, K. Fukuda, S. Fujimoto, M. Ike, M. Fujita Water Sci. Technol. 42 (2000) 81
161
Appendix 2
Bisphenol A
ELISA monoclonal Automated bacterial magnetic particles based immunoassay monoclonal ELISA Polyclonal Immunoaffinity Chromatography Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal
Fibre optic immunosensor
0.05
Takeda Chemical Industries L-EC Cited 27 May 2003 T.Matsunaga, F. Ueki, K. Obata, H. Tajima, T. Tanaka, H. Takeyama, Y. Goda, S. Fijumoto Anal. Chim Acta 475 (2003) 75 MP Zhao, YZ Li ZQ Guo, XX Zhang WB Chang. Talanta 57 (2000) 1205 MP Zhao, YZ Li ZQ Guo, XX Zhang WB Chang J. Chromatogr. 783 (2003) 401 M.A. Gonzlez, S. Morais, R. Puchades, A. Maqueira, A. Abad, A. Montoya, Anal. Chim. Acta, 247 (1997) 199 S.W. Jourdan A.M. Scutellaro J.R. Fleeker D. P. Herzog F. M. Rubio J. Agric. Food Chem 4 (1995) 2784 F.K. Koppataschek, R. A. Liebl, A. L. Kriz, L.L. Melhado, Agric. Food Chem, 38 (1990) 1519 K.E. Brummel, J. Wright M. E. Eldefrawi, Agric. Food Chem., 15 (1997) 3292
Bisphenol A
0.0023
Bisphenol A Bisphenol A Carbaryl Carbofuran Clomazone Chlordane
0.1 Nr 0.05 water, milk, honey urine and water 0.056 in water 0.01 soil 0.41 in buffer
Monoclonal Competitive Quenching Fluorescence Immunoassay based on laser induced fluorescence detection ELISA Monoclonal ELISA Polyclonal ELISA Monoclonal
Chlorophenols
0.04 buffer
M Nichkova,J.Feng,F. Sanchez-Baeza,M.-P Marco,B. D. Hammock, I M. Kennedy
Anal. Chem. 75 (2003), 83
Chlorpyrifos-ethyl Chlorpyrifos-ethyl Chlorpyrifos-methyl
Nr 0.015 water 1.0
J.J. Manclus A. Montoya, J. Agric. Food Chem., 44 (1996) 4063 A. Hill, J. H. Skerrit, R. J. Bushway, W. Pask K.A.M. Larkin, T.W. Korth, K. Bowmer, J. Agric. Food Chem., 42 (1994) 2051 J.H. Skerritt, A.S. Hill,H. L. Beasely, S. L. Edward, D. P. McAdam J. AOAC Int., 75 (1992)1466
162
Appendix 2
Cypermethrin Deltamethrin DDT DDT + DDE Diazinon Dicofol 2,4 Dinitrophenol 2,4 Dinitrophenol Diuron Diuron Diuron Endosulfan Fenitrothion Fenitrothion Fenitrothion Fenoxycarb
ELISA Polyclonal ELISA Monoclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal Bioimmunoassay ELISA Monoclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA polyclonal ELISA monoclonal ELISA polyclonal ELISA polyclonal
1.3 water 0.2 water, soil and grain River water 0.3 river water and fruit juices 0.05 surface water and fruit juices Nr buffer 0.26 Buffer and river water Buffer 0.6 buffer Nr in foods 0.04 buffer 0.2 water and soil 1.0 wheat 4.0 2.0 0.1 buffer
H-J LEE, G SHAN, K CHANG AHN, E-K PARK, T. WATANABE, S. J. GEE, B. D. HAMMOCK J. Agric. Food Chem. 52 (2004), 1039 N. Lee D. P. McAdam, J.H. Skerritt, J. Agric. Food Chem., 46 (1998) 520 H.L.Beasely, T. Phongkham, M. H. Daunt, S. L. Guihot, Agric. Food Chem., 46 (1998) 3339 M.Schwalbe, E. Dorm, K. Beyermann, J. Agric. Food Chem., 32 (1984) 734 H.L. Beasely, D. P. Mc.Adam, K.A. Larkin, B.S. Ferguson, R.J. Bushway, J.H. Skerritt, Bull. Environ. Contam. Toxicol., 59 (1997) 375 H.L.Beasely, T. Phongkham, M. H. Daunt, S. L. Guihot, Agric. Food Chem., 46 (1998) 3339 A Oubia, D. Barcel, M-P. Marco., Anal. Chim Acta (1999) 1 H. Zhijian, N. A. Olson, Y. Weimin, R. P. Haugland, J. Immunol. Methods, 149 (1992) 261 A. E. Karu, M.H.Goodrow, D.J. Schmidt, B.D.Hammock, M.W. Bigelow, , J. Agric. Food Chem., 42 (1994) 301 W.H. Newsome, P.G. Collins, , Food. Agric. Immunol. 2 (1990) 75 P. Schneider, S. J. Gee, B. D. Hammock, J. Agric. Food. Chem., 42 (1994) 413 N. Lee J.H. Skerritt, D.P. McAdam J. Agric. Food Chem., 43 (1995) 1730 D. P. McAdam, A.S. Hill, H.L. Beasely, J.H. Skerritt , J. Agric. Food. Chem.,40 (1992) 1466 D. P. McAdam, A.S. Hill, H.L. Beasely, J.H. Skerritt , J. Agric. Food. Chem.,40 (1992) 1466 D. P. McAdam, A.S. Hill, H.L. Beasely, J.H. Skerritt , J. Agric. Food. Chem.,40 (1992) 1466 Andrs Szkcs , Hong T.M. Le, Ferenc Szurdoki, Bruce D. Hammock ,Anal. Chimica Acta 487 (2003) 15.
163
Appendix 2
Hydroxyatrazine Hydroxipropazine Hydroxysimazine Irgarol Irgarol Isoproturon Isoproturon Linuron 1-Naphtol Molinate Monolinuron 4-nitrophenol Nonylphenols Nonylphenols Nonylphenols
ELISA Polyclonal ELISA Monoclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Polyclonal ELISA Monoclonal ELISA Polyclonal ELISA Polyclonal ELISA monoclonal ELISA monoclonal ELISA Polyclonal
0.10 water 0.05 water and soil Groundwater See water Groundwater
B. Dunbar, B. Riggle, G. Nisender, J. Agric. Food. Chem., 38 (1990) 433 J.M. Schalaeppi, W. Fory, K. Ramsteiner, J. Agric. Food. Chem., 37 (1989) 1532 H. Kido, M.H. Goodrow, V. Griffeth, A. D. Lucas S. J. Gee, B. D. Hammock, , J. Agric. Food. Chem., (1997) 414 B. Ballesteros, D. Barcel, F. Camps, M-P. Marco, Anal. Chim.Acta., 347 (1997) 139 H. Kido, M.H. Goodrow, V. Griffeth, A. D. Lucas S. J. Gee, B. D. Hammock, , J. Agric. Food. Chem., (1997) 414 Petra Krmer
0.03 water Foods 8.0 Buffer, urine and soil 1.0 buffer Food
M.F.Katmeh, D. Stevenson, G. W. Aheme, Analyst, 119 (1994) 431 P. Schneider, M.H. Goodrow, S. J. Gee, B. D. Hammock, J. Agric. Food. Chem., 42 (1994) 413 P.M. Krmer, M-P. Marco, B.D. Hammock, J. Agric. Food. Chem., 42 (1994) 934 C. RUFO,B D. HAMMOCK,S. J. GEE,J A. LAST, G GONZALEZ-SAPIENZA J.
Agric. Food Chem. 52 (2004), 182
W.H. Newsome, P.G. Collins, Food Agric. Immunol. 2 (1990) 75
0.62 buffer and river A. Oubia, B. Ballesteros, R. Galve, D. Barcel, M-P. Marco, Anal. Chim.Acta., water 387 (1999) 255 10 Nr Nr Y.Goda, A. Kobayashy, K. Fukuda, S. Fujimoto, M. Ike, M. Fujita Water Sci. Technol. 42 (2000) 81 Takeda Chemical Industries L-EC Cited 27 May 2003 M. Franek, J. Zeravik, SA Eremin, J. Yakovleva, M. Badea, A Danet, C. Nistor, N. Ocio, J. Emmeus Fresenius J Anal Chem 371 (2001) 456
164
Appendix 2
Nonylphenols Nonylphenol ethoxylated (10EO) Octylphenol Octylphenol Parathion Parathion Parathion PCBs Pentachlorophenol Permethrin Permethrin Pyrene Terbuthylazine Terbuthylazine Terbutryn
Polarization fluoroimmunoassay Polyclonal Flow-injection immunoassay ELISA monoclonal Immunosensor monoclonal ELISA monoclonal ELISA recombinant Fibre optic immunosensor ELISA Monoclonal ELISA Polyclonal ELISA Monoclonal ELISA Monoclonal ELISA Polyclonal ELISA Monoclonal Flow inject immunoassay ELISA Monoclonal
7.9
M. Franek, J. Zeravik, SA Eremin, J. Yakovleva, M. Badea, A Danet, C. Nistor, N. Ocio, J. Emmeus Fresenius J Anal Chem 371 (2001) 456 M. Franek, J. Zeravik, SA Eremin, J. Yakovleva, M. Badea, A Danet, C. Nistor, N. Ocio, J. Emmeus Fresenius J Anal Chem 371 (2001) 456 A. Rose, C. Nistor J. Emmeus, D. Pfeiffer, U. Wollemberg Biosen.Bioelectron., 17 (2002) 1033 A. Rose, C. Nistor J. Emmeus, D. Pfeiffer, U. Wollemberg Biosen.Bioelectron., 17 (2002) 1033 S.D. Garret, D.J.A. Appleford, G.M. Wyatt, H.A. Lee, , J. Agric. Food Chem., 45 (1997) 4183 S.D. Garret, D.J.A. Appleford, G.M. Wyatt, H.A. Lee, , J. Agric. Food Chem., 45 (1997) 4183 N.A. Anis, J. Wright, K.R. Rogers, R. G. Thompson, J. Valdes, Anal. Lett.., 25 (1992) 627 C. Ya-Wen, R.E. Carlson, K. L. Marcus A. E. Karu, Anal Chem., 67 (1995) 3829 P. Noguera, A. Maqueira, R. Puchades, E. Brunet, M.M. Carramolino, J.C. Rodrguez-Ubis, , Anal. Chim.Acta, 460 (2002) 279 L. H. Stanker, C. Bigbee, J. Van Emon, B. Watkins, R. H. Jense, C. Morris, M. Vanderlaan , J. Agric. Food. Chem., 37 (1998) 834
2.4 Nr Nr 16.0 rice, orange 23.0 1 buffer Nr 0.1 water Meat extract
2.0 grain and flour J.H. Skerritt, A.S. Hill, D. P. McAdam, L.H. Stanker, , J. Agric. Food. Chem.,40 methanolic extracts (1992) 1287 0.04 water 0.004 groundwater water 0.03 water K. Meisenecker, D. Knopp, R. Niessner, Anal. Methods Instru., 1 (1993) 114 M. Winklmair, M.G. Weller, J. Mangler, B. Schlosshauer, R. Niessner, Fres. J. Anal. Chem., 5 (1997) 614 P. Ulrich, S. Niessner, Fres. Environ. Bull, 354 (1992) 22 T. Giersch, K. Kramer, B. Hock, Sci. Total. Environ. 132 (1993) 435
165
Appendix 2
Terbutryn Trychlorophenol Triasulfuron Triasulfuron Triasulfuron
Flow inject immunoassay ELISA Polyclonal ELISA ELISA monoclonal Chemiluminiscence immuno assay
0.1 water 0.22 water 0.05 water, soil 0.1 water soil 0.02 water soil
M. Wortberg, K. Cammann, K. Strupat, F. Hillenkamp Fres. J. Anal. Chem 348 (1994) 240 R. Galve, F. Camps, F. Snchez-Baeza, M-P. Marco, Anal. Chem., 72 (2000) 2237 J. F. Brady, J. Turner, D. H. Skinner, J. Agric. Food. Chem 4 (1995) 2542 J.M.A. Schlaeppi, W. Meyer, K.A. Ramsteiner, J. Agric. Food. Chem 40 (1992) 1093 J.M.A. Schlaeppi,A Kesser, W. Foery, J. Agric. Food. Chem 42 (1994) 1914
166
Appendix 3
APPENDIX 3
Table 26. European Union funded research projects involving sensors and biosensors for monitoring water pollution
Acronym and contract No.
Title
Coordinator
EC Duration Contribut End date ion
Abstract
ARTDEMO EVK1-CT-200200114
Artificial recharge demonstration project
Mr. Bjoern Jensen DHI Water and Environment Tel.: 004545169406 Fax: 004545169292
36 months 1,615,262 30/11/2005
ALIANCE EVK1-CT-200100091
Advance Logging Investigations of Aquifers in Coastal Environments
Dr. Philippe Pezard CNRS Dlgation LanguedocRoussillon Institut des Sciences de La Terre, de l'Eau et de l'Espace de Montpellier
36 months 2,119,868 31/12/2004
The term Artificial Recharge (AR) covers a range of technologies that typically utilise the natural cleaning capacity of natural subsoil systems to produce drinking water from surface water. This project will contribute to achievement of the overall objective by demonstrating a management tool that uses sophisticated monitoring systems linking automatic real-time data acquisition and available online sensor systems and fast field analysis kits with intelligent decision support software, which compile and communicate digested data to action protocol. The increased surveillance will be combined with development and implementation of operations schemes that will decrease the risk of contaminated drinking water and at the same time ensures a stable water production. The goal of ALIANCE is to improve the investigation, characterisation and monitoring of coastal aquifers for vulnerability assessment. For this, ALIANCE proposes to develop a set of geophysical approaches for the quantitative evaluation of brine intrusion. This includes state of- the-art geological, geochemical, petrophysical, logging and hydrological methods, and the design of 5 new geophysical and hydrodynamic logging/testing sensors yielding new data for model validation. Two end-member sites in terms of hydrogeological behaviour will be set up for long-term experimentation, the testing of the new tools, and the validation of site-specific experimental and modelling protocols from m- to 100 m-scale. Active in-situ testing from short and longer-term injections with variable salinity fluids will
167
Appendix 3 (Laboratoire de Tectonophysique) Tel.: 00330467149310 Fax: 00330467149308 Dr. Raewyn Town The Queen's University of Belfast School of Chemistry Tel.: 00442890274415 Fax: 00442890382117 simulate over drafting or saline water intrusion. The electro-hydraulic coupling principle will be used to characterise and monitor water/brine hydrodynamics in coastal environments
BIOSPEC EVK1-CT-200100086
Sensor development for routine prediction of metal bio uptake in freshwaters and soil solutions
36 months 1,459,127 30/11/2004
COOL SENSE EVK1-CT-200230019
Minimizing Mr Ole Kristensen chemicals HYDRO-X discharge and health Tel.: hazards at cooling 004598282111 circuits Fax: by a novel sensing 004598283021 approach
24 months 367,625 31/10/2004
EXPRESS-
Development of a
Dr. Petra Kramer
36 months
417300
In collaboration with end-users, sensors for routine prediction of metal bio uptake based on in situ metal speciation measurements will be compared. Aims of Water Quality Directive 2000/60/EC to protect aquatic systems by setting environmental quality standards will be addressed. The results will aid implementation of this policy by formulation of appropriate speciation based parameters for heavy metals (Cu, Pb, Cd, Zn, Ni) and by provision of the tools to enable their routine measurement by end-users. Specifically, the project will: (i) determine simple predictive quantitative parameters for assessing metal bio uptake (ii) rigorously compare several dynamic speciation techniques (iii) assess the relative merits of the techniques in the field ( iv) assess the capabilities of the techniques to predict metal uptake by organisms under a range of natural conditions (v) apply the sensors and models to routine monitoring at the river basin level Controlling the process of chemicals injection is difficult with regard to the prevention of biofouling. Therefore these chemicals are provided in excess, with the consequence that biocide substances and disinfection by-products are unnecessarily released to the environment. The COOL SENSE project aims to provide a cost effective approach for the control of biofouling prevention. This approach is based on innovative sensor systems, which rely on the application of recently developed electronics manufacturing technologies. Secondary benefits will result from the project for the operation of any kind of closed loop circuit in the industry or domestic applications, where similar heat exchange or health hazard problems can arise. Further applications may be found in any kind of problem where the deposition of scale or biofouling is of importance, such as boiler operation, water quality measurement, food industry. Quantified objectives are to reduce quantities of chemicals used of 30-50%, reduce water quantity used at least 5% and reduce operation costs bio-fouling protection of 30%. The project is devoted to the development of express
168
Appendix 3 GSF-Research Centre for Environment & Health Ingolstaedter Landstr. 1 85764 Oberschleissheim Germany Tel+49-8931812213 Fax+49-8931873372 immunodetection systems for monitoring of water pollution by pesticides and surfactants. Three new assay formats will be developed, namely flow-injection technique with polyelectrolyte carriers, homogeneous enzyme-immunoassay based on modulation of hydrolytic enzymes' activity, and photoluminescence assay with formation of immune complexes on porous silicon. Kinetic properties of these homo- and heterogeneous systems will be determined for triazine herbicides, derivatives of phenoxyacetic acid, and industrial surfactants as the antigens studied. Optimal reactants and assay regimes will be chosen. Portable devices for on-site monitoring and diagnostic kits will be manufactured. The developed techniques will be applied for control of drinking, melting and river water pollution in FSU countries. AWACSS will focus on problems caused by pollution of water with respect to sources of pollution, social and industrial structure, and economic aspects. Recent improvements in biosensor systems have offered on-line advanced measurements. Therefore, adopting a problem-driven approach, different kind of waters and partners active in the area of water management and -controlling have been selected. The Consortium plans RTD activities to upgrade a network of prototype immunoanalysers including an intelligent data evaluation for an appropriate responds to sample matrices and analytes. Data will be collected over remote inquiry by a superordinated Internet based server. The development meet the stringent demands of endusers, to improve reliability, maintenance, robustness, and analytical scope and to add new capabilities including optical design for highly parallel analysis to allow non specialist personnel to carry out measurements in real water samples and monitor water pollution. In-situ on line sensors for general hydrocarbon pollution (including BTEX, MTBE and ETBE) in soil and groundwater will be deployed at contaminated sites owned by end users within the consortium. Robust immunoassay kits for the target analytes will be designed and tested onsite. A target compound database for environmental degradation behaviour, inhibiting and stimulating effects and ecotoxicological assessment will provide a basis for signal assessment and decision/management support. The sensor and management system will be installed and tested at three sites of two end users in order to prove the early warning and management system. Deliverables will
IMMUNOTECH ICA2-CT-200110007
new express enzyme immuno techniques for pesticides and surfactants monitoring in water
30-06-2004
AWACSS EVK1-CT-200000045
Prof. Dr. Guenter Gauglitz University of Tuebingen Institute for Automated Water Physical and Analyser Theoretical Computer Supported Chemistry System Tel.: 00497071297692 7 Fax: 00497071295490 Dr. Thomas Track Dechema Gesellschaft Fuer Chemische Technik und Biotechnologie E.V. Tel.: 0049697564427 Fax: 0049697564388
39 months 1,692,399 31/02/2005
WATCH EVK1-CT-200000059
Water Catchment Areas: Tools for management and control of hazardous compounds.
36 months 1,541,067 29/02/2004
169
Appendix 3 include (1), an integrated management tool for catchment areas with contaminant sources, including a risk management and reduction strategy; environmental impacts, economical and socio-economical effects and (2), in-situ sensors and rapid in field immunoassay kits for target analytes: development of an immunoassay for MTBE. To design, construct and test new real-time measurement techniques and methods for water quality. The approach is: to fingerprint natural water characteristics, to detect the presence of complex species, to measure accurately trace levels of priority pollutants. Pendant drop optical methods integrated with CCD colorimetric techniques will form the core technologies, having been demonstrated industrially for other applications. Alternative pendant drop techniques and other interface sensor technologies will be exploited depending on the priority water and environmental needs. The practicality of the engineered solutions will be proved using laboratory simulations and with the testing of in-field portable and on-line configurations. This proposal aims to develop a novel photo-electro-bio-catalytic (PEBCAT) reactor for the treatment of groundwater contaminated with nitrates, persistent organic pollutants, and chlorine resistant microorganisms. The proposed tandem reactor electrochemically links the photo catalytic destruction of organic pollutants and micro-organisms, to the electro-bio catalytic denitrification of water. A major proportion of the EC's drinking water is derived from groundwater sources and this project can make a substantial contribution to alleviating the pressures on our limited resources by allowing drinking water abstraction from contaminated sources. The consortium includes experts from photo-electrochemistry, biotechnology, sensor technology, engineering and chemical engineering. The principal objective is to develop a pilot scale PEBCAT Reactor capable of treating real water at an affordable cost.
AQUA-STEW EVK1-CT-200000066
Water quality surveillance techniques for early warning by Interface sensors
PEBCAT EVK1-CT-200000069
Photo-Electro-BioCatalytic Treatment of Drinking Water Supplies
Dr. Georges Pottecher IRH Genie de lEnvironnement Direction des Etudes et de la Recherche Tel.: 0033383503651 Fax: 0033383503699 Dr Brian Eggins University of Ulster School of Applied Biological And Chemical Sciences, University of Ulster Tel.: 00442890366113 Fax: 00442890366207
36 months 966,486 31/01/2004
36 months 1,272,574 31/01/2004
170
Appendix 3 The aim is to develop new applications and control strategies for the sustainable removal of ammonia from wastewater on the basis of the novel process of anoxic ammonia oxidation (Anammox). Application of this new process will ensure and extend the leading position of European waste technology industries. In order to meet recent European discharge standards, research in cooperation with two wastewater companies will focus on the development and optimisation of key parameters (community structure and functioning, biosensors, control models, new conversions). The innovative aspect is the Anammox process, a more energy- efficient nitrogen removal process. Microbiological methods, biosensor development, quantitative flux analysis, and environmental engineering will be improved in a multidisciplinary approach. The main output will be a new type of pilot plant with improved control of nitrogen removal from wastewater. The MUSIC project aims at developing a prototype of an integrated package which will improve the real time quantitative estimates of the precipitation field and the assessment of their uncertainty in particular for operational flood forecasting and warning purposes. Using an innovative Bayesian multivariate formulation, the system will combine together ground point measures based upon rain gauge tele-metering networks with meteorological radar precipitation estimates and with the estimates obtained from remotely sensed satellite images. The project will test the system on real world case studies on three test catchments the Reno and the Arno rivers in Italy and the Vistula river in Poland. The resulting DSS will also include new 3D Visual User Interface and Web dissemination capabilities aiming at better operational links between the forecasters and the end users. To increase the quality of natural waters, the current trend is to integrate technologies with water recycling and/or biodegradation of wastes. To succeed with this, fast and reliable monitoring of wastewater is required. In this context the main objective of the project is to create a methodology for fast monitoring of pollution levels in wastewater. The methodology relies on a biosensor arraypattern recognition system. Array will consist of enzyme-, DNA-, and cell-modified electrodes generating fast multivariate response due to interaction of pollutants (phenols, lignins, heavy metals, surfactants) with biomolecules. By the use of chemometrics this response will be
IcoN EVK1-CT-200000054
Improved control and application of nitrogen cycle bacteria for ammonia removal from wastewater
Prof. Dr. J. Gijs Kuenen Technische Universiteit Delft Department of Biotechnology Tel.: 0031152782342 Fax: 0031152782355
36 months 1,727,950 31/01/2004
MUSIC EVK1-CT-200000058
Prof. Ezio Todini Universita Di Bologna Multi-sensor Dipartimento Di precipitation Scienze Della measurements Terra E Geologico integration, Ambientali calibration and flood Tel.: forecasting 00390512094537 Fax: 00390512094522 Intelligent signal processing of biosensors array using pattern recognition for characterization of wastewater: aiming towards alarm systems Tautgirdas Ruzgas Dept. of Analytical Chemistry Lund University 221 00 Lund, Sweden Tel: 0046 462228191 Fax: 0046
36 months 1,363,026 31/01/2004
INTELLISENSE QLK3-2000-01481
36 month 1,114,738 01/10/2003
171
Appendix 3 462224544 converted into patterns and enable fast estimation of wastewater composition and toxicity. The patterns will be derived from simultaneous analysis of wastewater with array electrodes, classical analytical techniques and toxicity tests. The deviation of the pattern from allowed or known norms will generate alarm signal. The overall objective is to enhance the development of chemical sensors, biosensors and biomimetic systems for practical applications in the abatement of water pollution from contaminated land, landfills and sediments. The aim is to provide in situ monitoring of environmental pollutants in water and contaminated soils and sediments, to facilitate optimisation of remediation technologies and natural attenuation processes. The proposed work programme is based on a series of European meetings, a centralised information facility and a broad collaboration programme. SENSPOL will cluster the sensor development activities in the EUs environmental projects and act as a catalyst for the advancement of European technology for monitoring the environment. Paths will be identified to resolve the most effective sensor systems for use in monitoring multiple pollutants contaminating water, soil and sediments and for use in situ management in order to protect ground and surface water from pollution. PURE is aimed to prevent contamination of groundwater by priority pollutants from industrials sites: recalcitrant chloro organics, BTEX and heavy metals, innovative results will be of wide applicability being validated on three different sites. PURE includes two specific subprojects; SICHMORE, developing cost-saving solutions to sec-scribe the contaminated site through reduction of sampling / analytical load by use of biosensors, advanced modelling and fuzzy logic; evoluted risk assessment methodologies will also be developed as a support tool for optimal choice of remedial actions on the basis of cost and benefits; TREES, developing preferably in situ methods to treat : 1) the pollution core in the soil and prevent contaminants migration to groundwater; 2) the plume. PURE was originated within NIKILE and involves universities , R&D performers, site owners and service providers (end users) This project is one of the two project integrating the cluster "Decontamination of ground waters and soils from heavy metals". The present project is addressed to develop sensitive and robust sensing devices, including chemical sensors and biosensors, and
SENSPOL EVK1-CT-199920001
Sensors for monitoring water pollution from contaminated land, landfills and sediments
Dr. Susan Alcock Cranfield University Institute of Bioscience and Technology Tel.: 0044 1234754339 Fax: 0044 1234750907
36 months 31/01/2004
766,800
PURE EVK1-CT-199900030
Protection of Groundwater Resources at Industrially Contaminated Sites
Mr Paolo Cortesi EniChemSpA Centro Ricerche Novara Tel.: 0039 0321 447617 Fax: 0039 0321 447378
39 months 01/07/2003
2,878,900
DIMDESMOTOM EVK1-CT-199900002
Development of improved detection Systems for monitoring toxic
Professor Manuel Valiente Universitat Autonoma de
36 months 1,096,700 31/01/2003
172
Appendix 3 Barcelona Quimica Analitica Facultat de Ciencies Tel.:0034-93 581 29 03 Fax: 0034-93 58 19 85 biomimetic systems that are capable of on-line operation and real time measurements of THM, their effects and the corresponding risk assessment for various matrices of contained soils, groundwater bodies and surface waters. The project main goal is to identify the trends of pollution and control the efficiency of remediation activities. Such a objective will carry out by developing electrochemical biosensors/immunosensors and screen printed electrodes for stripping voltammetric analysis of heavy metal contamination, emphasizing the determination of the chemical speciation of these contaminants. A portable detection system for heavy metal detection in a contaminated soil and groundwater matrices will be also deigned and constructed Endocrine disrupting compounds (EDCs) are a class of potentially dangerous substances, which is not defined by chemical nature but by biological effect. Treatment of waste water and surface water is a critical point for minimising the environmental burden imposed by natural and synthetic EDC, and for the protection of man and environment from adverse effects of EDC. Therefore SANDRINE will: - study the behaviour of EDCs in waste water treatment plants (WWTPs) and sewage sludge; - make available and adapt bioanalytical tools (bioassays and biosensors) that respond to a broad range of EDCs by effect, rather that by chemical identification and allow to trace, to quantify, and to detect EDCs in complex samples; - validate the bioassay and biosensor measurements by comparing their data with established and instrument analytical techniques, using known endoestrogens and xenoestrogens. To develop rapid and portable biosensors for monitoring algal cells and toxins and an early warning system based on biotoxin detection by hemocytes of bivalves and their immunotoxic response
heavy metals in contaminated groundwater and soils
SANDRINE ENV4-CT98-0801
Biosensor tracing of endocrine disrupting compounds in surface water, waste water and sludge for water quality assessment.
Peter-Diedrich Hansen Technische Universitt Berlin Institut fr kologie und Biologie Keplerstrae 4-6 DE - 10589 Berlin Tel:49 30 314 21 675 Fax: 49 30 314 21 463
36 months 01/02/2002
815.000
ALGAETOX ENV4-CT98-0784
AQUA-SENSE
The application of integrated biosensors with antibody and macrocyclic receptor libraries in the measurement of algal cells and toxins in water. Water quality
Anthony Peter Francis Turner Cranfield University Biotechnology Centre Tel :44 1234 75 41 32 Anne Lise Etienne
36 months 01/01/2002
800.000
36 months
746.900
The general objective of the proposed research is to develop
173
Appendix 3 Centre National de la Recherche 01/01/2000 Scientifique URA 1810 Photoregulation et Dynamique des Membranes Vgtales Rue d'Ulm 46 Ecole Normale Suprieure FR - 75230 Paris Tel : +33-144323935 Fax : +33-144323519 Dr. Jenny Emnus Department of Analytical Integrated Immuno Chemistry, Extraction University of Lund, 36 months Sampling and Portable Biosensor S-221 00 Lund, Sweden, Phone: 01/01/2000 Prototype for In46 46 2220104 Field Monitoring Fax +46 46 2224544 monitoring by luminescent cyanobacterial biosensors: a novel early warming system against algal blooms. Dr. Jenny Emnus Department of Analytical Chemistry, Biological tools for University of Lund, 36 months S-221 00 Lund, sustainable water management Sweden, Phone: 01/01/2000 46 46 2220104 Fax +46 46 2224544 biosensors for the monitoring of nutrient concentration in water. We aim to apply this novel approach towards an understanding of the factors regulating algal and cyanobacterial proliferation, in order to guard against undesired blooms of these organisms. The prevention of such occurrence is of importance for improving the quality of water in general and drinking water in particular which is a top European priority.
ENV4-CT97-0493
The overall aim of INExSPORT is to develop a portable biosensor prototype coupled on-line to a stand alone sampling unit for the selective in-field analysis of phenols and surfactants in various effluent waters
INExSPORT ENV4-CT97-0476
BIOTOOLS IC15-CT98-0138
Innovative least-cost techniques for efficient water use and the management and protection of water resources are of key importance for long-term economic and social development in Europe. Surface active compounds (SACs) are used in industrial processes as well as in trade and households as washing and cleaning agents and also for personal hygiene. Although legislators prescribe SAC biodegradability, these cannot be completely mineralised in biological waste treatment plants. They still arrive together with their metabolites in rivers and some are found in drinking water. Due to the extreme amounts of SAC emitted into sewage plants and the persistence of some of the known metabolites, it is the group of environmental pollutants with the
174
Appendix 3 highest priority (Council Directives 73/404, 76/464 and its six daughters).
PRENDISENSOR ENV4-CT97-0473
Prediction of the behaviour of potential endocrine disruptors in soil using vitellogenin Elisa assays as biosensors.
Fernando Santana Universidade Nova de Lisboa Faculdade de Cincias e Tecnologia Departamento de Cincias e 36 months Engenharia do Ambiente 01/11/2000 Quinta da Torre PT - 2825 Monte de Caparica Tel :+351-12948554 Fax:+351-12948397 Richard Maurice Walmsley University of Manchester Institute of Science and Technology Department of Biochemistry and Applied Molecular Biology GB - Manchester M60 1QD: Tel: +44-1612360409 Fax: +44-1612004174
PRENDISENSOR focuses on the evaluation and prediction of environmental impacts of endocrine disruptors in soil/water ecosystems influenced by sludge disposal on agricultural soils. A biosensor was developed, based on increased vitellogenin levels in fish, a biomarker for the presence of endocrine disruptors.
749.850
To develop novel environmental biosensors which detect and report the presence of genotoxic and other stress-inducing chemicals in water.
EMFID ENV4-CT97-0480
Environmental monitoring by fluorescence induction and detection.
36 months 01/11/2000
649.900
175
Appendix 3
RIANA ENV4-CT95-0066
BIOMETSENSOR ENV4-CT95-0141
Andreas BRECHT Eberhard-KarlsUniversitt Tbingen Institut fr Physikalische und River analyser: an Theoretische analytical system Chemie for measuring Auf der multiple analytes Morgenstelle 8 in river water. DE - 72076 Tbingen Tel +49-7071296910 Fax +49-7071294667 Philippe CORBISIER VITO - Vlaamse Development of Instelling voor new multisensing Technologisch biosensors for the Onderzoek NV detection of Afdeling Milieu bioavailable heavy Boeretang 200 metals in solid BE - 2400 Mol matrices. Tel :+32-14320372 Fax: +32-143355116
38 month 01/07/1999
1.313.700
The objective of this project is to develop a system for monitoring organic compounds present in polluted river water and in surface water. The core device shall be a multiresidue bioanalytical device, allowing testing in one sample a multitude of simultaneously present agents. In accordance with the objectives of the Environmental Workprogramme the system envisaged is expected to be more cost effective than reference techniques, to allow the detection of a broader range of analytes with a single device than established reference techniques, and to avoid most of the sample pretreatment common in current environmental multiresidue analysis with concomitant advantages in speed.
40 months 01/06/1999
548.000
The principal goal is to establish the feasibility of a biosensor technology with enhanced specificity and selectivity for the detection of several bioavailable heavy metals and which works with solid matrices. The particular benefit of this new technology will be the ability to detect multiple parameters simultaneously, such as bioavailable concentrations of several heavy metals present in solid matrices together with their global acute toxicity.
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Table 27. Main achievements of European Union funded research projects involving sensors and biosensors for monitoring water pollution
Acronym and contract No.

BIOSPEC
Main Achievements
The work carried out was based on: The comparison, both in the laboratory and in the field, of several dynamic in situ metal speciation techniques recently developed by the partners, for example an stripping chronopotentiometric electrode for metal ion speciation analysis The comparison of these techniques with the metal uptake by algae and plants under a range of conditions to assess the relevance of various speciation parameters for bio availability and bio uptake Evaluation on the best predictive parameters. Application of above developments to routine monitoring at the river basin catchments level. The metal speciation determined by the analytical techniques and that taken up by the biota (algae, bacteria and plants) has been determined for a range of well defined metal-ligands systems, under laboratory conditions. For fully labile complexes, all analytical techniques measure the same amount of metal species. Differences between the techniques are observed for less labile complexes, and for isolated natural ligands with distributed diffusion coefficients. These results indicated that the set of analytical techniques being deployed in the project will provide a complementary suite of information. The in situ deployable methods seem to be relatively free from secondary effects such as adsorption of natural ligands on the sensor surface. Studies with algae and bacterial suggest that bio uptake of some metals will be best predicted by a steady-state model that incorporates the chemical species that are at the equilibrium in the bulk medium. The general dynamic features of the analytical techniques have been characterized. Computational tools for prediction of metal complex lability at the various sensors have been developed for homogeneous and heterogeneous ligands (and their mixtures) for a range of geometries, ligands to metal ratios, for both transients and steady-state conditions. The integrated approach that combines in situ analytical techniques and modelling, calibrated against bio uptake response, will provide a cost effective tool which can be routinely deployed by relatively unskilled personnel in institutes for water monitoring. Development and performance of different immunoassays, for example the development and performance of new ELISA tests for nonylphenol and LAS. These new assays were optimised and applied for the rapid assessment of nonylphenol and LAS in real wastewater samples, and results were compared with those from LC-MS-MS in order to evaluate the good performance of the immunoassays. The results of these comparative works showed a good concordance between different methodologies. Must be said that due to the advantages of immunoassays (rapidity, small sample volume, and economy) these assays must be considered as an useful tool for surfactants evaluation in complex samples at screening level.
Sensor development for routine prediction of metal bio uptake in freshwaters and soil solutions
EVK1-CT-2001-00086
EXPRESSIMMUNOTECH Development of a new express enzyme immuno techniques for pesticides and surfactants monitoring in
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water
ICA2-CT-2001-10007
AWACSS Automated Water Analyser Computer Supported System

EVK1-CT-2000-00045
This projects was based on the construction of an automated water analyser based on immunochemistry technology with detection via total internal reflection fluorescence (TIRF). AWACSS was building on the achievements of the device obtained during a previous EU-funded project entitled, RIver ANAlyser (RIANA), with major improvements in three critical areas: 1) expanded multi-analyte analysis capability allowing for up to 30 simultaneous analyte measurements, 2) novel design approaches to the optical detection and fluidics including miniaturised integrated optics and microfluidics, and 3) intelligent remote surveillance and control that will allow for unattended continuous monitoring. During a first period this instrument was designed and during the second year the major task was the construction of the first instrument. In the AWACSS device the development of the microfluidics system has progressed. The embossing process has been optimised with a minimal amount of distortion appearing in the acrylic block during processing. The additional polishing of the mould tool has resulted in the ability to produce a good surface towards the fluidic chamber. The surface of the chamber has been made more hydrophilic by sputtering approximately 60 nm silica. The optical transmission system has been designed, tested and integrated with the 32 photodiodes and individual amplifier circuits. The system has been built into a three-compartment enclosure, enabling the electronic sensor module to be effectively screened from digital noise and for the light sensitive components to be housed in a light-tight box. The first prototype instrument is currently undergoing commissioning trials to check weather all former specifications are achieved. The second instrument is currently under construction and will have an identical specification to the first prototype. 32-way immunofluorescence sensor chips are now routinely fabricated and pigtailed. The fabrication processes have been optimised to give good coupling to fibre and low waveguide loss and the silica isolation layer deposition and annealing process has been optimised. Regeneration protocols for the standard assay and for the auxiliary system have been established. Furthermore an auxiliary system for the detection of chemically and physically unstable compounds was developed. The new antibodies where characterized via lable-free biosensor technique (RIfS). Implementations of immunoassays with the RIANA system for the delivered antibodies and derivatives where made. Also the RIANA/PAL-system was improved with limits of detection under 10 ng/L for some compounds. Up to now immunoassays for a broad range of analytes are ready to use. The ongoing monitoring process of the field test partners indicates a very good field of application for the future AWACSS instrument. Also the comparison of the biosensor system to classical analytical methods shows a very good reproducibility and a comparable sensitivity. Most of the AWACSS compounds have frequently been detected in real water samples all over Europe. Together with the results out of the market survey this leads to great chances to successfully place this system to the market of analytical instruments.
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WATCH Water Catchment Areas: Tools for management and control of hazardous compounds.
EVK1-CT-2000-00059
The main achievement were: Sensor developments A prototype near infra red (NIR) sensor device, previously developed by Cranfield University, has been continually refined and developed in order to improve its performance in soil and water matrices. The basic sensor head incorporated an 11mm disc of highly reflective, hydrocarbon-specific Fluorotrans membrane, which turns translucent on contact with free-phase hydrocarbon matrices. Multi-channel sensor arrays have been constructed by linking sensors (currently to a maximum of 10 sensors) to a standard PC using via an interface board and ADC-11 multichannel data acquisition card. The re-designed sensors were examined within a simulated in-house tank. The 9-sensor multi-sensor array was evaluated in a number of matrix arrangements with positive results. A full experimental evaluation using underground storage tank simulations indicate that ultimately, sensor performance is dependent upon a wide range of external variables, including soil matrix type, groundwater flow, soil saturation, surrounding physico-chemical conditions. Immunoassay test kits For the development of MTBE immunoassay test kits and the refinement of BTEX immunoassay test kits concentration ranges of 10-20 g/L were found to be useful for on site analytics. For the MTBE immunoassay test kits, under development at Diaclone, Besancon, the antigens MTBE-BSA and MTBEn-BSA have been produced and were used for mice immunisation to produce monoclonal antibodies. After fusion with a myeloma cell line the hybridoma that are secreting antibodies which selectively react with MTBE-BSA or MTBEn-BSA are selected and tested. Polyclonal antibodies were produced out of MTBEn-BSA. BTEX immunoassay test kits were refined at Cranfield University to get first qualitative results at the concentration ranges of 10-20 g/L. Commercially available BTEX immunoassays (SDI Inc., Newark, DE, USA), with a dynamic assay range of 90-3000 g/L did not exhibit the detection limit necessary to measure at the 10-20 g/L. Consequently, work has focussed on strategies to enhance assay detection limits. Preliminary approaches centred on using an alternative fluorescent assay enzyme label substrate to enhance assay sensitivity via improvements in assay signal-to-noise (S/N) with limited success. The next approach involved varying the reagent quantities in order to favour the competitive binding of analyte, which proved successful in that it was possible to consistently differentiate between samples containing no BTEX and those containing 11 g/L BTEX, although absolute quantification of the analytes was not reliable. Nevertheless, as a field-based screening tool, the reduced reagent immunoassay approach has promise as an initial sample screening method. Current work is focussing on the use of commercially available solid-phase sorbent extraction techniques to concentrate water samples such that lower quantitative immunoassay detection limits can be obtained. MTBE/BTEX analysis For laboratory analysis a final purge and trap-GC-MS protocol for the analysis of MTBE, its main degradation products (TBA: tert-butyl alcohol and TBF: tert-butyl formate), other fuel additives including ETBE (ethyl tert-butyl ether), TAME (tert-amyl methyl ether) and DIPE (diisopropyl ether) and aromatics (BTEX) at low microgram per litre levels in groundwater has been accomplished. Different sampling methods for analysis of MTBE and its degradation products where investigated.
AQUA-STEW
Water quality surveillance Techniques for early Warning by
Development of a plastic optical fibre sensors for environmental monitoring: Biofouling and strain applications
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interface Sensors
EVK1-CT-2000-00066
PEBCAT Photo-Electro-BioCatalytic Treatment of Drinking Water Supplies

EVK1-CT-2000-00069
The technology developed in this project will use photocatalysis to destroy low-level organic compounds, such as pesticides, and micro organisms present in water. Simultaneously, it will use electrobio-catalysis to denitrify the same water from nitrate and nitrite. This technology is particularly applicable to the treatment of contaminated groundwater. The proposal was timely as the amended Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption. The developed technology was particularly valuable to assist member states to comply with the strict guidelines set down in the Directive to ensure that the drinking water so treated can be consumed on a life long basis.
180
Appendix 3 The main scientific achievements were the development of chemical sensors, biosensors and biomimetic systems for practical applications in the abatement of water pollution has been enhanced, and the new devices have been successfully demonstrated in field situations. SENSPOL issued eleven electronic newsletters which contained detailed information useful to European researchers from various disciplines relevant to sensors and the environment, as well as to manufacturers and end users. Talks were given at scientific and user group meetings to inform the audiences and others of the applicability, state of development and achievements of sensor technologies in the abatement of water pollution, and future directions for sensors for monitoring water pollution. Many publications were made in scientific journals and elsewhere. Three major international workshops were held, on Evaluation of Chemical Sensor, Biosensor and Biomimetic Technology, Response To New Pollution Challenges and Monitoring in Polluted Environments for Integrated WaterSoil Management. Each brought together 80-100 scientists and engineers who are developing sensor technologies for environmental applications, and end-users. Results from EU RTD projects were presented and discussed. The participants addressed important topics such as monitoring environmental and remediation processes, simultaneous measurement of multiple parameters, definition of emerging monitoring tasks, new parameters for sensor application, calibration and reference methods, and sensors to meet evolving demands. Smaller working groups focused on Technologies for Monitoring in Contaminated Sediments and Monitoring Technologies for the Abatement of Water Pollution: Communication. Two Technical Meetings to compare and validate sensors in the field were held, focusing respectively on Monitoring in Contaminated Soil and Problems Related to Diffuse Pollution Sources: Characterization of Sediment, Dredged Material. The sensor instruments were used on site to measure environmentally sensitive parameters in soil, sediments and river waters. Promising results were obtained with measurements of heavy metals, calcium, chloride, general toxicity and genotoxicity. The speed of data production was fast enough for daily decision making.
Collaboration was stimulated. More than 50 short visits were sponsored for researchers from European laboratories to learn techniques, use equipment and consult with other groups, and visit reports were published in the Newsletter. A database was constructed and assistance was provided to find suitable partners for EU funding proposals.
SENSPOL Sensors for monitoring water pollution from contaminated land, landfills and sediments
EVK1-CT-1999-20001
The activities undertaken by SENSPOL have accelerated the development of sensor systems for practical applications in the abatement of water pollution from contaminated land, landfills and sediment. The usefulness of new environmental monitoring devices that can be used on site has been demonstrated. Sensor technologies are sufficiently mature to be used in routine analysis where legislative compliance is not required. Enhanced sensor devices already in existence are able to provide useful assistance in monitoring pollutants in the environment and in remediation technology. They are suitable for on site determination of certain priority pollutants where there is advantage over existing methods or where no suitable method exists, and to monitor biological effects (as alarm systems and effect-related on site tests). Some of the sensors are already able to monitor several analytes simultaneously and sensing systems are being developed to make concurrent measurement of multiple parameters. Many of the instruments are ready for commercial demonstration. Sensing technologies that are under development already provide a strong foundation for responding to new pollution challenges. The facilitating role of SENSPOL has been very beneficial for the introduction of new approaches and instruments. Hindrances to moving from prototype environmental sensing devices to sensor system products remain. Although better analytical technologies, including toxicity sensors, are important to society and public health, the market size is a factor that often seems to deter serious investment. Further validation studies and the implementation of the prototype sensing devices require future mechanisms and funding.
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PURE Protection of Groundwater Resources at Industrially Contaminated Sites

EVK1-CT-1999-00030
One of the major achievements was the development of a toxicity biosensor. The Remedios company was launched in November 1999 to develop biological sensor technology for the diagnosis and clean-up of polluted land. The company's standard suite of biosensors assesses the overall toxicity of environmental samples such as soil, sludge, sediment, groundwater, waste material and industrial effluent. The biosensors, developed at the University of Aberdeen, are based on a spectrum of bacterial strains representative of those found in the environment, and those that would be used in any bioremediation process. The biosensor organisms, containing genes from bioluminescent marine bacteria, respond to a toxic challenge by reducing light output. Remedios are marketing this technology in a series of screening and clean-up services, called Toxmonitor, Toxmap, Interprotox. Restore and Trouble-shooter.
DIMDESMOTOM Development of the PalmSens potentiostat (now commercially available) The sensor system is based on disposable screen-printed electrodes (incorporating the three-electrode system) coupled to an Development of electroanalytical stripping technique (constant current stripping chronopotentiometry). The screen-printed electrodes (with graphite-carbon improved detection working electrode, silver/silver chloride reference electrode and carbon counter electrode) are fabricated in-house onto a plastic substrate. Systems for Measurements are made on the graphite-carbon working electrode or with the working electrode modified in-situ with bismuth (III) ions monitoring toxic (bismuth film electrode) and mercury (II) ions (mercury film electrode) or by incorporation of modifiers (2,5 dimercapto-1,3,4 thiadiazole and heavy metals in bismuth (II) oxide) onto the surface of the electrode. With this system, information about an analyte is derived from the measurement of contaminated potential as a function of time. groundwater and The main environmental relevance is Monitoring of contaminated sites with toxic heavy metals is important both for identification soils of trends of pollution and to control the efficiency of remediation activities.
EVK1-CT-1999-00002
SANDRINE Biosensor tracing of endocrine disrupting compounds in surface water, waste water and sludge for water quality assessment. ENV4-CT98-0801 Endocrine disrupting compounds (EDCs) are a class of potentially dangerous substances, which are not defined by chemical nature but by biological effect. Treatment of waste water and surface water is a critical point for minimizing the environmental burden imposed by natural and synthetic EDC, and for the protection of man and environment from adverse effects of EDC. The aim of the SANDRINE project was to: 1. study the behaviour of EDCs in waste water treatment plants (WWTPs) and sewage sludge; 2. make available and adapt bioanalytical tools (bioassays and biosensors) that respond to a broad range of EDCs by effect, rather than by chemical identification and allow to trace, to quantify, and to detect EDCs in complex samples; 3. validate the bioassay and biosensor measurements by comparing their data with established and instrumental analytical techniques, using known endoestrogens and xenoestrogens.
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ALGAETOX The application of integrated biosensors with antibody and The ALGAETOX project involves the application of integrated biosensors with antibody and macrocyclic receptor libraries in the macrocyclic measurement of algal cells and toxins in water. Several suitable sensing layers were developed and characterised and integrated into receptor libraries electrochemical and piezoelectric biosensors. in the measurement of algal cells and toxins in water. ENV4-CT98-0784 AQUA-SENSE Water quality monitoring by luminescent cyanobacterial biosensors: a novel early warming system against algal blooms. ENV4-CT97-0493 Inexpert Integrated Immuno Extraction Sampling and One of the main achievements of this project was the development of a portable prototype device with integrated biosensor using glucose dehydrogenase (GDH) modified thin-film electrodes for the rapid phenol index evaluation in water samples. The system includes a hand driven pump, an injection unit and a measuring cell. A miniaturised potentiostat feeds data to a display or to a portable computer. Catechol is the reference standard compound for experiments.
The main achievements are based on the bioavailable nitrate detection in water by an immobilized luminescent cyanobacterial reporter strain
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Portable Biosensor Prototype for InField Monitoring ENV4-CT97-0476 PRENDISENSOR Prediction of the behaviour of potential endocrine disruptors in soil using vitellogenin Elisa assays as biosensors. ENV4-CT97-0473 RIANA The main achievements of this project were the development of a multi-analyte water analyser and their application to real samples . It uses specific immunoassays for analyte recognition and Total Internal Reflection Fluorescence (TIRF) as transducer principle. The device consists of an optical detection unit, a flow cell, and an integrated fluid handling. Environmental pollutants, mainly pesticides and their metabolites, are detected by analyte specific antibodies that are labelled with a fluorescence marker. The VITELLO biosensor has been developed. It is based on an immunosensor device that uses either a sandwich or a competitive format. The biosensor measures increased vitellogenin levels in fish blood. VITELLO and the commonly used vitellogenin ELISA were applied to the detection of increased vitellogenin levels in trout exposed to different sewage effluents containing endocrine disrupting chemicals. The new VITELLO has the advantage of a fast response to the increased vitellogenin levels as compared to conventional ELISA and the data obtained between both methods correlates well.
River analyser: an analytical system for After a pre-incubation step of antibodies and sample, still unoccupied antibodies attach to a defined detection site of a glass transducer measuring locally modified with analyte derivatives. A laser beam is coupled into the transducer and propagates by total internal reflection. Bound multiple analytes fluorescence markers are excited in the evanescent field. in river water. ENV4-CT95-0066
Up to six reflection spots can be used to perform the simultaneous detection of a panel of analytes. The pollutants for which antibodies can be supplied are atrazine, simazine, isoproturon, Irgarol 1051, 2,4-dichlorophenoxyacetic acid (2,4-D), pentachlorophenol (PCP), methylchloro-phenoxypropionic acid (MCPP), paraquat, and alachlor.
The RIANA immunosensor is easy to handle and very robust. It is suitable for automated, unattended water analyses. Any time-consuming sample pre-treatment required in many other analytical techniques is unnecessary. Full regeneration of the transducer after each assay is possible, and allows its reuse for about 100 to 150 measurements. The principal goal of this project was to establish the feasibility of two biosensor technologies with enhanced specificity for the detection of BIOMETSENSOR several bioavailable heavy metals in environmental samples. Two strategies have been followed: one based on whole cell bacterial
184
Appendix 3 bioluminescence, or fluoresence; the other based on direct interaction between engineered proteins and heavy metal ions. In the latter case, conformational changes in the proteins are detected and enable the measurement of metals at femtomolar levels. Biomet heavy metal biosensors use a modified soil bacterium (Ralstonia metallidurans) which gives a light reaction when specific heavy metals go into the cell. Apart from grinding a coarse solid sample, no other sample preparation is needed. Specific sensors are available for zinc and cadmium; copper; lead; Cr6+; nickel; mercury. Biomet sensors are patented (US, 5,786,162) and recognised by OVAM as being relevant biotests for detecting bioavailable metals in polluted soils.
Development of new multisensing biosensors for the detection of bioavailable heavy metals in solid matrices.
ENV4-CT95-0141
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APPENDIX 4
Table 28. Published ISO Water and Effluent Standards ISO cataloque page
13.060.01
ISO Standard Number

Water quality in general ISO 6107-1:2004 ISO 6107-2:1997 ISO 6107-3:1993 ISO 6107-3:1993/Amd 1:2001 ISO 6107-4:1993 ISO 6107-5:2004 ISO 6107-6:2004 ISO 6107-7:1997 ISO 6107-8:1993 ISO 6107-8:1993/Amd 1:2001 ISO 6107-9:1997 ISO 8466-1:1990 ISO 8466-2:2001 ISO 15839:2003
Name/description of the standard method
Water quality Vocabulary Water quality Vocabulary Water quality Vocabulary Water quality Vocabulary Water quality Vocabulary Water quality Vocabulary Water quality Vocabulary Water quality Vocabulary Water quality -- Vocabulary Water quality -- Vocabulary Water quality -- Vocabulary -- Part 9: Alphabetical list and subject index Water quality -- Calibration and evaluation of analytical methods and estimation of performance characteristics -- Part 1: Statistical evaluation of the linear calibration function Water quality -- Calibration and evaluation of analytical methods and estimation of performance characteristics -- Part 2: Calibration strategy for non-linear second-order calibration functions Water quality -- On-line sensors/analysing equipment for water -- Specifications and performance tests
13.060.10
Water of natural resources ISO 5667-4:1987 ISO 5667-6:1990 ISO 5667-9:1992 ISO 5667-11:1993 ISO 5667-18:2001 ISO 5667-19:2004 ISO 8265:1988 ISO 8689-1:2000
Water quality -- Sampling -- Part 4: Guidance on sampling from lakes, natural and man-made Water quality -- Sampling -- Part 6: Guidance on sampling of rivers and streams Water quality -- Sampling -- Part 9: Guidance on sampling from marine waters Water quality -- Sampling -- Part 11: Guidance on sampling of groundwaters Water quality -- Sampling -- Part 18: Guidance on sampling of groundwater at contaminated sites Water quality -- Sampling -- Part 19: Guidance on sampling in marine sediments Water quality -- Design and use of quantitative samplers for benthic macro-invertebrates on stony substrata in shallow freshwaters Water quality -- Biological classification of rivers -- Part 1: Guidance on the interpretation of biological quality data from surveys of benthic macroinvertebrates
186
Appendix 4
Water quality -- Biological classification of rivers -- Part 2: Guidance on the presentation of biological quality data from surveys of benthic macroinvertebrates Water quality -- Sampling in deep waters for macro-invertebrates -- Guidance on the use of colonization, qualitative and quantitative samplers
ISO 8689-2:2000 ISO 9391:1993 13.060.20 Drinking water 71.100.80 ISO 5667-5:1991 ISO 10359-1:1992 91.140.60 67.160.20 Water for industrial use ISO 5667-7:1993 Sewage water ISO 5667-10:1992 ISO 5667-13:1997 ISO 5667-15:1999 ISO 10304-2:1995 91.140.80 13.030.20 ISO 5667-10:1992 ISO 5667-13:1997 ISO 5667-15:1999 ISO 10304-2:1995 93.030 13.060.45 Examination of water in general ISO 5667-1:1980 ISO 5667-1:1980/Cor 1:1996 ISO 5667-2:1991 ISO 5667-3:2003 ISO 5667-4:1987 ISO 5667-5:1991 ISO 5667-6:1990 ISO 5667-7:1993 ISO 5667-8:1993 ISO 5667-9:1992 ISO 5667-11:1993 ISO 5667-12:1995
13.060.25 13.060.30
Chemicals for purification of water, see Water quality -- Sampling -- Part 5: Guidance on sampling of drinking water and water used for food and beverage processing Water quality -- Determination of fluoride -- Part 1: Electrochemical probe method for potable and lightly polluted water Drinking water supply systems, see Mineral water, see Including water for commercial use: for swimming pools, fish breeding, etc. Water quality -- Sampling -- Part 7: Guidance on sampling of water and steam in boiler plants Including sewage water disposal and treatment Water quality -- Sampling -- Part 10: Guidance on sampling of waste waters Water quality -- Sampling -- Part 13: Guidance on sampling of sludges from sewage and water-treatment works Water quality -- Sampling -- Part 15: Guidance on preservation and handling of sludge and sediment samples Water quality -- Determination of dissolved anions by liquid chromatography of ions -- Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water Drainage systems, see Liquid wastes, see Water quality -- Sampling -- Part 10: Guidance on sampling of waste waters Water quality -- Sampling -- Part 13: Guidance on sampling of sludges from sewage and water-treatment works Water quality -- Sampling -- Part 15: Guidance on preservation and handling of sludge and sediment samples Water quality -- Determination of dissolved anions by liquid chromatography of ions -- Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water Sewage systems, see Water quality -- Sampling -- Part 1: Guidance on the design of sampling programmes Water quality -- Sampling -- Part 2: Guidance on sampling techniques Water quality -- Sampling -- Part 3: Guidance on the preservation and handling of water samples Water quality -- Sampling -- Part 4: Guidance on sampling from lakes, natural and man-made Water quality -- Sampling -- Part 5: Guidance on sampling of drinking water and water used for food and beverage processing Water quality -- Sampling -- Part 6: Guidance on sampling of rivers and streams Water quality -- Sampling -- Part 7: Guidance on sampling of water and steam in boiler plants Water quality -- Sampling -- Part 8: Guidance on the sampling of wet deposition Water quality -- Sampling -- Part 9: Guidance on sampling from marine waters Water quality -- Sampling -- Part 11: Guidance on sampling of groundwaters Water quality -- Sampling -- Part 12: Guidance on sampling of bottom sediments
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Appendix 4
ISO 5667-13:1997 ISO 5667-14:1998 ISO 5667-15:1999 ISO 5667-16:1998 ISO 5667-17:2000 ISO 5667-18:2001 ISO 5667-19:2004 ISO 7828:1985 ISO 9391:1993 ISO/TR 13530:1997 ISO 15839:2003 ISO 17381:2003 13.060.50 ISO 5663:1984 ISO 5664:1984 ISO 5666:1999 ISO 5813:1983 ISO 5814:1990 ISO 5815-1:2003 ISO 5815-2:2003 ISO 5961:1994 ISO 6058:1984 ISO 6059:1984 ISO 6060:1989 ISO 6332:1988 ISO 6333:1986 ISO 6439:1990 ISO 6468:1996 ISO 6703-1:1984 ISO 6703-2:1984 ISO 6703-3:1984 ISO 6777:1984 ISO 6778:1984 ISO 6878:2004 ISO 7150-1:1984 ISO 7150-2:1986 ISO 7393-1:1985 Water quality -- Sampling -- Part 13: Guidance on sampling of sludges from sewage and water-treatment works Water quality -- Sampling -- Part 14: Guidance on quality assurance of environmental water sampling and handling Water quality -- Sampling -- Part 15: Guidance on preservation and handling of sludge and sediment samples Water quality -- Sampling -- Part 16: Guidance on biotesting of samples Water quality -- Sampling -- Part 17: Guidance on sampling of suspended sediments Water quality -- Sampling -- Part 18: Guidance on sampling of groundwater at contaminated sites Water quality -- Sampling -- Part 19: Guidance on sampling in marine sediments Water quality -- Methods of biological sampling -- Guidance on handnet sampling of aquatic benthic macro-invertebrates Water quality -- Sampling in deep waters for macro-invertebrates -- Guidance on the use of colonization, qualitative and quantitative samplers Water quality -- Guide to analytical quality control for water analysis Water quality -- On-line sensors/analysing equipment for water -- Specifications and performance tests Water quality -- Selection and application of ready-to-use test kit methods in water analysis Water quality -- Determination of Kjeldahl nitrogen -- Method after mineralization with selenium Water quality -- Determination of ammonium -- Distillation and titration method Water quality -- Determination of mercury Water quality -- Determination of dissolved oxygen -- Iodometric method Water quality -- Determination of dissolved oxygen -- Electrochemical probe method Water quality -- Determination of biochemical oxygen demand after n days (BODn) -- Part 1: Dilution and seeding method with allylthiourea addition Water quality -- Determination of biochemical oxygen demand after n days (BODn) -- Part 2: Method for undiluted samples Water quality -- Determination of cadmium by atomic absorption spectrometry Water quality -- Determination of calcium content -- EDTA titrimetric method Water quality -- Determination of the sum of calcium and magnesium -- EDTA titrimetric method Water quality -- Determination of the chemical oxygen demand Water quality -- Determination of iron -- Spectrometric method using 1,10-phenanthroline Water quality -- Determination of manganese -- Formaldoxime spectrometric method Water quality -- Determination of phenol index -- 4-Aminoantipyrine spectrometric methods after distillation Water quality -- Determination of certain organochlorine insecticides, polychlorinated biphenyls and chlorobenzenes -- Gas chromatographic method after liquid-liquid extraction Water quality -- Determination of cyanide -- Part 1: Determination of total cyanide Water quality -- Determination of cyanide -- Part 2: Determination of easily liberatable cyanide Water quality -- Determination of cyanide -- Part 3: Determination of cyanogen chloride Water quality -- Determination of nitrite -- Molecular absorption spectrometric method Water quality -- Determination of ammonium -- Potentiometric method Water quality -- Determination of phosphorus -- Ammonium molybdate spectrometric method Water quality -- Determination of ammonium -- Part 1: Manual spectrometric method Water quality -- Determination of ammonium -- Part 2: Automated spectrometric method Water quality -- Determination of free chlorine and total chlorine -- Part 1: Titrimetric method using N,N-diethyl-1,4phenylenediamine
Examination of water for chemical substances
188
Appendix 4
ISO 7393-1:1985/Cor 1:2001 ISO 7393-2:1985 ISO 7393-3:1990 ISO 7875-1:1996 ISO 7875-1:1996/Cor 1:2003 ISO 7875-2:1984 ISO 7890-1:1986 ISO 7890-2:1986 ISO 7890-3:1988 ISO 7980:1986 ISO 8165-1:1992 ISO 8165-2:1999 ISO 8245:1999 ISO 8288:1986 ISO 8467:1993 ISO 9174:1998 ISO 9297:1989 ISO 9377-2:2000 ISO 9390:1990 ISO 9562:1998 ISO 9963-1:1994 ISO 9963-2:1994 ISO 9964-1:1993 ISO 9964-2:1993 ISO 9964-3:1993 ISO 9965:1993 ISO 10260:1992 ISO 10301:1997 ISO 10304-1:1992 ISO 10304-2:1995 ISO 10304-3:1997 ISO 10304-4:1997 Water quality -- Determination of free chlorine and total chlorine -- Part 2: Colorimetric method using N,N-diethyl-1,4phenylenediamine, for routine control purposes Water quality -- Determination of free chlorine and total chlorine -- Part 3: Iodometric titration method for the determination of total chlorine Water quality -- Determination of surfactants -- Part 1: Determination of anionic surfactants by measurement of the methylene blue index (MBAS) Water quality -- Determination of surfactants -- Part 2: Determination of non-ionic surfactants using Dragendorff reagent Water quality -- Determination of nitrate -- Part 1: 2,6-Dimethylphenol spectrometric method Water quality -- Determination of nitrate -- Part 2: 4-Fluorophenol spectrometric method after distillation Water quality -- Determination of nitrate -- Part 3: Spectrometric method using sulfosalicylic acid Water quality -- Determination of calcium and magnesium -- Atomic absorption spectrometric method Water quality -- Determination of selected monovalent phenols -- Part 1: Gas-chromatographic method after enrichment by extraction Water quality -- Determination of selected monovalent phenols -- Part 2: Method by derivatization and gas chromatography Water quality -- Guidelines for the determination of total organic carbon (TOC) and dissolved organic carbon (DOC) Water quality -- Determination of cobalt, nickel, copper, zinc, cadmium and lead -- Flame atomic absorption spectrometric methods Water quality -- Determination of permanganate index Water quality -- Determination of chromium -- Atomic absorption spectrometric methods Water quality -- Determination of chloride -- Silver nitrate titration with chromate indicator (Mohr's method) Water quality -- Determination of hydrocarbon oil index -- Part 2: Method using solvent extraction and gas chromatography Water quality -- Determination of borate -- Spectrometric method using azomethine-H Water quality -- Determination of adsorbable organically bound halogens (AOX) Water quality -- Determination of alkalinity -- Part 1: Determination of total and composite alkalinity Water quality -- Determination of alkalinity -- Part 2: Determination of carbonate alkalinity Water quality -- Determination of sodium and potassium -- Part 1: Determination of sodium by atomic absorption spectrometry Water quality -- Determination of sodium and potassium -- Part 2: Determination of potassium by atomic absorption spectrometry Water quality -- Determination of sodium and potassium -- Part 3: Determination of sodium and potassium by flame emission spectrometry Water quality -- Determination of selenium -- Atomic absorption spectrometric method (hydride technique) Water quality -- Measurement of biochemical parameters -- Spectrometric determination of the chlorophyll-a concentration Water quality -- Determination of highly volatile halogenated hydrocarbons -- Gas-chromatographic methods Water quality -- Determination of dissolved fluoride, chloride, nitrite, orthophosphate, bromide, nitrate and sulfate ions, using liquid chromatography of ions -- Part 1: Method for water with low contamination Water quality -- Determination of dissolved anions by liquid chromatography of ions -- Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water Water quality -- Determination of dissolved anions by liquid chromatography of ions -- Part 3: Determination of chromate, iodide, sulfite, thiocyanate and thiosulfate Water quality -- Determination of dissolved anions by liquid chromatography of ions -- Part 4: Determination of chlorate,
189
Appendix 4
chloride and chlorite in water with low contamination Water quality -- Determination of fluoride -- Part 1: Electrochemical probe method for potable and lightly polluted water Water quality -- Determination of fluoride -- Part 2: Determination of inorganically bound total fluoride after digestion and distillation Water quality -- Determination of pH Water quality -- Determination of dissolved sulfide -- Photometric method using methylene blue Water quality -- Determination of aluminium -- Spectrometric method using pyrocatechol violet Water quality -- Determination of selected organic nitrogen and phosphorus compounds -- Gas chromatographic methods Water quality -- Determination of chromium(VI) -- Spectrometric method using 1,5-diphenylcarbazide Water quality -- Determination of selected plant treatment agents -- Method using high performance liquid chromatography with UV detection after solid-liquid extraction Water quality -- Determination of selected organic plant-treatment agents -- Automated multiple development (AMD) technique Water quality -- Determination of benzene and some derivatives -- Part 1: Head-space gas chromatographic method Water quality -- Determination of benzene and some derivatives -- Part 2: Method using extraction and gas chromatography Water quality -- Determination of ammonium nitrogen by flow analysis (CFA and FIA) and spectrometric detection Water quality -- Determination of 33 elements by inductively coupled plasma atomic emission spectroscopy Water quality -- Determination of nitrogen -- Part 1: Method using oxidative digestion with peroxodisulfate Water quality -- Determination of nitrogen -- Part 2: Determination of bound nitrogen, after combustion and oxidation to nitrogen dioxide, chemiluminescence detection Water quality -- Determination of arsenic -- Atomic absorption spectrometric method (hydride technique) Water quality -- Determination of aluminium -- Atomic absorption spectrometric methods Water quality -- Determination of easily released sulfide Water quality -- Determination of nitrite nitrogen and nitrate nitrogen and the sum of both by flow analysis (CFA and FIA) and spectrometric detection Water quality -- Determination of phenol index by flow analysis (FIA and CFA) Water quality -- Determination of total cyanide and free cyanide by continuous flow analysis Water quality -- Determination of dissolved Li+, Na+, NH4+, K+, Mn2+, Ca2+, Mg2+, Sr2+ and Ba2+ using ion chromatography -- Method for water and waste water Water quality -- Determination of dissolved bromate -- Method by liquid chromatography of ions Water quality -- Guidelines for selective immunoassays for the determination of plant treatment and pesticide agents Water quality -- Determination of trace elements using atomic absorption spectrometry with graphite furnace Water quality -- Digestion for the determination of selected elements in water -- Part 1: Aqua regia digestion Water quality -- Digestion for the determination of selected elements in water -- Part 2: Nitric acid digestion Water quality -- Gas-chromatographic determination of a number of monocyclic aromatic hydrocarbons, naphthalene and several chlorinated compounds using purge-and-trap and thermal desorption Water quality -- Determination of orthophosphate and total phosphorus contents by flow analysis (FIA and CFA) -- Part 1: Method by flow injection analysis (FIA) Water quality -- Determination of orthophosphate and total phosphorus contents by flow analysis (FIA and CFA) -- Part 2: Method by continuous flow analysis (CFA) Water quality -- Determination of chloride by flow analysis (CFA and FIA) and photometric or potentiometric detection Water quality -- Determination of the chemical oxygen demand index (ST-COD) -- Small-scale sealed-tube method
ISO 10359-1:1992 ISO 10359-2:1994 ISO 10523:1994 ISO 10530:1992 ISO 10566:1994 ISO 10695:2000 ISO 11083:1994 ISO 11369:1997 ISO/TS 11370:2000 ISO 11423-1:1997 ISO 11423-2:1997 ISO 11732:1997 ISO 11885:1996 ISO 11905-1:1997 ISO/TR 11905-2:1997 ISO 11969:1996 ISO 12020:1997 ISO 13358:1997 ISO 13395:1996 ISO 14402:1999 ISO 14403:2002 ISO 14911:1998 ISO 15061:2001 ISO 15089:2000 ISO 15586:2003 ISO 15587-1:2002 ISO 15587-2:2002 ISO 15680:2003 ISO 15681-1:2003 ISO 15681-2:2003 ISO 15682:2000 ISO 15705:2002
190
Appendix 4
Water quality -- Determination of selected phenoxyalkanoic herbicides, including bentazones and hydroxybenzonitriles by gas chromatography and mass spectrometry after solid phase extraction and derivatization Water quality -- Determination of soluble silicates by flow analysis (FIA and CFA) and photometric detection Water quality -- Determination of six complexing agents -- Gas-chromatographic method Water quality -- Determination of mercury -- Methods involving enrichment by amalgamation Water quality -- Application of inductively coupled plasma mass spectrometry (ICP-MS) -- Part 2: Determination of 62 elements Water quality -- Determination of selected nitrophenols -- Method by solid-phase extraction and gas chromatography with mass spectrometric detection Water quality -- Determination of 15 polycyclic aromatic hydrocarbons (PAH) in water by HPLC with fluorescence detection after liquid-liquid extraction Water quality -- Determination of tetra- to octa-chlorinated dioxins and furans -- Method using isotope dilution HRGC/HRMS
ISO 15913:2000 ISO 16264:2002 ISO 16588:2002 ISO 16588:2002/Amd 1:2004 ISO 16590:2000 ISO 17294-2:2003 ISO 17495:2001 ISO 17993:2002 ISO 18073:2004 13.060.60
Examination of physical properties of water ISO 7027:1999 Water quality -- Determination of turbidity ISO 7887:1994 Water quality -- Examination and determination of colour ISO 7888:1985 Water quality -- Determination of electrical conductivity ISO 9696:1992 Water quality -- Measurement of gross alpha activity in non-saline water -- Thick source method ISO 9697:1992 Water quality -- Measurement of gross beta activity in non-saline water ISO 9698:1989 Water quality -- Determination of tritium activity concentration -- Liquid scintillation counting method ISO 10703:1997 Water quality -- Determination of the activity concentration of radionuclides by high resolution gamma-ray spectrometry ISO 11923:1997 Water quality -- Determination of suspended solids by filtration through glass-fibre filters Examination of biological properties of water Microbiology of water, see 07.100.20 Water quality -- Determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea) -- Acute ISO 6341:1996 toxicity test ISO 6341:1996/Cor 1:1998 Water quality -- Determination of the acute lethal toxicity of substances to a freshwater fish [Brachydanio rerio HamiltonISO 7346-1:1996 Buchanan (Teleostei, Cyprinidae)] -- Part 1: Static method Water quality -- Determination of the acute lethal toxicity of substances to a freshwater fish [Brachydanio rerio HamiltonISO 7346-2:1996 Buchanan (Teleostei, Cyprinidae)] -- Part 2: Semi-static method Water quality -- Determination of the acute lethal toxicity of substances to a freshwater fish [Brachydanio rerio HamiltonISO 7346-3:1996 Buchanan (Teleostei, Cyprinidae)] -- Part 3: Flow-through method Water quality -- Evaluation in an aqueous medium of the "ultimate" aerobic biodegradability of organic compounds -- Method ISO 7827:1994 by analysis of dissolved organic carbon (DOC) ISO 8192:1986 Water quality -- Test for inhibition of oxygen consumption by activated sludge ISO 8692:1989 Water quality -- Fresh water algal growth inhibition test with Scenedesmus subspicatus and Selenastrum capricornutum Water quality -- Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium by determination of ISO 9408:1999 oxygen demand in a closed respirometer Water quality -- Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium -- Carbon dioxide ISO 9439:1999 evolution test
13.060.70
191
Appendix 4
Water quality -- Method for assessing the inhibition of nitrification of activated sludge micro-organisms by chemicals and waste waters Water quality -- Evaluation of the aerobic biodegradability of organic compounds in an aqueous medium -- Semi-continuous activated sludge method (SCAS) Water quality -- Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium -- Static test (ZahnWellens method) Water quality -- Determination of the prolonged toxicity of substances to freshwater fish -- Method for evaluating the effects of substances on the growth rate of rainbow trout (Oncorhynchus mykiss Walbaum (Teleostei, Salmonidae)) Water quality -- Marine algal growth inhibition test with Skeletonema costatum and Phaeodactylum tricornutum Water quality -- Guidance for the preparation and treatment of poorly water-soluble organic compounds for the subsequent evaluation of their biodegradability in an aqueous medium Water quality -- Determination of long term toxicity of substances to Daphnia magna Straus (Cladocera, Crustacea) Water quality -- Evaluation in an aqueous medium of the "ultimate" aerobic biodegradability of organic compounds -- Method by analysis of biochemical oxygen demand (closed bottle test) Water quality -- Evaluation in an aqueous medium of the ultimate aerobic biodegradability of organic compounds -Determination of biochemical oxygen demand in a two-phase closed bottle test Water quality -- Pseudomonas putida growth inhibition test (Pseudomonas cell multiplication inhibition test) Water quality -- Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) -- Part 1: Method using freshly prepared bacteria Water quality -- Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) -- Part 2: Method using liquid-dried bacteria Water quality -- Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) -- Part 3: Method using freeze-dried bacteria Water quality -- Determination of the elimination and biodegradability of organic compounds in an aqueous medium -Activated sludge simulation test Water quality -- Evaluation of the "ultimate" anaerobic biodegradability of organic compounds in digested sludge -- Method by measurement of the biogas production Water quality -- Determination of toxicity to embryos and larvae of freshwater fish -- Semi-static method Water quality -- Determination of inhibition of gas production of anaerobic bacteria -- Part 1: General test Water quality -- Determination of inhibition of gas production of anaerobic bacteria -- Part 2: Test for low biomass concentrations Water quality -- Determination of the genotoxicity of water and waste water using the umu-test Water quality -- Guidelines for algal growth inhibition tests with poorly soluble materials, volatile compounds, metals and waste water Water quality -- Evaluation of the aerobic biodegradability of organic compounds at low concentrations -- Part 1: Shake-flask batch test with surface water or surface water/sediment suspensions Water quality -- Evaluation of the aerobic biodegradability of organic compounds at low concentrations -- Part 2: Continuous flow river model with attached biomass Water quality -- Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium -- Method by analysis of inorganic carbon in sealed vessels (CO2 headspace test) Water quality -- Determination of acute lethal toxicity to marine copepods (Copepoda, Crustacea) Water quality -- Selection of tests for biodegradability
ISO 9509:1989 ISO 9887:1992 ISO 9888:1999 ISO 10229:1994 ISO 10253:1995 ISO 10634:1995 ISO 10706:2000 ISO 10707:1994 ISO 10708:1997 ISO 10712:1995 ISO 11348-1:1998 ISO 11348-2:1998 ISO 11348-3:1998 ISO 11733:2004 ISO 11734:1995 ISO 12890:1999 ISO 13641-1:2003 ISO 13641-2:2003 ISO 13829:2000 ISO 14442:1999 ISO 14592-1:2002 ISO 14592-2:2002 ISO 14593:1999 ISO 14669:1999 ISO/TR 15462:1997
192
Appendix 4
ISO 15522:1999 ISO 16221:2001 ISO 17994:2004 ISO 18749:2004 13.060.99 Water quality -- Determination of the inhibitory effect of water constituents on the growth of activated sludge microorganisms Water quality -- Guidance for determination of biodegradability in the marine environment Water quality -- Criteria for establishing equivalence between microbiological methods Water quality -- Adsorption of substances on activated sludge -- Batch test using specific analytical methods
Other standards related to water quality
193
Appendix 4
Table 29. Draft ISO Water and Effluent Standards ISO Standard Number
Vocabulary
ISO/WD 6107-2 ISO 6107-6 ISO/WD 6107-7 ISO/CD 5667 -1 ISO/CD 5667 -5 ISO/DIS 5667-6 ISO/AWI 19493 ISO/DIS 16665 ISO/CD TS 20281 ISO/WD 13530 ISO/CD TS 16489 ISO/WD TS 20192-1 ISO/CD 20612 Water quality -- Vocabulary Water quality -- Vocabulary Water quality -- Vocabulary Water quality -- Sampling -- Part 1: General guidance Water quality -- Sampling -- Part 5: Guidance on sampling of drinking water and water used for food and beverage processing Water quality -- Sampling -- Part 6: Guidance on sampling of rivers and streams Water quality -- Guidance on marine biological surveys of littoral and sublittoral hard bottom Water quality -- Guidelines for quantitative sampling and sample processing of marine soft bottom macro fauna (available in English only) Water quality -- Guidance on statistical interpretation of ecotoxicity data Water quality -- Guidance on analytical quality control for water analysis Water quality -- Guidance for establishing the equivalency of results Water quality -- Analytical quality control in microbiology -- Part 1: Quality control of culture media Water quality -- Interlaboratory comparisons for proficiency testing of laboratories Water quality -- Detection and enumeration of Clostridium perfringens -- Part 2: Method by membrane filtration Water quality -- Isolation and enumeration of Cryptosporidium oocysts and Giardia cysts from water Water quality -- Detection and enumeration of Pseudomonas aeruginosa -- Membrane filtration method Water quality -- Detection and enumeration of Legionella -- Part 1: General method Water quality -- Detection and enumeration of thermotolerant Campylobacter spp. Water quality -- Detection of enterohaemorrhagic Escherichia coli -- Part 1: Detection of Escherichia coli 0157 using immunomagnetic separation Water quality -- Determination of Salmonella species Water quality -- Sampling for microbiological analysis Water quality -- Determination of microcystins -- Method using solid phase extraction (SPE) and high performance liquid chromatography (HPLC) with ultraviolet (UV) detection Water quality -- General guidance on the enumeration of micro-organisms by culture
Name/description of the standard method
General guidance/Quality assurance
Detection of Microorganisms
ISO/CD 6461 -2 ISO/DIS 15553 ISO/CD 16266 ISO/AWI 11731-1 ISO/DIS 17995 ISO/AWI 20692-1 ISO/DIS 19250 ISO/CD 19458 ISO/DIS 20179 ISO/DIS 8199
Sampling/determination of organic compounds

ISO/DIS 7981-1 Water quality -- Determination of polycyclic aromatic hydrocarbons (PAH) -- Part 1: Determination of six PAH by high-performance thin-layer chromatography with fluorescence detection after liquid extraction
194
Appendix 4
Water quality -- Determination of polycyclic aromatic hydrocarbons (PAH) -- Part 2: Determination of six PAH by high-performance liquid chromatography with fluorescence detection after liquid- liquid extraction Water quality -- Determination of adsorbable organically bound halogens (AOX) Water quality -- Determination of selected organotin compounds -- Gas chromatographic method Water quality -- Determination of co-planar polychlorinated biphenyls -- Method using gas chromatography/ mass spectrometry Water quality -- Determination of selected phthalates using gas chromatography/mass spectrometry Water quality -- Determination of selected alkylphenols -- Part 1: Method for non-filtered samples using liquid extraction and gas chromatography with mass selective detection Water quality -- Determination of dalapon, trichloroacetic acid and selected haloacetic acids -- Method using gas chromatography (GD-ED and/or GC-MS detection) after liquid extraction and derivatisation Water quality -- Determination of selected polybrominated diphenyl ethers in sediment and sewage sludge --Method using extraction and gas chromatography/mass spectrometry Water quality -- Determination of selected explosives and related compounds -- Method using high performance liquid chromatography (HPLC) with UV detection Water quality -- Determination of MBAS index -- Method by flow analysis (CFA and FIA)
ISO/DIS 7981-2 ISO/FDIS 9562 ISO/FDIS 17353 ISO/CD 17858 ISO/PRF 18856 ISO/FDIS 18857-1 ISO/CD 23631 ISO/CD 22032 ISO/DIS 22478 ISO/DIS 16265
Sampling/determination of inorganic compounds

ISO/CD 23914-2 ISO/CD 10304 ISO/FDIS 11732 ISO/WD 11885 ISO/AWI 17378-1 ISO/AWI 17378-2 ISO/AWI 17379-1 ISO/AWI 17379-2 ISO/CD 17852 ISO/DIS 18412 ISO/PRF 17294-1 ISO/CD 23913 ISO/CD 22743 Water quality -- Determination of antimony -- Part 2: Method using hydride generation atomic absorption spectrometry (HG-AAS) Water quality -- Determination of dissolved bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate -- Method by liquid chromatography of ions Water quality -- Determination of ammonium nitrogen -- Method by flow analysis (CFA and FIA) and spectrometric detection Water quality -- Determination of 33 elements by inductively coupled plasma atomic emission spectroscopy Water quality -- Determination of arsenic -- Part 1: Method using hydride generation atomic fluorescence spectrometry (HG-AFS) Water quality -- Determination of arsenic -- Part 2: Method using hydride generation atomic absorption spectrometry (HG-AAS) Water quality -- Determination of selenium -- Part 1: Method using hydride generation atomic fluorescence spectrometry (HG-AFS) Water quality -- Determination of selenium -- Part 2: Method using hydride generation atomic absorption spectrometry (HG-AAS) Water quality -- Determination of mercury -- Method using atomic fluorescence spectrometry Water quality -- Determination of chromium(VI) -- Photometric method for low contaminated water Water quality -- Application of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of elements -- Part 1: General guidelines and basic principles (available in English only) Water quality -- Determination of chromium (VI) and the sum of chromium (III) and chromium (VI) -- Method using flow analysis (FIA and CFA) Water quality -- Determination of sulfates by flow analysis (CFA and FIA) Documents found: 63 Search criteria Search scope: Technical programme (standards under development only) Committee: TC 147
Tests for biodegradability

ISO/FDIS 11733 ISO/CD TR 15462 Water quality -- Determination of the elimination and biodegradability of organic compounds in an aqueous medium -- Activated sludge simulation test Water quality -- Selection of tests for biodegradability Water quality -- Determination of acute lethality to freshwater and marine fish Water quality -- Test for inhibition of oxygen consumption by activated sludge
Toxicity
ISO/AWI 7346 ISO/CD 8192
195
Appendix 4
ISO/FDIS 8692 ISO/CD 9509 ISO/CD 15088-1 ISO/CD 10253 ISO/CD 14442 ISO/DIS 16240 ISO/DIS 16712 ISO/DIS 20079 ISO/CD 21427-1 ISO/CD 21427-2 ISO/WD 21338 Water quality -- Freshwater algal growth inhibition test with unicellular green algae Water quality -- Method for assessing the inhibition of nitrification of activated sludge microorganisms by chemicals and waste waters Water quality -- Determination of the non-acute toxicity of waste water to fish eggs -- Part 1: Danio rerio Water quality -- Marine algal growth inhibition test with Skeletonema costatum and Phaeodactylum tricornutum Water quality -- Guidance on algal growth inhibition tests with poorly soluble materials, volatile compounds, metals and waste water Water quality -- Determination of the genotoxicity of water and waste water -- Salmonella/microsome test (Ames test) Water quality -- Determination of acute toxicity of marine or estuarine sediment to amphipods Water quality -- Determination of toxic effect of water constituents and waste water to duckweed (Lemna minor) -- Duckweed growth inhibition test Water quality -- Evaluation of genotoxicity by measurement of the induction of micronuclei -- Part 1: Evaluation of genotoxicity using amphibian larvae Water quality -- Evaluation of genotoxicity by measurement of the induction of micronuclei -- Part 2: "Mixed population" method using the cell line V79 Water quality -- Kinetic determination of the inhibitory effects of sediment and other solids and colour containing samples on the light emission of Vibrio fischeri (kinetic luminescent bacteria test)
196
Appendix 4
Table 30. Published and Draft CEN Water and Effluent Standards (http://www.cenorm.beindex.htm)
Parameter
Toxicity Measurement
CEN method identification
Name/description of the standard
EN ISO 5667-16:1998
Water quality - Sampling - Part 16: Guidance on biotesting of samples (ISO 5667-16:1998) Active Published 60.60.0000 Water quality - Pseudomonas putida growth inhibition test (pseudomonas cell multiplication inhibition test)(ISO 10712:1995) Active Published 90.99.0000 Water quality - Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) - Part 1: Method using freshly prepared bacteria (ISO 11348-1:1998) Active Published 60.60.0000 Water quality - Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) - Part 2: Method using liquid-dried bacteria (ISO 11348-2:1998) Active Published 60.60.0000 Water quality - Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test) - Part 3: Method using freeze-dried bacteria (ISO 11348-3:1998) Active Published 60.60.0000 Water quality - Test for the inhibition of oxygen consumption by activated sludge (ISO 8192:1986) Active Published 90.99.0000 Water quality - Method for assessing the inhibition of nitrification of activated sludge micro-organisms by chemicals and waste water (ISO 9509:1989) Active Published 90.99.0000 Water quality - Method for assessing the inhibition of nitrification of activated sludge micro-organisms by chemicals and waste water Active Not Published 10.99.0000 Water quality - Freshwater algal growth inhibition test with unicellular green algae (ISO/FDIS 8692:2004) Active Not Published 50.20.0000 Water quality - Marine algal growth inhibition test with Skeletonema costatum and Phaeodactylum tricornutum Active Not Published 10.99.0000 Water quality - Fresh water algal growth inhibition test with Scenedesmus subspicatus and Selenastrum capricornutum (ISO 8692:1989) Active Published 90.99.0000 Water quality - Marine algal growth inhibition test with Skeletonema costatum and Phaeodactylum tricornutum (ISO 10253:1995) Active Published 90.99.0000
Microbial
P. putida V. fischeri EN ISO 10712:1995 EN ISO 11348-1:1998
V. fischeri
EN ISO 11348-2:1998 EN ISO 11348-3:1998
V. fischeri Sewage Sludge Nitrification Nitrification EN ISO 8192:1995 EN ISO 9509:1995 prEN ISO 9509:1995 rev
Algal
Green algae S. costatum P. tricornutum S. subcapitus S. capricornutum S. costatum P. tricornutum prEN ISO 8692 prEN ISO 10253:1998 rev EN 28692:1993 EN ISO 10253:1998
Vertebrates
197
Appendix 4
Fish Fish Fish Fish EN ISO 7346-1:1997
Toxicity to fish Split Not Published 10.99.0000 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 1: Static method (ISO 7346-1:1996) Active Published 90.99.0000 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 2: Semi-static method (ISO 7346-2:1996) Active Published 90.99.0000 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 3: Flow-through method (ISO 7346-3:1996) Active Published 90.99.0000 Water quality - Determination of biochemical oxygen demand after n days (BODn) - Part 2: Method for undiluted samples (ISO 5815:1989, modified) Active Published 60.60.0000 Water quality -- Determination of acute lethality to freshwater and marine fish Active Not Published 10.99.0000 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 1: Static method (ISO 7346-1:1996) Merged Not Published 10.99.0000 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 2: Semi-static method (ISO 7346-2:1996), Merged Not Published 10.99.0000 Water quality - Determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea) - Acute toxicity test (ISO 6341:1996) Active Published 90.99.0000 Water quality - Determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea) - Acute toxicity test (ISO 6341:1996) Active Published 60.60.0000 Water quality - Determination of acute toxicity of marine or estuarine sediments to amphipods (ISO 16712) Active Not Published 10.99.0000 Water quality - Determination of the toxic effect of water constituents and waste water to duckweed (Lemna minor) - Duckweed growth inhibition test (ISO 20079) Active Not Published 10.99.0000
EN ISO 7346-2:1997
EN ISO 7346-3:1997 EN 1899-2:1998
Fish Fish Fish
prEN ISO 7346 rev prEN ISO 7346-1 rev
prEN ISO 7346- 2 rev
Invertebrates
D. magna D. magna Amphipods EN ISO 6341:1996 EN ISO 6341:1996/AC:1998 prEN ISO 16712
Macrophyte
Duckweed L. minor prEN ISO 20079
Determination of inorganic compounds and heavy metals

As As Hg EN 26595:1992/AC:1992 EN 26595:1992 EN 1483:1997 Water quality - Determination of total arsenic - Silver diethyldithiocarbamate spectrophotometric method (ISO 6595:1982) Active Published 60.60.0000 Water quality - Determination of total arsenic - Silver diethyldithiocarbamate spectrophotometric method (ISO 6595:1982) Active Published 90.99.0000 Water quality - Determination of mercury Active Published 90.99.0000
198
Appendix 4
Water quality - Determination of chromium - Atomic absorption spectrometric methods Active Published 90.99.0000 Water quality - Determination of total mercury by flameless atomic absorption spectrometry - Part 2: Method after pretreatment with ultraviolet radiation (ISO 5666-2:1983) Merged Not Published 50.60.0000 Water quality - Determination of cadmium by atomic absorption spectrometry (ISO 5961:1994) Active Published 90.99.0000 Water quality - Determination of arsenic - Atomic absorption spectrometric method (hydride technique) (ISO 11969:1996) Active Published 90.99.0000 Water quality - Determination of mercury - Enrichment methods by amalgamation Active Published 60.60.0000 Water quality - Determination of mercury by atomic fluorescence spectrometry Active Published 60.60.0000 Water quality - Determination of mercury Active Not Published 10.99.0000 Water quality - Determination of arsenic Split Not Published 10.99.0000 Water quality - Determination of selenium Split Not Published 10.99.0000 Water quality - Determination of antimony Split Not Published 10.99.0000 Water quality - Determination of thallium Abandoned Not Published 10.99.0000 EN ISO 12020:2000 EN ISO 15587-1:2002 EN ISO 15587-2:2002 Water quality - Determination of aluminium - Atomic absorption spectrometric methods (ISO 12020:1997) Active Published 60.60.0000 Water quality - Digestion for the determination of selected elements in water - Part 1: Aqua regia digestion (ISO 15587-1:2002) Active Published 60.60.0000 Water quality - Digestion for the determination of selected elements in water - Part 2: Nitric acid digestion (ISO 15587-2:2002) Active Published 60.60.0000 Water quality - Determination of selenium - Part 1: AFS hybride method Active Not Published 10.99.0000 Water quality - Determination of selenium - Part 2: AAS hybride method Active Not Published 10.99.0000 Water quality - Determination of antimony - Part 1: AFS hybride method Active Not Published 10.99.0000 Water quality - Determination of antimony - Part 2: AAS hybride method Active Not Published 10.99.0000 ISO/CD 15587 EN ISO 11885:1997 EN ISO 14403:2002 Water quality - Digestion method for the determination of trace elements Split Not Published 10.99.0000 Water quality - Determination of 33 elements by inductively coupled plasma atomic emission spectroscopy (ISO 11885:1996) Active Published 90.99.0000 Water quality - Determination of total cyanide and free cyanide by continuous flow analysis (ISO 14403:2002) Active Published 60.60.0000
Cr Hg Cd As Hg Hg Hg As Se Sb Th Al Trace elements Trace elements Se Se Sb Sb Trace Elements Trace elements Cyanide
EN 1233:1996 ISO 5666-2 EN ISO 5961:1995 EN ISO 11969:1996 EN 12338:1998 EN 13506:2001 prEN 1483 rev
199
Appendix 4
Cr As As Trace elements Trace elements Trace elements As Cr Sn EN ISO 15586:2003 prEN ISO 17294-2 ISO 17294-1 prEN ISO 11969:1996 rev prEN 1233:1996 rev ISO/WD 17353
Water quality - Determination of Chromium VI Active Not Published 10.99.0000 Water quality - Determination of arsenic - Part 1: AFS hydride technique Active Not Published 10.99.0000 Water quality - Determination of arsenic - Part 2: AAS hydride technique Active Not Published 10.99.0000 Water quality - Determination of trace elements using atomic absorption spectrometry with graphite furnace (ISO 15586:2003) Active Published 60.60.0000 Water quality - Application of inductively coupled plasma mass spectrometry (ICP -MS) - Part 2: Determination of 62 elements (ISO 17294-2:2003) Active Not Published 50.20.0000 Water quality - Application of inductively coupled plasma mass spectrometry (ICP -MS) - Part 1: General guideline Active Not Published 10.99.0000 Water quality - Determination of arsenic - Atomic absorption spectrometric method (hydride technique) Abandoned Not Published 10.99.0000 Water quality - Determination of chromium - Atomic absorption spectrometric methods Abandoned Not Published 10.99.0000 Water quality - Determination of selected organotin compounds Active Not Published 10.99.0000
General Parameters Inorganic ions

N EN 26777:1993 ENV 12260:1996 EN ISO 11905-1:1998 EN 25663:1993 EN ISO 11732:1997 EN ISO 13395:1996 prEN ISO 11732rev EN 12260:2003 Cl EN ISO 7393-1:2000 EN ISO 7393-2:2000 Water quality - Determination of nitrite - Molecular absorption spectrometric method (ISO 6777:1984) Active Published 90.99.0000 Water quality - Determination of nitrogen - Determination of bound nitrogen, after combustion and oxidation to nitrogen dioxide, using chemiluminescence detection Closed Withdrawn 99.60.0000 Water quality - Determination of nitrogen - Part 1: Method using oxidative digestion with peroxodisulfate (ISO 11905-1:1997) Active Published 60.60.0000 Water quality - Determination of Kjeldahl nitrogen - Method after mineralization with selenium (ISO 5663:1984) Active Published 90.99.0000 Water quality - Determination of ammonium nitrogen by flow analysis (CFA and FIA) and spectrometric detection (ISO 11732:1997) Active Published 90.00.0000 Water quality - Determination of nitrite nitrogen and nitrate nitrogen and the sum of both by flow analysis (CFA and FIA) and spectrometric detection (ISO 13395:1996) Active Published 90.99.0000 Water quality - Determination of ammonium nitrogen - Method by flow analysis (CFA and FIA) and spectrometric detection (ISO/DIS 11732:2003) Active Not Published 40.60.0000 Water quality - Determination of nitrogen - Determination of bound nitrogen (TNb), following oxidation to nitrogen oxides Active Published 60.60.0000 Water quality - Determination of free chlorine and total chlorine - Part 1:Titrimetric method using N, Ndiethyl-1,4-phenylenediamine (ISO 7393 -1:1985)Active Published 60.60.0000 Water quality - Determination of free chlorine and total chlorine - Part 2: Colorimetric method using N, Ndiethyl-1, 4-phenylenediamine, for routine control purposes (ISO 7393-2:1985) Active Published
200
Appendix 4
60.60.0000 Water quality - Determination of free chlorine and total chlorine - Part 3: Iodometric titration method for the determination of total chlorine (ISO 7393-3:1990) Active Published 60.60.0000 Water quality - Determination of chloride by flow analysis (CFA and FIA) and photometric or potentiometric detection (ISO 15682:2000) Active Published 60.60.0000 Water quality - Determination of orthophosphate and total phosphorus contents by flow analysis (FIA and CFA) - Part 1: Method by flow injection analysis (FIA) (ISO 15681-1:2003) Active Not Published 50.20.0000 Water quality - Determination of orthophosphate and total phosphorus contents by flow analysis (FIA and CFA) - Part 2: Method by continuous flow analysis (CFA) (ISO 15681-2:2003) Active Not Published 50.20.0000 Water quality - Determination of phosphorus - Ammonium molybdate spectrometric method Closed Withdrawn 99.60.0000 Water quality - Determination of phosphate and total phosphorus contents by flow analysis (FIA and CFA) - Part 1: Method by FIA Split Not Published 20.60.0979 Water quality - Determination of phosphorus - Ammonium molybdate spectrometric method (ISO 6878:2004) Active Published 60.60.0000 Water quality - Determination of dissolved fluoride, chloride, nitrite, orthophosphate, bromide, nitrate and sulfate ions, using liquid chromatography of ions - Part 1: Method for water with low contamination (ISO 10304 -1:1992) Active Published 90.99.0000 Water quality - Determination of dissolved anions by liquid chromatography of ions - Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water (ISO 10304 -2:1995) Active Published 90.99.0000 Water quality - Determination of dissolved anions by liquid chromatography of ions - Part 3: Determination of chromate, iodide, sulfite, thiocyanate and thiosulfate (ISO 10304-3:1997) Active Published 90.99.0000 Water quality - Determination of dissolved anions by liquid chromatography of ions - Part 4: Determination of chlorate, chloride and chlorite in water with low contamination (ISO 10304-4:1997) Active Published 60.60.0000 Water quality - Determination of calcium and magnesium - Atomic absorption spectrometric method (ISO 7980:1986) Active Published 60.60.0000 Water quality - Determination of dissolved bromate - Method by liquid chromatography of ions (ISO 15061:2001) Active Published 60.60.0000 waste water (ISO 14911:1998) Water quality - Determination of dissolved Li+, Na+, NH4+, K+, Mn2+, Ca2+, Mg2+, Sr2+ and Ba2+ using ion chromatography - Method for water and Active Published 60.60.0000 Water quality - Determination of soluble silicates by flow analysis (FIA and CFA) and photometric detection (ISO 16264:2002) Active Published 60.60.0000 Water quality - Determination of dissolved oxygen - Electrotechnical probe method (ISO 5814:1990) Active Published 90.99.0000
EN ISO 7393-3:2000 EN ISO 15682:2001 prEN ISO 15681-1
prEN ISO 15681-2 EN 1189:1996 prEN ISO 15681-1 EN ISO 6878:2004 EN ISO 10304-1:1995
Anions
EN ISO 10304-2:1996 EN ISO 10304-3:1997 EN ISO 10304-4:1999 EN ISO 7980:2000 EN ISO 5061:2001 EN ISO 14911:1999 EN ISO 16264:2004
Cations
DO
EN 25814:1992
201
Appendix 4
Water quality - Determination of dissolved oxygen - Iodometric method (ISO 5813:1983) Active Published 90.99.0000 Water analysis - Guidelines for the determination of total organic carbon (TOC) and dissolved organic carbon (DOC) Active Published 90.99.0000
EN 25813:1992
TOC
EN 1484:1997
Odour/colour
EN ISO 7887:1994 EN 1622:1997 Water quality - Examination and determination of colour (ISO 7887:1994) Active Published 90.99.0000 Water analysis - Determination of the threshold odour number (TON) and threshold flavour number (TFN) Active Published 90.99.0000 Water quality - Determination of odour Merged Not Published 10.99.0000 prEN 1622 rev Water analysis - Determination of the threshold odour number (TON) and threshold flavour number (TFN) Active Not Published 10.99.0000
Suspended solids
Suspended solids Split Not Published 10.99.0000 EN 872:1996 prEN 872 rev Water quality - Determination of suspended solids - Method by filtration through glass fibre filters Active Published 90.99.0000 Water quality - Determination of suspended solids - Method by filtration through glass fibre filters Active Not Published 45.00.0979 Water quality - Determination of alkalinity - Part 2: Determination of carbonate alkalinity (ISO 9963-2:1994) Active Published 90.99.0000 Water quality - Determination of alkalinity - Part 1: Determination of total and composite alkalinity (ISO 9963-1:1994) Active Published 90.99.0000
Alkalinity
EN ISO 9963-2:1995 EN ISO 9963-1:1995
Electrical conductivity
EN 27888:1993 Water quality - Determination of electrical conductivity (ISO 7888:1985) Active Published 90.99.0000
Turbidity
EN 27027:1994 EN ISO 7027:1999 Water quality - Determination of turbidity (ISO 7027:1990) Closed Withdrawn 99.60.0000 Water quality - Determination of turbidity (ISO 7027:1999) Active Published 60.60.0000
BOD
202
Appendix 4
Water quality - Determination of biochemical oxygen demand after n days (BODn) - Part 1: Dilution and seeding method with allylthiourea addition (ISO 5815:1989, modified) Active Published 60.60.0000 Water Quality - Guidance standard for assessing the hydromorphological features of rivers Active Not Published 45.00.0979
EN 1899-1:1998
Hydromorphology
prEN 14614
Determination of organic compounds PAHs and hydrocarbons

prEN ISO 9377-1 EN ISO 15680:2003 EN ISO 14402:1999 EN ISO 9377-2:2000 EN ISO 17993:2003 Water quality - Determination of hydrocarbon oil index - Part 1: Method using solvent extraction and gravimetry (ISO/DIS 9377 -1:2000) Abandoned Not Published 40.60.0000 Water quality - Gas-chromatographic determination of a number of monocyclic aromatic hydrocarbons, naphthalene and several chlorinated compounds using purge-and-trap and thermal desorption (ISO 15680:2003) Active Published 60.60.0000 Water quality - Determination of phenol index by flow analysis (FIA and CFA) (ISO 14402:1999) Active Published 60.60.0000 Water quality - Determination of hydrocarbon oil index - Part 2: Method using solvent extraction and gas chromatography (ISO 9377-2:2000) Active Published 60.60.0000 Water quality - Determination of 15 polycyclic aromatic hydrocarbons (PAH) in water by HPLC with fluorescence detection after liquid-liquid extraction (ISO 17993:2002) Active Published 60.60.0000 Water quality - Determination of anionic surfactants by measurement of the methylene blue index MBAS (ISO 7875-1:1984 modified) Active Published 90.99.0000 Water quality - Determination of methylene blue index (MBAS) by flow analysis (CFA and FIA) Active Not Published 10.99.0000 Water quality - Determination of permanganate index (ISO 8467:1993) Active Published 90.99.0000 Water quality - Determination of certain organochlorine insecticides, polychlorinated biphenyls and chlorobenzenes - Gas chromatographic method after liquid-liquid extraction (ISO 6468:1996) Active Published 90.99.0000 Water analysis - Determination of DDT including DDD and DDE Merged Not Published 10.99.0000
Surfactants
EN 903:1993 ISO/NP 16265
EN ISO 8467:1995
Organochlorines
EN ISO 6468:1996
Halogenated/Chlorinated hydrocarbons
Water analysis - Determination of hexachlorobenzene Merged Not Published 10.99.0000 Water analysis - Determination of 1,2-dichloroethane (based on ISO/C10301) Merged Not Published 10.99.0000
203
Appendix 4
Water analysis - Determination of trichloroethylene (based on ISO/CD 10301) Merged Not Published 10.99.0000 Water analysis - Determination of tetrachloroethylene (based on ISO/CD10301) Merged Not Published 10.99.0000 Water analysis - Determination of 1,2,4 trichlorobenzene and technical mixture Merged Not Published 10.99.0000 Water quality - Determination of adsorbable organically bound halogens (AOX) Active Published 90.99.0000 Water quality - Determination of highly volatile halogenated hydrocarbons - Gas-chromatographic methods (ISO 10301:1997) Active Published 90.99.0000 Water analysis - Determination of chloroform (based on ISO/CD 10301) Merged Not Published 10.99.0000 prEN ISO 9562 Water quality - Determination of adsorbable organically bound halogens (AOX) Active Not Published 50.20.0000 Water analysis - Determination of aldrin Merged Not Published 10.99.0000 Water analysis - Determination of dieldrin Merged Not Published 10.99.0000 Water analysis - Determination of endrin Merged Not Published 10.99.0000 Water analysis - Determination of endosulfan Merged Not Published 10.99.0000 EN ISO 11369:1997 Water quality - Determination of selected plant treatment agents Method using high performance liquid chromatography with UV detection after solid liquid extraction (ISO 11369:1997) Active Published 90.99.0000 Water quality - Determination of parathion, parathion-methyl and some other organophosphorus compounds in water by dichloromethane extraction and gas chromatographic analysis Active Published 60.60.0000 Water quality - Determination of parathion, parathion-methyl and some other organophosphorus compounds in drinking waters, ground waters and surface waters - Solid liquid extraction and gas chromatographic method Abandoned Not Published 10.99.0000 Water quality - Dalapon and selected halogenated acetic acids Active Not Published 10.99.0000 Water quality - Determination of glyphosate and AMPA Active Not Published 10.99.0000 EN ISO 15913:2003 Water quality - Determination of selected phenoxyalkanoic herbicides, including bentazones and hydroxybenzonitriles by gas chromatography and mass spectrometry after solid phase extraction and derivatization (ISO 15913:2000) Active Published 60.60.0000 Water analysis - Determination of polychlorynated phenol (based on ISO/CD 8165-2) Merged Not Published 10.99.0000
EN 1485:1996 EN ISO 10301:1997
Other pesticides
EN 12918:1999
Phenols
204
Appendix 4
Water quality - Gas chromatographic determination of some selected chlorophenols in water Active Published 60.60.0000 Water quality - Determination of selected nitrophenols - Method by solid - phase extraction and gas chromatography with mass spectrometric detection (ISO 17495:2001) Active Published 60.60.0000 Water quality - Determination of selected alkylphenols - Part 1: Method for non-filtered samples using liquid extraction and gas chromatography with mass selective detection Active Not Published 10.99.0000 Water quality - Determination of selected alkylphenols - Part 2: Method for filtered samples using solid phase extraction and gas chromatography with mass selective detection Active Not Published 10.99.0000 Water quality - Determination of selected organic nitrogen and phosphorus compounds - Gas chromatographic methods (ISO 10695:2000) Active Published 60.60.0000 Water quality - Determination of selected explosives and related compounds - Method using high performance liquid chromatography (HPLC) with UV Active Not Published 40.20.0000 Page 9 of 11 10/06/2004 https://www.cenorm.be/projex/projex.asp detection (ISO/DIS 22478:2004) Water quality - Determination of epichlorohydrin Active Published 60.60.0000 Water quality - Determination of six complexing agents Gas chromatographic method (ISO 16588:2002) - Active Published 60.60.0000 Water quality - Determination of selected phthalates by gas chromatography/mass spectrometry Active Not Published 10.99.0000
EN 12673:1998 EN ISO 17495:2003 ISO 18857-1 ISO 18857-2
Others
EN ISO 10695:2000 prEN ISO 22478 EN 14207:2003 EN ISO 16588:2003 ISO 18856
Detection of microorganisms
prEN ISO 19458 EN ISO 17994:2004 ENV ISO 13843:2001 Water quality -- Sampling for microbiological analysis Active Not Published 10.99.0000 Water quality - Criteria for establishing equivalence between microbiological methods (ISO 17994:2004) Active Published 60.60.0000 Water quality - Guidance on validation of microbiological methods (ISO/TR 13843:2000) Active Published 60.60.0000 Water quality - Analytical control in microbiology - Part 1: Quality control of culture media Active Not Published 10.99.0000 Water quality - Detection of human enteroviruses by monolayer plaque assay Active Not Published 40.60.0000 Water quality - Determination of enteroviruses - Part 2: Detection by culture Abandoned Not Published 10.99.0000 Water quality - Enteroviruses in bathing waters Split Not Published 10.99.0000
Enteroviruses
prEN 14486
Culturing
EN ISO 6222:1999 Water quality - Enumeration of culturable micro-organisms - Colony count by inoculation in a nutrient agar culture medium (ISO 6222:1999) Active Published 60.60.0000
205
Appendix 4
P. aeruginosa
Water quality - Detection and enumeration of Pseudomonas aeruginosa Part 1: Method by enrichment in liquid medium (based on ISO 8360-1:1988) Split Not Published Water quality - Detection and enumeration of Pseudomonas aeruginosa Part 2: Membrane filtration method Merged Not Published Water quality - Detection and enumeration of Pseudomonas Aeruginosa in bottled water Merged Not Published 40.60.0000 Water quality - Detection and enumeration of Pseudomonas aeruginosa by membrane filtration Active Published 60.60.0000 Water quality - Detection and enumeration of Escherichia coli and coliform bacteria - Part 1: Membrane filtration method (ISO 9308 -1:2000) Active Published 60.60.0000 Water quality - Detection and enumeration of coliform organisms, thermotolerant coliform organisms and presumptive Escherichia coli - Part 2: Multiple tube (most probable number) method Abandoned Not Published 40.20.0000 Water quality - Detection and enumeration of Escherichia coli and coliform bacteria in surface and wastewater - Part 3: Miniaturized method (Most Probable Number) by inoculation in liquid medium (ISO 9308-3:1998) Active Published 60.60.0000 Water quality - Detection and enumeration of Escherichia coli and coliform bacteria in surface and wastewater - Part 3: Miniaturized method (Most Probable Number) by inoculation in liquid medium (ISO 9308-3:1998) Active Published 60.60.0000 Water quality - Detection and enumeration of intestinal enterococci in surface and wastewater - Part 1: Miniaturized method (Most Probable Number) by inoculation in liquid medium (ISO 7899-1:1998) Active Published 60.60.0000 Water quality - Detection and enumeration of intestinal enterococci - Part 2: Membrane filtration method (ISO 7899-2:2000) Active Published Water quality - Detection and enumeration of intestinal enterococci in surface and wastewater - Part 1: Miniaturized method (Most Probable Number) by inoculation in liquid medium (ISO 7899-1:1998) Active Published 60.60.0000
prEN 12780 EN 12780:2002
E. coli
EN ISO 9308-1:2000 ISO 9308-2
EN ISO 9308-3:1998
EN ISO 9308-3:1998/AC:2000
Intestinal enterococci
EN ISO 7899-1:1998 EN ISO 7899-2:2000 60.60.0000 EN ISO 7899- 1:1998/AC:2000
Sulfite-reducing anaerobes
EN 26461-1:1993 prEN 26461-1:1993 rev EN 26461-2:1993 Water quality - Detection and enumeration of the spores of sulfite-reducing anaerobes (clostridia) - Part 1: Method by enrichment in a liquid medium (ISO 6461-1:1986) Active Published 90.99.0000 Water quality - Detection and enumeration of the spores of sulfite-reducing anaerobes (clostridia) - Part 1: Method by enrichment in a liquid medium Abandoned Not Published 10.99.0000 Water quality - Detection and enumeration of the spores of sulfite-reducing anaerobes (clostridia) - Part 2: Method by membrane filtration (ISO 6461-2:1986) Active Published 90.99.0000
206
Appendix 4
Water quality - Detection and enumeration of the spores of sulfite-reducing anaerobes (clostridia) - Part 2: Method by membrane filtration Active Not Published 10.99.0000
prEN 26461-2:1993 rev
Others
prEN ISO 6340 Water quality - Detection of Salmonella species (ISO 6340:1995) Abandoned Not Published 50.60.0000 Water quality - Staphylococci in swimming pool waters Abandoned Not Published 10.99.0000 prEN ISO 19250 EN ISO 10705-1:2001 EN ISO 10705-2:2001 Water quality - Determination of Salmonella species (ISO/DIS 19250:2003) Active Not Published 40.60.0000 Water quality - Detection and enumeration of bacteriophages - Part 1 Enumeration of F-specific RNA bacteriophages (ISO 10705-1:1995) Active Published 60.60.0000 Water quality - Detection and enumeration of bacteriophages - Part 2: Enumeration of somatic coliphages (ISO 10705-2:2000) Active Published 60.60.0000 Water quality - Guidance for the preparation and treatment of poorly water soluble organic compounds for the subsequent evaluation of their biodegradability in an aqueous medium (ISO 10634:1995) Active Published 90.99.0000 Water quality - Evaluation in an aqueous medium of the "ultimate" aerobic biodegradability of organic compounds - Method by analysis of released carbon dioxide (ISO 9439:1990) Closed Withdrawn 99.60.0000 Water quality - Evaluation of the aerobic biodegradability of organic compounds in an aqueous medium Static test (Zahn-Wellens method) (ISO 9888:1991) Closed Withdrawn 99.60.0000 Water quality - Evaluation in an aqueous medium of the "ultimate" aerobic biodegradability of organic compounds - Method of determining the oxygen demand in a closed respirometer (ISO 9408:1991) Closed Withdrawn 99.60.0000 Water quality - Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium Carbon dioxide evolution test (ISO 9439:1999) Active Published 60.60.0000 Water quality - Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium Static test (Zahn -Wellens method) (ISO 9888:1999) Active Published 60.60.0000 Water quality - Evaluation in an aqueous medium of the "ultimate" aerobic biodegradability of organic compounds - Method by analysis of dissolved organic carbon (DOC) (ISO 7827:1994) Active Published 90.99.0000 Water quality - Evaluation in an aqueous medium of the "ultimate" aerobic biodegradability of organic compounds - Method by analysis of biochemical oxygen demand (closed bottle test) (ISO 10707:1994) Active Published 90.99.0000 Water quality - Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium by determination of oxygen demand in a closed respirometer (ISO 9408:1999) Active Published 60.60.0000
Biodegradability
EN ISO 10634:1995
Aerobic
EN 29439:1993 EN 29888:1993 EN 29408:1993 EN ISO 9439:2000 EN ISO 9888:1999 EN ISO 7827:1995
EN ISO 10707:1997
EN ISO 9408:1999
207
Appendix 4
Anaerobic
EN ISO 11734:1998 Water quality - Evaluation of the "ultimate" anaerobic biodegradability of organic compounds in digested sludge - Method by measurement of the biogas production (ISO 11734:1995) Active Published 90.99.0000 Water quality - Evaluation of the aerobic biodegradability of organic compounds in an aqueous medium Semi-continuous activated sludge method (SCAS) (ISO 9887:1992) Active Published 90.99.0000 Water quality - Determination of the elimination and biodegradability of organic compounds in an aqueous medium - Activated sludge simulation test Active Not Published 50.20.0000 Water quality - Evaluation of the elimination and biodegradability of organic compounds in an aqueous medium - Activated sludge simulation test (ISO 11733:1995) Active Published 60.60.0000
Activated sludge
EN ISO 9887:1994 prEN ISO 11733 EN ISO 11733:1998
Sampling techniques/biological assessment

prEN 14996 Water quality - Guidance on assuring the quality of biological and ecological assessments in the aquatic environment Active Not Published 30.99.0979 Water quality - Biological classification of rivers - Part 3: Guidance on biological boundaries Abandoned Not Published 10.99.0000 Water quality - Guidance standard for the sampling of zooplankton from standing waters Active Not Published 10.99.0000 Water quality - Guidance standard for the routine analysis of phytoplankton abundance and composition using inverted microscopy (Utermohl technique) Active Not Published 10.99.0000 Water quality - Guidance standard for the routine sampling of benthic algae in fast flowing, shallow waters Active Not Published 10.99.0000 Water quality - Guidance standard for the routine sampling and pre-treatment of benthic diatoms from rivers Active Published 60.60.0000 Water quality - Guidance standard for the identification, enumeration and interpretation of benthic diatom samples from running waters Active Not Published 60.55.0000 Water quality - Guidance on quality assurance aspects of the sampling and analysis of benthic diatoms Abandoned Not Published 10.99.0000 Water quality - Methods of biological sampling - Guidance on handnet sampling of aquatic benthic macroinvertebrates (ISO 7828:1985) Active Published 90.99.0000 Water quality - Design and use of quantitative samplers for benthic macroinvertebrates on stony substrata in shallow freshwaters (ISO 8265:1988) Active Published 90.99.0000 Water quality - Methods of biological sampling - Guidance on handnet sampling of aquatic benthic macroinvertebrates Active Not Published 10.99.0000 Water quality - Guidelines for quantitative sampling and sample processing of marine soft-bottom macro fauna (ISO/DIS 16665:2003) Active Not Published 40.60.0000
Algae/plankton
EN 13946:2003 prEN 14407
Macro-invertebrates
EN 27828:1994 EN 28265:1994 prEN 27828:1994 rev prEN ISO 16665
208
Appendix 4
Water quality - Sampling in deep waters for macro-invertebrates Guidance on the use of colonization, qualitative and quantitative samplers (ISO 9391:1993) Active Published 90.99.0000 Water quality - Biological classification of rivers - Part 1: Guidance on the interpretation of biological quality data from surveys of benthic macroinvertebrates (ISO 8689-1:2000) Active Published 60.60.0000 Water quality - Biological classification of rivers - Part 2: Guidance on the presentation of biological quality data from surveys of benthic macroinvertebrates (ISO 8689-2:2000) Active Published 60.60.0000
EN ISO 9391:1995 EN ISO 8689-1:2000 EN ISO 8689-2:2000
Fish
EN 14011:2003 prEN 14962 prEN 14757 Water quality - Sampling of fish with electricity Active Published 60.60.0000 Water quality - Guidance on the scope and selection of fish sampling methods Active Not Published 40.20.0000 Water quality - Sampling of fish with gillnets Active Not Published 40.60.0000
Macrophyte
EN 14184:2003 Water quality - Guidance standard for the surveying of aquatic macrophytes in running waters Active Published 60.60.0000 Water quality - Guidance on the data collation, interpretation and classification of running waters based on aquatic macrophytes Abandoned Not Published 10.99.0000 Water quality - Guidance on quality assurance aspects of aquatic macrophytes surveying and analysis in running waters Abandoned Not Published 40.60.0000 Water quality - Sampling - Part 3: Guidance on the preservation and handling of samples (ISO 56673:1994) Closed Withdrawn 99.60.0000 Water quality - Sampling - Part 1: Guidance on the design of sampling programmes (ISO 5667 -1:1980) Active Published 90.99.0000 Water quality - Sampling - Part 2: Guidance on sampling techniques (ISO 5667-2:1991) Active Published 90.99.0000 Water quality - Sampling - Part 1: Guidance on the design of sampling programmes Active Not Published 10.99.0000 Water quality - Sampling - Part 3: Guidance on the preservation and handling of water samples (ISO 56673:2003) Active Published 60.60.0000 Water quality - Guide to analytical quality control for water analysis (ISO/TR 13530:1997) Active Published 60.60.0000 Water quality - Sampling - Part 19: Guidance on sampling in marine sediments (ISO 5667-19:2004) Active Not Published 60.60.0000
prEN 14393
Sampling
EN ISO 5667-3:1995 EN 25667-1:1993 EN 25667-2:1993 prEN ISO 5667-1 rev EN ISO 5667-3:2003 ENV ISO 13530:1998 EN ISO 5667-19:2004
209
Appendix 4
Table 31. Published and Draft SCA Water and Effluent Standards
Parameter
Index of methods Protocols for oil spills
Name/Description
Index of Methods for the Examination of Waters and Associated Materials 1976 - 1992 A guide to practices, procedures and methodologies following oil spill contamination incidents (2004) April 2004 Emission Spectrophotometric Multi-element Methods of Analysis for Waters, Sediments and other materials of interest to the Water Industry 1980. Atomic Absorption Spectrophotometry An Essay Review 1979 . A Survey of Multi-element and Related Methods of Analysis for Waters, Sediments and other materials of interest to the Water Industry 1980 The Determination of Twelve Trace Metals in Marine and other Waters by Voltammetry or AAS 1987 Extractable Metals in soils, sewage sludge-treated soils and related materials 1982 Methods for the Determination of Metals in Soils, Sediments, and Sewage Sludge, and Plants by Hydrochloric-Nitric Acid Digestion, with a note on the determination of Insoluble Metal Contents 1986 7 The Determination of Anions and Cations, Transition Metals, Other Complex Ions and Organic Acids and Bases in Water by Chromatography 1990 Antimony, Arsenic, Beryllium, Chromium, Cobalt, Copper, Gallium, Germanium, Indium, Nickel, Selenium, Silver, Thallium, Vanadium, and Zinc by Electrothermal AAS 1988 Cadmium, Chromium, Copper, Lead, Nickel and Zinc in Sewage Sludges by Nitric Acid/AAS 1981 Lithium, Magnesium, Calcium, Strontium and Barium in Waters and Sewage Effluents by Atomic Absorption Spectrophotometry 1987 Silver in Waters, Sewages and Effluents by Atomic Absorption Spectrophotometry 1982 Acid Soluble Aluminium in Raw and Potable Waters by Spectrophotometry (using Pyrocatechol Violet) 1979. Acid Soluble Aluminium in Marine, Raw and Potable Waters (Second Edition) 1987 Arsenic in Potable and Sea Water by Spectrophotometry (Arsenomolybdenum Blue procedure) 1978 Tentative Method Arsenic in potable waters by Atomic Absorption Spectrophotometry (Semi Automatic Method) 1982 Selenium in Waters 1984 Selenium and Arsenic in Sludges, Soils and Related Materials 1985 A note on the Use of Hydride Generator Kits 1987. Determination of Iodine, Iodate, Iodide and Traces of Bromide in Waters (Tentative Method) 1984 Cadmium in potable waters by atomic absorption spectrophotometry 1976. Cobalt in Potable Waters 1981 Chromium in Raw and Potable Waters and Sewage Effluents 1980 3. Copper in Potable Waters by Atomic Absorption Spectrophotometry 1980 Iron in raw and potable waters by spectrophotometry (using 2, 4, 6 - tripyridyl - 1, 3, 5 - triazine) 1977.
ISBN number
011752669X
Determination of inorganic compounds and and heavy metals

0117500151 0117514616 0117515299 0117520861 0117516899 0117519081 0117523313 0117520950 0117516155 0117520160 0117516783 0117514640 0117520403 0117514519 0117516791 0117519332 0117517607 0117511366 0117516031 0117515280 0117515426 011751327X
210
Appendix 4
Iron and Manganese in Potable Waters by Atomic Absorption Spectrophotometry 1983 Mercury in Waters, Effluent, Soils and Sediments etc. (additional methods) 1985 Mercury in waters, effluents, and sludges by flameless atomic absorption spectrophotometry 1978. Manganese in raw and potable waters by spectrophotometry (using formaldoxime) 1977 2. Molybdenum, especially in sewage sludges and soils by Spectrophotometry 1982 Nickel in Potable Waters 1981 Lead in potable waters by atomic absorption spectrophotometry 1976. Lead and Cadmium in fresh Waters by Atomic Absorption Spectrophotometry.(2nd edition). A General Introduction to Electrothermal Atomization Atomic Absorption Spectrophotometry 1986 Antimony in Effluents and Raw, Potable and Sea Waters by Spectrophotometry (using Crystal Violet) 1982 Tentative Method. The Determination of Organic, Inorganic, Total and Specific Tin Compounds in Water, Sediments and Biota 1992 Zinc in Potable Waters by Atomic Absorption Spectrophotometry 1980 Cyanide in Waters etc 1988 0117517275 0117519073 0117513261 0117513288 0117516805 011751604X 0117511374 0117520039 0117516562 0117523607 0117515418 0117522198
Determination of organic compounds Chemical Disinfecting Agents in Waters and Effluents, and Chlorine Demand 1980 Hydrocarbons Gas Chromatographic and Associated Methods for the Characterization of Oils, Fats, Waxes and Tars 1982 Classical methods for the Characterization of Oils, Fats and Waxes by saponification, hydroxyl, iodine and acid values 1983 The Determination of Oils and Fats in Waste Water by Filtration, Solvent Extraction and Gravimetry 1987 Thin layer chromatograhic characterization of Oils, Fats, Waxes and Tars 1983 Determination of Volatile Fatty Acids in Sewage Sludge 1979. The Determination of Formaldehyde, other Volatile Aldehydes, Ketones and Alcohols in Water 1988 10 Formaldehyde, Methanol, and Related Compounds in raw, waste and potable waters 1982 (Tentative Methods) Determination of Acrylamide monomer in Waters and Polymers 1987 The determination of polycyclic aromatic hydrocarbons in soil by dichloromethane extraction using gas chromatography with mass spectrometric detection (2003) The determination of polynuclear aromatic hydrocarbons in waters (additional methods) 1997 12 The Determination of six Polynuclear Aromatic Hydrocarbons in Waters (with notes on the determination of other PAH) 1985 The Tentative Identification of Volatilizable Organic Compounds by Linear Temperature Programmed Gas Chromatographic Retention Indices, with Notes on Other Methods for Identifying Organic Substances 1988 The determination of Methane and other Hydrocarbon Gases in Water 1988 Analysis of Hydrocarbons in Waters - A Review, and An Ultra-Violet Fluorescence Spectrometric Method 1988 Determination of very low concentrations of Hydrocarbons and Halogenated Hydrocarbons in Water 1984-5 The Determination of Hydrocarbon Oils in Waters by Solvent Extraction, Infra Red Absorption and Gravimetry1983 Chloro- and Bromo- Tri Halogenated Methanes in Water 1980 0117516775 0117517291 0117520764 0117517917 0117514624 011752235X 0117516902 011752039X 0117514934
0117520322 0117522228 0117521280 0117521701 0117520047 0117517283 0117515442
211
Appendix 4 The determination of volatile organic compounds in waters and complex matrices by purge and trap or by headspace techniques 1998 Pesticides Organochlorine insecticides and polychlorinated biphenyls in waters 1978 Pyrethrins and Permethrin in Potable Waters by Electron Capture Gas Chromatography 1981 Organo-Phosphorus Pesticides in River and Drinking Water 1980 Tentative Method The Determination of Organochlorine Insecticides and Polychlorinated Biphenyls in Sewages, Sludges, Muds and Fish 1978 Organochlorine Insecticides and Polychlorinated Biphenyls in Water, an addition, 1984 Chlorophenoxy Acidic Herbicides, Trichlorobenzoic acid, Chlorophenols, Triazines and Glyphosate in Water 1985 Organophosphorus pesticides in Sewage Sludge; Organophosphorus pesticides in River and Drinking Water, an addition, 1985 Determination of Diquat and Paraquat in River and Drinking Waters. Spectrophotometric Methods Tentative 1987 The Determination of Carbamates, Thiocarbamates, Related Compounds and Ureas in Water 1987 Determination of Synthetic Pyrethroid Insecticides in Water by Gas Liquid Chromatography 1992 Chlorphenylid, Flucofuron and Sulcofuron in Waters (Tentative Methods) 1993 Phenylurea herbicides (urons), Dinocap, Dinoseb, Benomyl, Carbendazim and Metamitron in waters 1994 Determination of aldicarb and other N-methyl carbamates in waters 1994 The determination of acidic herbicides, bromoxynil, ioxynil and pentachlorophenol in waters 1997 The determination of organochlorine pesticides and polychlorinated Phenols The Determination of Microgram and Submicrogram Amounts of Individual Phenols in River and Potable Waters 1988 Phenols in Waters and Effluents by Gas Chromatography, 4-aminoantipyrine and 3-methyl-2-benzothiazolinehydrazone 1981 Surfactants Analysis of Surfactants in Waters, Waste Waters and Sludges 1981 4. The Permanganate Index and Permanganate Value Tests for Waters and Effluents 1983 The determination of Material Extractable by Carbon Tetrachloride and of certain hydrocarbon oil and grease components in sewage sludge 1978. Linear Alkylbenzene Sulphonates (LAS) and Alkylphenol Ethoxylates (APE) in Waters, Wastewaters and Sludges by High Performance Liquid Chromatography 1993 PCBs biphenyls in waters and complex matrices (2000) The determination of polychlorinated biphenyls by gas chromatography using mass spectrometric detection (2003) Toxins Determination of microcystin-LR in drinking waters by HPLC 1994 The determination of microcystin algal toxins in raw and treated waters by high performance liquid chromatography 0117529273 0117516058 011751960X 0117514365 0117527149 0117520993 0117516171 0117513733 0117516287 0117516600 0117517771 0117518867 011751912X 0117520756 0117521515 0117523763 0117527122 0117529281 0117529923
212
Appendix 4 1998 Others Urea in Waters 1984 Chlorobenzenes in waters. Organochlorine Insecticides and PCBs in Turbid Waters Halogenated Solvents and Related Compounds in Sewage Sludge and Waters 1985 General Parameters Chemical oxygen demand (dichromate value) of polluted and waste waters 1977. Determination of long alkyl chain quaternary ammonium compounds in environmental matrices by high performance liquid chromatography 1996 Determination of the pH value of sludge, soil, mud and sediment; and lime requirement of soil 1977. Magnesium in waters and sewage effluents by atomic absorption spectrophotometry 1977. Calcium in waters and sewage effluents by atomic absorption spectrophotometry 1977. The measurement of Electrical Conductivity and the Laboratory Determination of the pH value of natural, treated and waste waters 1978. Dissolved oxygen in natural and waste waters 1979. The Instrumental Determination of Total Organic Carbon, Total Oxygen Demand and Related Determinands 1979. The Instrumental Determination of Total Organic Carbon and Related Determinands 1995 Sulphate in Waters, Effluents and Solids 1979 superseded by 136 Bromide in Waters, High Level Titrimetric Method 1981 Dissolved Potassium in Raw and Potable Waters 1980 Tentative Methods Dissolved Sodium in Raw and Potable Waters 1980 Tentative Methods Silicon in Waters and Effluents 1980 Phosphorus in Waters, Effluents and Sewages 1980 Phosphorus and Silicon in Waters, Effluents and Sludges 1992 Boron in Waters, Effluents, Sewage and Some Solids 1980 Oxidized Nitrogen in Waters 1981 Odour and Taste in Raw and Potable Waters 1980 The Determination of Taste and Odour in Potable Waters 1994 The assessment of taste, odour and related aesthetic problems in drinking waters 1998 Hydrazine in Waters Spectrophotometric Method 1981 Total Hardness, Calcium Hardness and Magnesium Hardness in raw and potable waters by EDTA titrimetry 1981 The Determination of Alkalinity and Acidity in Water 1981 Titrimetric Determination of Total and Bicarbonate Alkalinity and Volatile Fatty Acids in Sewage Sludge 1980/89 Ammonia in Waters 1981 0117512494 0117532614 0117512524 0117513121 011751313X 0117514284 011751442X 0117514586 0117529796 0117514926 0117515434 0117515450 0117515469 0117515574 0117515825 0117523771 0117515833 0117515930 0117515973 0117529672 011751599X 0117516007 0117516015 0117522252 0117516139 0117518638 0117519138
213
Appendix 4 Chloride in Waters, Sewage and Effluents 1981 Biochemical Oxygen Demand 1981 superseded by 130 5 Day Biochemical Oxygen Demand (BOD5) Second Edition 1988 (with Amendments to Dissolved Oxygen in Waters). The Assessment of the Nitrifying Ability of Activated Sludge 1980 (Tentative Methods) Determination of Cation Exchange Capacity and Exchangeable Cations (including water soluble ions) in Soils, Related Materials and Sewage Sludge 1979 The Determination of Alkali Extractable Organic Matter in Ash 1981 Fluoride in Waters, Effluents, Sludges, Plants and Soils 1982 The Determination of Chlorophyll a in Aquatic Environments 1980 Sulphide in Waters and Effluents 1983 Tentative Methods The Conditionability, Filterability, Settleability and Solids Content of Sludge 1984. A Compendium of Methods and Tests Total Nitrogen and Total Phosphorus in Sewage Sludge. 1985 Chemical Oxygen Demand (Dichromate Value) of Polluted and Waste Waters 1986 (Second Edition) The Determination of Carbon Dioxide in Natural, Treated and Beverage Waters, with a supplement on Sampling Bottled and Canned Waters 1986 Determination of Sulphite, Sulphur Dioxide, Thiosulphate and Thiocyanate, with notes on the determination of Total Sulphur and other Sulphur compounds 1985 Sulphate in Waters, Effluents and Solids 1988 (2nd Edn.) The determination of bromate, chlorate and chlorite in waters by ion chromatography 1997 Colour and Turbidity of Waters 1981 Suspended, Settleable and Total Dissolved Solids in Waters and Effluents 1980 8 Temperature Measurement for Natural, Waste and Potable Waters and other items of interest in the Water and Sewage Disposal Industry 1986 The Determination of Colour of Waters and Wastewaters. A supplement, 1988 9 The Determination of pH in low ionic strength waters 1988 Determination of the pH Value of Sludge, Soil, Mud and Sediment and the Lime Requirement of Soil (Second Edition) 1992 11 Kjeldahl Nitrogen in Waters 1987 Biodegradability Assessment of Biodegradability 1981 The Assessment of Biodegradability in Anaerobic Digesting Sludge 1988 Detection of Microorganisms The Bacteriological Examination of Drinking Water Supplies 1982 (Report 71) Methods for the Isolation and Identification of Salmonellae (other than Salmonella Typhi) from Water and 0117516759 0117516643 0117516619 0117521914 0117516260 0117516309 0117522120 0117516554 0117516570 0117516597 0117516627 0117516740 0117517186 0117517879 0117518883 0117519154 0117519278 0117519340 0117522406 0117519553 011751957X 0117520179 0117520837 0117520845 0117524174 0117521299
214
Appendix 4 Associated Materials 1982 Isolation and Identification of Giardia Cysts, Cryptosporidium Oocysts and Free Living Pathogenic Amoebae in Water etc 1989 Methods for the isolation and identification of human enteric viruses from waters and associated materials 1995 The Microbiology of Water 1994 - Part 1 - Drinking Water Method for isolation and identification of Escherichia coli O157:H7 1996 An evaluation of presence-absence tests for coliform organisms and Escherichia coli 1996 Evaluation trials for two media for the simultaneous detection and enumeration of Escherichia coli and coliform organisms 1998 Isolation and identification of Cryptosporidium oocysts and Giardia cysts in waters 1999 The Microbiology of Recreational and Environmental Waters (2000) The Microbiology of Drinking Water (2002) - Part 1 - Water Quality and Public Health The Microbiology of Drinking Water (2002) - Part 2 - Practices and procedures for sampling The Microbiology of Drinking Water (2002) - Part 3 - Practices and procedures for laboratories The Microbiology of Drinking Water (2002) -Part 4 - Methods for the isolation and enumeration of coliform bacteria and Escherichia coli (including E. coli O157:H7) The Microbiology of Drinking Water (2002) - Part 5 - Isolation and enumeration of enterococci by membrane filtration The Microbiology of Drinking Water (2002) - Part 6 - Methods for the isolation and enumeration of sulphite-reducing clostridia and Clostridium perfringens by membrane filtration (Superceded by 192) 13 The Microbiology of Drinking Water (2002) -Part 7 - The enumeration of heterotrophic bacteria by pour and spread plate techniques The Microbiology of Drinking Water (2002) - Part 8 - Methods for the isolation and enumeration of Aeromonas and Pseudomonas aeruginosa by membrane filtration The Microbiology of Drinking Water (2002) - Part 9 - Methods for the isolation and enumeration of Salmonella and Shigella by selective enrichment, membrane filtration and multiple tube most probable number techniques The Microbiology of Drinking Water (2002) - Part 10 - Methods for the isolation of Yersinia, Vibrio and Campylobacter by selective enrichment The Microbiology of Sewage Sludge (2003) - Part 1 - An overview of the treatment and use in agriculture of sewage sludge in relation to its impact on the environment and public health The Microbiology of Sewage Sludge (2003) - Part 2 - Practices and procedures for sampling and sample preparation The Microbiology of Sewage Sludge (2003) - Part 3 - Methods for the isolation and enumeration of Escherichia coli, including verocytotoxigenic Escherichia coli The Microbiology of Sewage Sludge (2003) - Part 4 - Methods for the detection, isolation and enumeration of Salmonellae The Microbiology of Drinking Water (2004) - Part 6 - Methods for the isolation and enumeration of sulphite-reducing
0117522821 0117531391 0117530107 0117532290 0117532436
215
Appendix 4 clostridia and Clostridium perfringens by membrane filtration Biological assessment Methods of Biological Sampling, Sampling Macroinvertebrates in water supply systems 1983 Methods of Biological Sampling. A colonization sampler for collecting Macroinvertebrate. Indicators of water quality in lowland rivers 1983 Quantitative Samplers for Benthic Macroinvertebrates in Shallow Flowing Waters 1980 Methods for Biological Sampling, Sampling of Benthic Macro-invertebrates in Deep Rivers 1983 6 Methods for Biological Sampling Handnet Sampling of Aquatic Benthic Macroinvertebrates 1978. Sampling for Nonplanktonic Algae (Benthic Algae or Priphyton) 1982 A review and methods for the use of epilithic diatoms for detecting and monitoring changes in river water quality 1993 The Direct Determination of Biomass of Aquatic Macrophytes and Measurement of Underwater Light 1985 Methods for the Use of Aquatic Macrophytes for Assessing Water Quality 1985- 6 Methods for Sampling Fish Populations in Shallow Rivers and Streams 1983 Toxicity Acute Toxicity Testing with Aquatic Organisms 1981 5 Determination of the Inhibitory effects of chemicals and Waste Waters on the Anaerobic Digestion of Sewage Sludge 1986. Methods for assessing the Treatability of Chemicals and Industrial Waste Waters and their Toxicity to sewage treatment processes 1982 Examining Biological Filters, Toxicity to Aerobic Bacteria, Effect of SRT and Temperature 1985-6 The Enumeration of Algae, Estimation of Cell Volume, and use in Bioassays 1990 Use of Plants to Monitor Heavy Metals in Freshwaters 1991 Sampling and analysis Amenability of sewage sludge to anaerobic digestion 1977 The sampling and initial preparation of sewage and waterworks' sludge, soils, sediments and plant materials Superseded by 89 prior to analysis 1977 Air Segmented Continuous Flow Automatic Analysis. An Essay Review 1979. The Sampling of Oils, Fats, Waxes and Tars, in aqueous and solid systems 1983 General Principles of Sampling and Accuracy of Results 1980 superseded by 143 Ultra Violet and Visible Solution - Spectrophotometry and Colorimetry 1980 Gas Chromatography an Essay Review 1982 High Performance Liquid chromatography, Ion Chromatography, Thin Layer and Column Chromatography of Water Samples 1983 0117512508 0117512516 0117514705 0117519561 0117514918 0117515388 0117516589 0117517267 0117516724 011751943X 0117519596 0117520373 0117523070 0117523712 0117517895 0117517909 0117516279 0117517402 0117514527 0117517259 0117527718 0117518832 0117520004 0117520853
216
Appendix 4 The Sampling and Initial Preparation of Sewage and Waterworks sludges, soils, sediments, plants and contaminated wildlife (2nd Edition) 1986 Material Extractable by Light Petroleum from Sewage Sludge (Tentative Method) 1985 The Sampling of Oils, Fats, Waxes and Tars, in aqueous and solid systems 1983 Discrete and Air Segmented Automated Methods of Analysis including Robots An Essay Review (Second Edition) 1988 Flow Injection Analysis An Essay Review and Analytical Methods 1990 General Principles of Sampling Water and Associated Materials (second edition) 1996; Estimation of Flow and Load 1996 Information on Concentration and Determination Procedures in Atomic Spectrophotometry 1992 Determination of the Adsorption Characteristics of Organic Test Substances in Sewage Treatment Processes (Tentative Method) 1992 Inductively Coupled Plasma Spectrometry 1996 The Analysis of Sludge Digester Gas 1979 . Radiation/radioactivity Measurement of Alpha and Beta Activity of Water and Sludge Samples. The Determination of Radon-222 and Radium-226. The Determination of Uranium (including General X-ray Fluorescent Spectrometric Analysis ) 1985-6 Determination of Radioactivity in Water by Multinuclide Gamma Ray Spectrometry 1989 The determination of tritium (tritiated water) activity concentration by alkaline distillation and liquid scintillation counting 1999 Four Essay Reviews on applications of Radiation Measurement in the Water Industry 1984 011751909X 0117522201 0117517763
0117518859 0117519421 0117519561 0117522546 0117523399 011752364X 0117523755 0117524166 0117532444 0117514632
217
Appendix 4
Table 32. Standard methods for Inorganic species and metals
Method Reference
Number (CAS #)
EPA SW-846
EPA 40 CFR Part 136 1

200.7, 200.8 2 200.7, 200.8 2, 200.9 200.7, 200.8 2, 200.9, 206.2 200.7 200.7, 200.8 2, 200.9, 210.2 200.7 200.7, 200.8 2, 200.9, 213.2 200.7 200.7, 200.8 2, 200.9, 218.6 218.6 200.7 200.7, 200.8 2, 200.9, 220.2 200.7, 200.8 2, 200.9 200.7, 200.8 2, 200.9, 239.2 200.7 200.7 200.7, 200.8 2, 200.9 245.1 200.7, 200.8 2 200.7, 200.8 2, 200.9, 249.2 200.7 200.7, 258.1 200.7, 200.8 2, 200.9, 270.2 200.7 200.7, 200.8 2, 200.9, 272.2 200.7, 273.1 200.7
EPA 40 CFR Parts 141 & Standard Methods 143 1

200.7, 200.8 200.8, 200.9 200.7, 200.8, 200.9 200.7, 200.8 200.7, 200.8, 200.9 200.7, 200.8 200.7, 200.8, 200.9 200.7 200.7, 200.8, 200.9 218.6 200.7, 200.8, 200.9 200.7, 200.9 3500 Fe-D 200.7, 200.8 200.7 200.7, 200.8, 200.9 200.8, 245.1 200.7, 200.8, 200.9 200.7 200.8, 200.9 200.7, 200.8, 200.9 200.7
Aluminium Antimony Arsenic Barium Beryllium Boron Cadmium Calcium Chromium Chromium VI Cobalt Copper Iron Iron, Ferrous Lead Lithium Magnesium Manganese Mercury Molybdenum Nickel Phosphorus Potassium Selenium Silicon Silver Sodium Strontium
7429-90-5 7440-36-0 7440-38-2 7440-39-3 7440-41-7 7440-42-8 7440-43-9 7440-70-2 7440-47-3 7440-48-4 7440-50-8 7439-89-6 7439-92-1 7439-93-2 7439-95-4 7439-96-5 7439-97-6 7439-98-7 7440-02-0 7723-14-0 7440-09-7 7782-49-2 7440-21-3 7440-22-4 7440-23-5 7440-24-6
6010, 6020 6010, 6020, 7041 6010, 6020, 7060 6010, 6020 6010, 6020, 7091 6010 6010, 6020, 7131 6010, 6020 6010, 6020, 7191 7196, 7199 6010, 6020 6010, 6020, 7211 6010, 6020 6010, 6020, 7421 6010 6010 6010, 6020 7470, 7471 6010, 6020 6010, 6020, 7521 6010, 6020 6010, 6020, 7610 6010, 6020, 7740 6010 6010, 6020, 7761 6010, 7770 6010
3500Cr-D
218
Appendix 4
200.7, 200.8 2, 200.9, 279.2 200.8, 200.9 200.7 200.7 200.7, 200.8 2 200.8, 200.9 200.7, 200.8 2 200.7, 200.8 200.7
Thallium Titanium Tungsten Vanadium Zinc Zirconium
7440-25-7 7440-32-6 7440-33-7 7440-62-2 7440-66-6 7440-67-7
6010, 6020, 7841 6010 6010 6010, 6020 6010, 6020 6010
219
Appendix 4
Table 33. EPA methods for inorganic species and metals
METHOD NUMBERS
Method 6010B Method 6020 Method 7000A Method 7020 Method 7040 Method 7041 Method 7060A Method 7061A Method 7062 Method 7063: Method 7080A Method 7081 Method 7090 Method 7091 Method 7130 Method 7131A Method 7140 Method 7190 Method 7191
SPECIES (Methods)
Inductively Coupled Plasma-Atomic Emission Spectrometry Inductively Coupled Plasma-Mass Spectrometry Atomic Absorption Methods Aluminium (Atomic Absorption, Direct Aspiration) Antimony (Atomic Absorption, Direct Aspiration) Antimony (Atomic Absorption, Furnace Technique) Arsenic (Atomic Absorption, Furnace Technique) Arsenic (Atomic Absorption, Gaseous Hydride) Antimony and Arsenic (Atomic Absorption, Borohydride Reduction) Arsenic in Aqueous Samples and Extracts by Anodic Stripping Voltammetry (ASV) Barium (Atomic Absorption, Direct Aspiration) Barium (Atomic Absorption, Furnace Technique) Beryllium (Atomic Absorption, Direct Aspiration) Beryllium (Atomic Absorption, Furnace Technique) Cadmium (Atomic Absorption, Direct Aspiration) Cadmium (Atomic Absorption, Furnace Technique) Calcium (Atomic Absorption, Direct Aspiration) Chromium (Atomic Absorption, Direct Aspiration) Chromium (Atomic Absorption, Furnace Technique)
METHOD NUMBERS
Method 7420 Method 7421 Method 7430 Method 7450 Method 7460 Method 7461 Method 7470A Method 7471A Method 7472 Method 7480 Method 7481 Method 7520 Method 7521 Method 7550 Method 7580 Method 7610 Method 7740 Method 7741A Method 7742
SPECIES (Methods)
Lead (Atomic Absorption, Direct Aspiration) Lead (Atomic Absorption, Furnace Technique) Lithium (Atomic Absorption, Direct Aspiration) Magnesium (Atomic Absorption, Direct Aspiration) Manganese (Atomic Absorption, Direct Aspiration) Manganese (Atomic Absorption, Furnace Technique) Mercury in Liquid Waste (Manual Cold-Vapour Technique) Mercury in Solid or Semisolid Waste (Manual ColdVapour Technique) Mercury in Aqueous Samples and Extracts by Anodic Stripping Voltammetry (ASV) Molybdenum (Atomic Absorption, Direct Aspiration) Molybdenum (Atomic Absorption, Furnace Technique) Nickel (Atomic Absorption, Direct Aspiration) Nickel (Atomic Absorption, Furnace Method) Osmium (Atomic Absorption, Direct Aspiration) White Phosphorus (P4) by Solvent Extraction and Gas Chromatography Potassium (Atomic Absorption, Direct Aspiration) Selenium (Atomic Absorption, Furnace Technique) Selenium (Atomic Absorption, Gaseous Hydride) Selenium (Atomic Absorption, Borohydride Reduction)
220
Appendix 4
Method 7195 Method 7196A Method 7197 Method 7198 Method 7199 Method 7200 Method 7201 Method 7210 Method 7211 Method 7380 Method 7381
Chromium, Hexavalent (Coprecipitation) Chromium, Hexavalent (Colorimetric) Chromium, Hexavalent (Chelation/Extraction) Chromium, Hexavalent (Differential Pulse Polarography) Determination of Hexavalent Chromium in Drinking Water, Groundwater and Industrial Wastewater Effluents by Ion Chromatography Cobalt (Atomic Absorption, Direct Aspiration) Cobalt (Atomic Absorption, Furnace Technique) Copper (Atomic Absorption, Direct Aspiration) Copper (Atomic Absorption, Furnace Technique) Iron (Atomic Absorption, Direct Aspiration) Iron (Atomic Absorption, Furnace Technique)
Method 7760A Method 7761 Method 7770 Method 7780 Method 7840 Method 7841 Method 7870 Method 7910 Method 7911 Method 7950 Method 7951
Silver (Atomic Absorption, Direct Aspiration) Silver (Atomic Absorption, Furnace Technique) Sodium (Atomic Absorption, Direct Aspiration) Strontium (Atomic Absorption, Direct Aspiration) Thallium (Atomic Absorption, Direct Aspiration) Thallium (Atomic Absorption, Furnace Technique) Tin (Atomic Absorption, Direct Aspiration) Vanadium (Atomic Absorption, Direct Aspiration) Vanadium (Atomic Absorption, Furnace Technique) Zinc (Atomic Absorption, Direct Aspiration) Zinc (Atomic Absorption, Furnace Technique)
221
Appendix 4
Table 34. EPA methods for groundwater and wastewater analyses (www.speclab.com)
METHOD NUMBERS
Method 601 Method 603 Method 604
SPECIES (Methods)
Purgeable halocarbons (Gas Chromatography) Acrolein and acrylonitrile (Gas Chromatography) Phenols (Gas Chromatography) Determination of hexachlorophene and dichlorophen in industrial and municipal wastewaters (Liquid Chromatography) Benzidines (Liquid Chromatography)
METHOD NUMBERS
Method 622.1 Method 625 Method 627
SPECIES (Methods)
Thiophosphate pesticides (Gas Chromatography) Semi-volatile organics in waters (Gas Chromatography) The determination of dinitroaniline pesticides in industrial and municipal wastewater (Gas Chromatography) The determination of cyanazine in industrial and municipal wastewater (Liquid Chromatography) The determination of benomyl and carbendazim in industrial and municipal wastewater (Liquid Chromatography) The determination of carbamate and urea pesticides in industrial and municipal wastewater (Liquid Chromatography) Analysis of carbamate and amide pesticides in wastewater (Liquid Chromatography) The determination of organonitrogen pesticides in industrial and municipal wastewater (Liquid Chromatography) Determination of thiocarbamate pesticides in industrial and municipal wastewaters (Gas Chromatography) Determination of rotenone in industrial and municipal wastewaters (Liquid Chromatography) Determination of bensulide in industrial and municipal wastewaters (Liquid Chromatography) Determination of mbts and tcmtb in municipal and industrial wastewaters (Liquid Chromatography) Determination of oryzalin in industrial and municipal wastewaters (Liquid Chromatography)
Method 604.1
Method 629
Method 605
Method 631
Phthalate esters (Gas Chromatography) Nitrosamines (Gas Chromatography) Organochlorine pesticides and PCBs (Gas Chromatography) Analysis of certain organochlorine pesticides in wastewater by gas chromatography (Gas Chromatography) Nitroaromatics and isophorone (Gas Chromatography) Polynuclear aromatic hydrocarbons (Liquid Chromatography) Haloethers (Gas Chromatography) Chlorinated hydrocarbons (Gas Chromatography)
Method 632 Method 632.1 Method 633
Method 608.2 Method 609 Method 610 Method 611 Method 612
Method 634 Method 635 Method 636 Method 637 Method 638
222
Appendix 4
Method 613
Dioxin (Gas Chromatography)
Method 639
Determination of bendiocarb in municipal and industrial wastewaters (Liquid Chromatography) Determination of mercaptobenzothiazole in wastewaters (liquid chromatography) Analysis of thiabendazole in wastewater (liquid chromatography) Analysis of bentazon in wastewater by liquid chromatography Analysis of picloram in wastewater (liquid chromatography) Analysis of certain amine pesticides and lethane in wastewater (Gas Chromatography) Analysis of dinitro aromatic pesticides in wastewater (Gas Chromatography)
The determination of chlorinated herbicides in industrial and municipal wastewater (Gas Chromatography) C, h, and o compounds (Gas Chromatography) The determination of organohalide pesticides and pcbs in industrial and municipal wastewater (Gas Chromatography) Determination of volatile pesticides in municipal and industrial wastewaters by gas chromatography (Gas Chromatography) Determination of triazine pesticides in industrial and municipal wastewater (Gas Chromatography) Determination of diphenylamine in municipal and industrial wastewaters (Gas Chromatography)
223
Appendix 4
Table 35. EPA standard immunoassays The EPA has compiled a list of methods which are specific for immunoassays. The following are the method numbers and titles:
METHOD
Method 4000 Method 4010 Method 4015 Method 4020 Method 4030 Method 4035 Method 4040 Method 4041 Method 4042 Method 4050 Method 4051 Immunoassay
APPLICATION
Screening for Pentachlorophenol by Immunoassay Screening for 2,4-Dichlorophenoxyacetic Biphenyls by Immunoassay Screening for Polychlorinated Biphenyls by Immunoassay Soil screening for Petroleum Hydrocarbons by Immunoassay Soil screening for Polynuclear Aromatic Hydrocarbons (PAHs) by immunoassay Soil screening for Toxaphene by immunoassay Soil screening for Chlordane by immunoassay Soil screening DDT by immunoassay TNT Explosives in Water and soils by immunoassay Hexahydro -1,3,5 - trinitro - 1,3,5 -triazine(RDX) in Soil and water by Immunoassay
224
Bibliography and References

Tables 4: WFD Organic (table 4a) and inorganic (table 4b) Priority Pollutants with Typical Levels and Principal Uses
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Table 5. Physicochemical Properties of Organic (table 5a), inorganic (table 5b) Priority Pollutants and of other water contaminants (table 5c)
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227
16 Akcha F., Burgeot T., Leskowicz A., Budzinski H., Narbonne J.F. (2000), Induction and removal of bulky B[a]P-related DNA adducts and 8-oxoGuo in mussels Mytilus galloprovincialis exposed in vivo to B[a]P-contaminated feed. Mar. Ecol. Prog. Ser. 205, 195-206. 17 Akcha, F., Vincent Hubert, F., Pfhol-Leszkowicz, A. (2003), Potential value of the comet assay and DNA adduct measurement in dab (Limanda limanda) for assessment of in situ exposure to genotoxic compounds. Mutation Res. 534, 21-32. 18 Canova S., Degan P., Peters L.D., Livingstone D.R., Voltan R. and Venier P. (1998). Tissue dose, DNA adducts, oxidative DNA damage and CYP1A-immunopositive proteins in mussels exposed to waterbone benzo[a] pyrene. Mutat. Res., 399, 17-30. 19 Malins D.C., Haimanot R. (1990), 4,6-Diamino-5-formamidopyrimidine, 8-hydroxyguanine and 8-hydroxyadenine in DNA from neoplastic liver of english sole exposed to carcinogens. Biochem. Biophys. Res. Commun., 173, 614-619. 20 Rodriguez-Ariza, A., Alhama, J., Diaz-Mendez, F.M., Lopez-Barea, J. (1999), Content of 8oxodG in chromosomal DNA of Sparus aurata fish as biomarker of oxidative stress and environmental pollution. Mutation Res., 438, 97-107. 21 Everaarts J. M., Sleiderink H. M., Den Besten P. J., Halbrook R. S., Shugart L. R. (1994), Molecular responses as indicators of marine pollution: DNA damage and enzyme induction in Limanda limanda and Asteria rubens. Environ. Health. Perspect., 102, 37-43. 22 Mitchelmore C. L., Birmelin C., Livingstone D. R. and Chipman J. K. (1998a), Detection of DNA strand breaks in isolated mussel (Mytilus edulis L.) digestive gland cells using the Comet assay. Ecotoxicol. Environ. Safety, 41, 51-58. 23 Mitchelmore C. L. and Chipman J. K. (1998b), DNA strand breakage in aquatic organisms and the potential value of the comet assay in environmental monitoring. Mutat. Res., 399, 135-147. 24 Escartin E. and Porte C. (1999), Assessment of PAH Pollution in Coastal Areas from the NW Mediterranean through the Analysis of Fish Bile. Marine Pollution Bulletin, 38, 12, pp. 1200-1206 25 Bocquen, Suivi des effets biologiques du ptrole de lErika sur la moule Mytilus Edulis, www.suivi-erika.info/data/etude/ fichier/dqelu1022857999.pdf , April 2004 26 Dellali M., Gnassia Barelli M., Romeo M. and Aissa P. (2001), The use of acetylcholinesterase activity in Ruditapes decussatus and Mytilus galloprovincialis in the biomonitoring of Bizerta lagoon. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 130 2, pp. 227-235 27 Payne J. F., Mathieu A., Melvin W. and Fancey L. L. (1996), Acetylcholinesterase, an old biomarker with a new future? Field trials in association with two urban rivers and a paper mill in Newfoundland. Marine Pollution Bulletin, 32, 2, pp. 225-231 28 Sol M., Porte C. and Barcelo D. (2001), Analysis of the estrogenic activity of sewage treatment works and receiving waters using vitellogenin induction as a biomarker in fish. Trends in analytical chemistry, 20, 9. 29 Sumpter J. P. and Jobling S. (1995), Vitellogenesis as a Biomarker for Estrogenic Contamination of the Aquatic Environment.Environ Health Perspect 103(Suppl 7):pp.173-178. 30 Goksyr A., Beyer J., Egaas E., Grsvik B. E., Hylland K., Sandvik M. and Skaare J. U. (1996), Biomarker responses in flounder (Platichthys flesus) and their use in pollution monitoring. Marine Pollution Bulletin, 33, 1-6, pp. 36-45 31 Hansen P. -D., Dizer H., Hock B., J. Sherry A. M., McMaster M. and Blaise Ch. (1997), Vitellogenin a biomarker for endocrine disruptors. TrAC Trends in Analytical Chemistry, 17, 7, pp. 448-451
228
32 Lomax D.l P., Roubal W. T., Moore J. D. and Johnson L. L. (1998), An enzyme-linked immunosorbent assay (ELISA) for measuring vitellogenin in English sole (Pleuronectes vetulus): development, validation and cross-reactivity with other pleuronectids. Comparative Biochemistry and Physiology Part B: Biochemistry and Molecular Biology, 121, 4, pp. 425-436 33 Lye C. M., Frid C. L. J., Gill M. E. and McCormick D. (1997), Abnormalities in the reproductive health of flounder Platichthys flesus exposed to effluent from a sewage treatment works. Marine Pollution Bulletin, 34, 1, pp. 34-41 34 Fossi M. C., Casini S., Ancora S., Moscatelli A., Ausili A. and Notarbartolo-di-Sciara G. (2001), Do endocrine disrupting chemicals threaten Mediterranean swordfish? Preliminary results of vitellogenin and Zona radiata proteins in Xiphias gladius. Marine Environmental Research, 52, 5, pp. 477-483 35 Cajaraville M. P., Bebianno M. J., Blasco J., Porte C., Sarasquete C. and Viarengo A. (2000), The use of biomarkers to assess the impact of pollution in coastal environments of the Iberian Peninsula: a practical approach. The Science of The Total Environment, 247, 2-3, pp. 295-311 36 Wester P. W., Van der Ven L., T. M., Vethaak A. D., Grinwiss G. C. M., Vos J. G. (2002), Aquatic Toxicology : opportunities for enhancement through histopathology. Environmental Toxicology and Pharmacology, 11, 289-295. 37 Etxeberria M., Cajaraville M. P. and Marigomez I. (1995), Changes in digestive cell lysosomal structure in mussels as biomarkers of environmental stress in the Urdaibai Estuary (Biscay coast, Iberian Peninsula). Marine Pollution Bulletin, 30, 9, pp. 599-603 38 Bebianno M. J. and Serafim M. A. (1998), Comparison of metallothionein induction in response to cadmium in the gills of the bivalve molluscs Mytilus galloprovincialis and Ruditapes decussates. The Science of The Total Environment, 214, 1-3, pp. 123-131 39 de Lafontaine Y., Gagn.F, Blaise C., Costan G., Gagnon P. and Chan H. M. (2000), Biomarkers in zebra mussels (Dreissena polymorpha) for the assessment and monitoring of water quality of the St Lawrence River (Canada). Aquatic Toxicology, 50, 1-2, pp. 51-71 40 Pedersen S. N., Lundebye A. -K.and Depledge M. H. (1997), Field application of metallothionein and stress protein biomarkers in the shore crab (Carcinus maenas) exposed to trace metals. Aquatic Toxicology, 37, 2-3, pp. 183-200 41 Hylland K., Sandvik M., Utne Skre J., Beyer J., Egaas E. and Goksyr A. (1996), Biomarkers in flounder (Platichthys flesus): an evaluation of their use in pollution monitoring. Marine Environmental Research, 42, 1-4, pp. 223-227 42 Rotchell J. M., Clarke K. R., Newton L. C. and Bird D. J. (2001), Hepatic metallothionein as a biomarker for metal contamination: age effects and seasonal variation in European flounders (Pleuronectes flesus) from the Severn Estuary and Bristol Channel. Marine Environmental Research, 52, 2, pp. 151-171 43 Geret F. and Cosson R. P. (2000), Utilisation des mtallothionines comme biomarqueur de la contamination mtallique : variabilit entre sites et organes chez l'hutre Crassostrea gigas. Oceanologica Acta, 23, pp. 261-271 44 A-Assa S., Palluel O., Porcher J-M (2003), Biomarqueurs prcoces dcotoxicit. Rapport final, INERIS, 2003 45 Lundebye A-K., Vedel G. R., Krogsdam Christensen A. M., Kristiansen K., Hunter D. and Depledge M. H. (1995), Improved quantification of stress proteins by western blotting. Analytica Chimica Acta, 311, 1, pp. 109-114
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Table 12. Bioassays/bioensors

1 O. Atteia, (2001) Kinetics of natural attenuation of BTEX : review of the critical chemical conditions and measurements at bore scale. Prsentation orale, workshop :"Analysis, toxicity and biodegradation of organic pollutants in groundwater from contaminated land, landfills and sediments" Barcelona, 8-10 November 2001. 2 O. Atteia (2002) In situ measurement of biodegradation and its use for natural attenuation study or geochemical modelling. Poster, colloque Response to new pollution challenges, 4-7 Juin 2002 London 3 Rabbow E, Rettberg, P, Baumstark-Khan, C and Horneck, G SOS-LUX- and LACFLUOROTEST for the quantification of genotoxic and/or cytotoxic effects of heavy metal salts. Anal. Chim. Acta 456, 31-39, 2002. 4 Rettberg, P., C. Baumstark-Khan, K. Bandel, et al., Microscale application of the SOSLUXTEST as biosensor for genotoxic agents, Anal. Chim. Acta, 387, pp. 289-296, 1999. 5 Rettberg, P., K. Bandel, C. Baumstark-Khan, et al., Increased sensitivity of the SOS-LUXTest for the deetection of hydrophobic genotoxic substances with Salmonella typhimurium TA1535 as host strain, Anal. Chim. Acta, 426, 167-173, 2000. 6 Baumstark-Khan, C., A. Rode, P. Rettberg, et al., Application of the Lux-Fluoro test as bioassay for combined genotoxicity and cytotoxicity measurements by means of recombinant Salmonella typhimurium TA1535 cells, Anal. Chim. Acta 437, 23-30, 2001. 7 Polyak, B., E. Bassis, A. Novodvorets, S. Belkin and R. S. Marks (2000). Optical fibre bioluminescent whole-cell microbial biosensor to genotoxicants. Water Science andTechnology, 42: 305 311. 8 Polyak, B., E. Bassis, A. Novodvorets, S. Belkin and R. S. Marks (2001). Bioluminescent whole cell optical fiber sensor to genotoxicants: system optimization. Sensors and Actuators B., 74, 18-26. 9 Premkumar R. J., O. Lev, R. R. Marks, B. Polyak, R. Rosen and S. Belkin (2001). Antibodybased immobilization of bioluminescent bacterial sensor cells. Talanta, 55(5), 1029-1038. 10 Billinton N., Barker M.G., Michel C.E., Knight A. W., Heyer W.-D., Goddard N.J., Fielden P.R. and Walmsley, R.M. Development of a green Fluorescent Protein Reporter for a yeast genotoxicity biosensor. Biosensors and Bioelectronics 13 (1998) 831-838. 11 Walmsley R.M., Billinton N. and Heyer W.-D. Green Fluorescent Protein as a reporter for the DNA damage-induced gene RAD54 from Saccharomyces cerevisiae. Yeast 13 (1997) 1535-1545. 12 Knight A.W., Goddard N.J., Fielden P.R., Barker M.G., Billinton N. and Walmsley, R.M. Measurement Science and Technology 10 (1999) 211-217. Development of a green Fluorescent Protein Reporter for a yeast genotoxicity biosensor. 13 Krumbeck, H. und Hansen, P.-D. (1995). Auswirkungen der Belastung des Teltowkanals auf die Havelseenkette im Hinblick auf Eutrophierung und Nutzung als Badegewsser; Bericht im Auftrag der Senatsverwaltung fr Stadtentwicklung und Umweltschutz, Abtlg. IV, 109 S. 14 de Maagd, G.-J. (1998). Genotoxicity of effluents - relevance and assays - a comparative literature study. RIZA EMPO: 63p. 15 16 4369. Chiti G., Marrazza G., Mascini M., Analytica Chimica Acta, 2001, 427, 155-164. Wang J., Rivas G., Luo D., Cai X., Valera F. S., Dontha N., Anal. Chem., 1996, 68, 4365-
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17 Naessens M. and Tran Minh C., "Biosensor using immobilized Chlorella microalgae for determination of volatile organic compounds", Sensors and Actuators B, 1999, 59, 100-102 18 Naessens M., Leclerc J. C. and Tran-Minh C., "Fiber optic biosensor using Chlorella vulgaris for determination of toxic compounds". Ecotoxicol. Environ. Safety, 2000, 46, 181- 185 19 Durrieu C. and Tran-Minh C., "Optical Algal Biosensor using Alkaline Phosphatase for Determination of Heavy Metals", Ecotoxicol. Environ. Safety, 2002, 51, 206-209. 20 Vedrine C., Leclerc J.C., Durrieu C. and Tran-Minh C., "Fiber optic biosensor using Chlorella vulgaris design for herbicides monitoring" Biosensors and Bioelectronics, 2002 21 Jenner, H,A., 1990 Biomonitoring in Chlorination Anti-Fouling Procedures de Zwart, D., Kramer, K.J.M., Jenner, H.A. 1995 Practical experiences with the Biological Early Warning System MOSSELMONITOR 22 Kramer, K.J.M., Foekema, E.M. 2000 The Musselmonitor as biological early warning system; The first Decade 23 Preston, S., Coad, N., Townend, J., Killham, K. and Paton, G. I. 2000. Biosensing the acute toxicity of metal interactions: are they additive, synergistic or antagonistic? Environmental Toxicology and Chemistry, 19, 775-780. 24 Chaudri, A.M., Lawlor, K., Preston, S., Paton, G.I., Killham, K. and McGrath, S.P. 2000. Response of a Rhizobium-based luminescence biosensor to Zn and Cu in soil solutions from sewage treated soils. Soil Biology and Biochemistry, 32, 383-388. 25 Boyd, E. M., Killham, K. and Meharg, A. A. 2000. Toxicity of mono, di and tri chlorophenols to lux marked terrestrial bacteria, Burkholderia species RASC C2 Tn 4431 and Pseudomonas fluorescens. Chemosphere,43,157-166. 26 Shaw, L. J., Beaton, Y., Killham, K. and Meharg, A. A. 2000. Soil-bacterial-toxicant interactions during soil-contact lux-based toxicity testing. Environmental Toxicology and Chemistry 19, 1247-1252. 27 Shaw, L.J., Beaton, Y., Glover, L.A., Killham, K., Osborn, D. and Meharg, A.A. 2000. Bioavailability of 2,4-dichlorophenol associated with soil water-soluble humic material. Environmental Science and Technology, 34, 4721-4726. 28 Durand MJ, Thouand G, Dancheva-Ivanova T, Vachon P and MS DuBow, Specific detection of organotin compounds with a recombinant luminescent bacteria, submitted to Chemosphere. 29 Thouand G, Durand MJ, Chahov B. and MS DuBow, 2001, Bioassay for the detection of organotin compounds with a recombinant luminescent bacteria, Quatrime colloques FrancoJaponais Biosensors and Bioelectrochemistry, 23-26 Octobre, Tokyo, Japon. 30 Farr, M. Pasini, O, MC Alonso, M. Castillo, D. Barcel Toxicity assessment of organic pollution in wastewaters using a bacterial biosensor Anal. Chim. Acta 426 (2001) 155-165 31 Farr M, Barcel.D.: "Characterisation of wastewater toxicity by means of a whole cell bacterial biosensor, using Pseudomonas putida, in conjunction with chemical analysis". Fresenius. J. Anal .Chem. 371 (2001) 467-473 32 Farr M. Gonalves C. Lacorte S. Barcel D. Pesticide toxicity assessment using an electrochemical biosensor with Pseudomonas putida and a bioluminescence inhibition assay with Vibrio fischeri Anal. Bioanal. Chem. 373 (2002) 696-703 33 Farr, M. Garcia, M.-J. Riu, J. Barcel, D. Identification of surfactants degradation products as toxic organic compounds present in sewage sludge J. Environ. Monit. 3 (2001) 232237
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34 Farr, M. Garcia, M.-J. Tirapu, LL. Ginebreda, A. Barcel D. Wastewater toxicity screening of non-ionic surfactants by ToxAlert and Microtox bioluminescence inhibition assays Anal. Chim Acta 427 (2001) 181-189 35 Prez S. Farr M. Garca MJ. Barcel D. Occurrence of polycyclic aromatic hydrocarbons in sewage sludge and their contribution to its toxicity in the ToxAlert100 bioassays 36 Farr, M. Klter, G. Petrovic, M. Alonso M.-C. Lpez de Alda, M. Barcel, D. Identification of toxic compounds in wastewater treatment plants during a field experiment Anal. Chim Acta 456 (2002) 19-30 37 Farr M. Barcel D. Toxicity testing of wastewater and sewage sludge by biosensors, bioassays and chemical analysis Trends in Analytical Chemistry 22 (2003) 299-24 38 The US EPA produced a verification report (EPA/600/R-97/019) and a verification statement in January 1997 for the ROST system. In " Bodem" of August 1998 and article titled" de Rapid Optical Screening Tool Voor Detectie Van Bodemverontreiniging" was published Several Posters where presented at different conferences (among other Consoil 2000) 39 Barczewski, B., Batereau, K., Klaas, N., Schmid, G. (2000): Sensors for on-site assessment of contaminated sites, Abstracts of lecture group Environmental Technology, Achema 2000, Frankfurt am Main, 22.-27.05.2000 40 Batereau, K., Klaas, N., Barczewski, B. (2001): On-Site Assessment of Contaminated Sites: Application of Sensors for On-Site Instrumentation, Field Screening Europe 2001, ISBN 1- 40200739-6, Kluwer Academic Publishers, 2002 41 Klaas, N., Batereau, K., Barczewski, B. (2001): Assessment of Contaminated Sites: Development of Field Screening Instruments, Field Screening Europe 2001, ISBN 1-4020- 0739-6, Kluwer Academic Publishers, 2002 42 Batereau, K. (2002) : Application of sensors for site characterization, NICOLE Meeting Costeffective site characterization Dealing with uncertainties, innovation, legislation constrains, Pisa, 2002 43 Batereau, K., Barczewski, B., Mller, M. (2002) : Application of sensors for site characterization, Response to New Pollution Challenges, 2nd SENSPOL Workshop, June 2002 44 Barzen C, Brecht A, Gauglitz G, (2002) Optical multiple-analyte immunosensor for water pollution control. Biosens. Bioelectron. 17: 289-295. 45 CoilleI, Reder S, Bucher S, Gauglitz G, (2002) Comparison of two fluorescence immunoassay methods for the detection of endocrine disrupting chemicals in water. Biomolecular Engineering 18(6): 273-280. 46 Kroeger K, Jung A, Reder S, Gauglitz G, (2002) Versatile biosensor surface based on peptide nucleic acid with label free and total internal reflection fluorescence detection for quantification of endocrine disruptors. Anal. Chim. Acta. 469: 37-48. 47 Lopez de Alda, Maria, J.; Gil, A.; Paz, E.; and Barcelo, D. Occurrence and analysis of estrogens and progestogens in river sediments by liquid chromatography-electrospray-mass spectrometry. Analyst, 297, (2002), 1279-398. 48 S. Rodriguez-Mozaz, S. Reder, M. Lpez de Alda, G. Gauglitz, D. Barcel. Simultaneous multi-analyte determination of estrone, isoproturon and atrazine in natural waters by the River Analysed (RIANA) an optical immunosensor. Biosensors and bioelectronics 19 (2004) 633-640.
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49 S. Rodriguez Mozaz, M-P. Marco, M. Lpez de Alda, D. Barcel Biosensors for environmental monitoring of endocrine disruptors: a review article 378 Anal. Bioanal. Chem (2004) 588-598 50 Rose, D. Pfeiffer, F.W.Scheller, U. Wollemberg, Fresenius J. Anal. Chem. 369 (2001) 175
51 Nistor, A. Rose, M. Farr, L. Stoica U. Wollemberg, T. Ruzgas, D. Pfeiffer, D. Barcel, L. Gorton, J. Emmeus Anal. Chim Acta 456 (2002) 3-17 52 Hedenmo, A. Narvez, E. Domnguez and I. Katakis. (1997). Improved mediated tyrosinase amperometric enzyme electrodes. J. Electroanal. Chem., 425, 1-11 53 J. Parellada, A. Narvez, M.A. Lpez, E. Domnguez, J. J. Fernndez, V. Pavlov and I. Katakis. (1998). Amperometric enzyme sensors and immunosensors for environmental applications. Anal. Chim. Acta, 362, 47-57. 54 E A Cummings, B R Eggins, S Linquette- Mailley, E T McAdams, S Cosnier and P Mailley, Novel Biosensors based on Polypyrrole modified Carbon Paste Electrodes, SAC99 (Dublin City University 28th July 99). 55 E A Cummings, B R Eggins, E McAdams, C Coleman, M Clements and D Madigan, Biosensing to ensure the perfect pint, The Irish Scientist Year Book 1999, 88 56 E A Cummings, D Madigan, B R Eggins et al, Development of a tyrosinase based screenprinted amperometric electrode for the detection of flavanoid polyphenols in lager beers, J. American Soc. of Brewing Chemists, 2001, 59(2), 84 89. 57 J.L. Marty, N. Mionetto, S. Lacorte and D. Barcel. Validation of an enzymatic biosensor with various liquid-chromatographic techniques for determining organophosphorus pesticides and carbaryl in freeze-dried waters. Analytica Chimica Acta, 1995, 311, 265-271. 58 D. Barcel, S. Lacorte and J.L. Marty. Validation of an enzymatic biosensor with liquidchromatography for pesticide monitoring. Trends in Analytical Chemistry, 1995, 14 (7),334-340. 59 Turpeinen, R., M. Virta and M. M. Hggblom (2003). Analysis of arsenic bioavailability in contaminated soils. Environmental Toxicology and Chemistry 22(1):16. 60 Ivask, A., M. Virta and A. Kahru (2002). Construction and use of specific luminescent recombinant bacterial sensors for the assessment of bioavailable fraction of cadmium, zinc, and mercury in the soil. Soil Biology and Biochemistry 34(10): 1439-1447. 61 Petnen, T., M. Virta, M. Karp and M. Romantschuk (2001). Construction and Use of Broad Host Range Mercury and Arsenite Sensor Plasmids in the Soil Bacterium Pseudomonas fluorescens OS8. Microbial Ecology 41(4): 360-368. 62 Ivask, A., K. Hakkila and M. Virta (2001). Detection of organomercurials with sensor bacteria. Analytical Chemistry 73(21): 5168-5171. 63 Bello Rodriguez, B. and Tothill I.E. Fifth Biosensors for the determination of heavy metals in waters. Workshop on Biosensors and Biological Techniques in Environmental Analysis. Ithaca, NY, USA, 31 May-04 June 2002. 64 Bello Rodriguez, B. And Tothill, Biosensors for the determination of heavy metals in waters. I.E. Biosensors 2002, Kyoto, Japan, 15-17 May 2002. 65 Buckup, K.and P. and M Neue methodisch-technische Aspekte des Impuls-NeutronNeutron-Verfahrens, paper to be presented on the DGG-conference 2003, Jena 66 Buckup, K. andP. Mulipurpos application of the Pulse Neutron Method (PNM), paper presented on the VIII Krajowa Konferencja Naukowo-Techniczna, Szymbark/Poland, Sept., 2002
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67 Buckup, K. and P. and M., Yakovlev, K. Neue Anwendungen der Impuls-NeutronenMessungen, 62. Jahrestagung DGG, March, 2002, Hannover 68 Piorek, Stanislaw, Determination of Metals in Soils by Field-Portable XRF Spectrometry. Current Protocols In Field Analytical Chemistry, 3B.1.1 3B.1.18, 1998. US EPA Method 6200 Field Portable X-Ray Spectrometry for The Determination of Elemental Concentrations in Soil and Sediment January 1998. 69 Sterling, David, Roger Lewis, Douglas Luke, and Brooke Shadel, A Portable X-Ray Fluorescence Instrument for Analyzing Dust Wipe Sample for Lead: Evaluation with Field Samples. Environmental Research, Section A, number 83, pp. 174-179, 2000. 70 C. M. A. Brett and D. A. Fungaro. Poly(ester sulphonic acid) coated mercury thin film electrodes: characterization and application in batch injection analysis stripping voltammetry of heavy metal ions , Talanta, 50 (2000) 1223. 71 C.M.A. Brett, D.A. Fungaro, Modified Electrode Voltammetric Sensors for Trace Metals in Environmental Samples J. Braz. Chem. Soc., 11(3) (2000) 298. 72 C.M.A. Brett, J.M. Morgado, Development of batch injection analysis for electrochemical measurements of trace metal ions in ecotoxicological test media. J Appl Toxicol. 2000 NovDec;20(6):477-81.. 73 M.-L. Tercier-Waeber, J. Pei, J. Buffle, G. C. Fiaccabrino, M. Koudelka-Hep, G. Riccardi, F. Confalonieri, A. Sina, F. Graziottin A Novel Voltammetric Probe with Individually Addressable GelIntegrated Microsensor Arrays for Real-Time High Spatial Resolution Concentration Profile Measurements? Electroanalysis ,12, 2000, 27-34 74 J. Pei, M.-L. Tercier-Waeber, J. Buffle, G. C. Fiaccabrino, and M. Koudelka-Hep, Individually Addressable Gel-Integrated Voltammetric Microelectrode Array for High-Resolution Measurement of Concentration Profiles at Interfaces, Anal. Chem., 2001, 73(10), 2273-81. 75 Pauwels H,. Tercier-Waeber M.-L., Arenas M., Castroviejo R., Deschamps Y., Lassin A., Graziottin F., Elorza F.-J. Chemical characteristics of groundwaters at two massive sulphide deposits in an area of previous mining contamination South Iberian Pyrite Belt Spain. J. Geochem. Expl, 75, 17-41 (2002) 76 Ch. 2 in :Environmental Electrochemistry: Analysis of Trace Element Biogeochemistry American Chemical Society, Symposium Series No. 811, Washington DC, 2002. 77 M.-L. Tercier-Waeber, J. Buffle, M. Koudelka-Hep, F. Graziottin? Submersible/portable voltammetric probes for real-time continuous trace element monitoring and speciation in aquatic systems : State of the art and futur prospects. American Chemical Society 221th National Meeting ; Divisions of Industrial, Engineering Chemistry and Environmental Chemistry ; Invited lecture for the session: Process Analytical Chemistry in Support of Green Chemistry. San-Diego, CA, April 1-5, 2001 78 Corbisier,P, G Ji, G Nuyts, M Mergeay, and S Silver.1993. luxAB gene fusions with the arsenic and cadmium resistance operons of Staphylococcus aureus plasmid pI258. FEMS Microbiol Lett, 110(2): 231-238 79 Corbisier, P., E. Thiry, A. Masolijn, and L. Diels. 1994. Construction and development of metal ion biosensors. In: Bioluminescence and chemoluminescence fundamentals and applied aspects. Campbell, Kricka, and Stanley (eds). John Wiley and Sons. 80 Nies, A, DH Nies, and S Silver. 1990. Nucleotide sequence and expression of a plasmidencoded chromate resistance determinant from Alcaligenes eutrophus. J. Biol. Chem, 265: 5648 - 5653. 81 Corbisier, P., et al. 1999. Whole cell- and protein-based biosensors for the detection of bioavailable heavy metals in environmental samples. Anal. Chim. Acta, 378: 235-244.
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Table 14. Non-biological methods available for monitoring environmental substances

1 J. N. Huckins, J. D. Petty, J. A. Lebo, C. E. Orazio, H. F. Prest, D. E. Tillitt, G. S. Ellis, B. T. Johnson and G. K. Manuweera, Semipermeable membrane devices (SPMDs) for the concentration and assessment of bioavailable organic contaminants in aquatic environments. In Techniques in Aquatic Toxicology (Edited by G. K. Ostrander), CRC Press (Lewis Publishers), Boca Raton. Florida, USA (1996). 2 Huckins, J. N., Manuweera, G. K., Petty, J. D., Mackay, D., and Lebo, J. A. Lipid-containing semipermeable membrane devices for monitoring organic. Environmental Science & Technology 27, 2489-2496. 1993. 3 Sdergren, A. Solvent-filled dialysis membranes simulate uptake of pollutants by aquatic organisms. Environmental Science & Technology 21, 855-859. 1987. 4 Sdergren, A. Monitoring of persistent, lipophilic pollutants in water and sediment by solventfilled dialysis membrane. Ecotoxicology and Environmental Safety 19, 143-149. 1990. 5 Sabaliunas, D. and Sdergren, A. Uptake of organochlorien pesticides by solvent-filled cellulose and polyethylene membranes. Ecotoxicology and Environmental Safety 35, 150-155. 1996. 6 Martin, H., Patterson, B. M., Davis, G. B., and Grathwohl, P. Field trial of contaminant groundwater monitoring: comparing time-. Environmental Science & Technology 37. 2003. 7 DiGiano, F. A., Elliot, D., and Leith, D. Application of passive dosimetry to the detection of trace organic. Environmental Science & Technology 22, 1365-1367. 1988. 8 Petty, J. D., Huckins, J. N., Alvarez, D. A., Brumbaugh, W. G., Cranor, W. L., Gale, R. W., Rastall, A. C., Jones-Lepp, T. L., Leiker, T. J., Rostad, C. E., and Furlong, E. T. A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants. Chemosphere 54, 695-705. 2004 9 Alvarez, D.A., Petty, J.D., Huckins, J.N., Jones-Lepp, T.L., Getting, D.T., Manahan, S.E. Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments. Environ. Sci. Technol., in press. 10 Kingston, J. K., Greenwood, R., Mills, G. A., Morrison, G. M., and Persson, B. L. Development of novel passive sampling system for the time-averaged of a range of organic pollutants in aquatic environment. Journal of Environmental Monitoring 2, 487-495. 2000. 11 Persson, L. B., Morrison, G. M., Friemann, J. U., Kingston, J., Mills, G., and Greenwood, R. Diffusional behaviour of metals in a passive sampling system for for monitoring aquatic pollution. Journal of Environmental Monitoring 3, 639-645. 2001. 12 Blom, L. B., Morrison, G. M., Kingston, J., Mills, G., Greenwood, R., Petersson, T. J. R., and Rauch, S. Performance of an in situ passive sampling system for metals in stormwater. Journal of Environmental Monitoring 4, 258-262. 2002. 13 Blind, T., Gerschwitz, M., Gessler, H., Slama, H., Sorge, H., Gttzelmann, P., and Nallinger, M. Vergleichsuntersuchungen bei der Grundwasserprobenahme: Passives Adsorptiuonsverfahren zur Erkundung organischer Kontaminationen. TerraTech: TerraTech 4, 26-28. 1994. 14 Haas, R. and Oeste, F. D. Passivsammler zur Wasseruntersuchung. Z. Umweltchem. Oekotox. 13, 1-3. 2001. 15 Vrana, B., Popp, P., Paschke, A., and Schuurmann, G. Membrane-enclosed sorptive coating. An integrative passive sampler for monitoring organic contaminants in water. Analytical Chemistry 73, 5191-5200. 2001.
235
16 Zhang H. and Davison W. Performance-Characteristics of Diffusion Gradients in Thin- Films for the in-Situ Measurement of Trace-Metals in Aqueous- Solution, Analytical Chemistry 67, pp. 33913400 (1995). 17 Pawliszyn J., Solid phase microextraction. In Sampling and sample preparation for field and laboratory (Edited by Pawliszyn J.), Elsevier, Amsterdam, The Netherlands (2002). 18 http://www.alcontrol.se/content.asp?p=1117 19 Leonard, A. W., Hyne, R. V., Lim, R. P., Pablo, F., and Van Den Brink, P. J. Riverine Endosulfan Concentrations in the Mamoi River, Australia: Link to. Environmental Toxicology and Chemistry 19, 1540-1551. 2000. 20 Leonard, A. W., Hyne, R. V., and Pablo, F. Trimethylpentane-containing passive samplers for predicting time-. Environmental Toxicology and Chemistry 21, 2591-2599. 2002. 21 Booij, K., Smedes, F., and van Weerlee, E. M. Spiking of performance reference compounds in low density polyethylene and and silicone passive water samplers. Chemosphere 46, 1157-1161. 2002. 22 Zhang, Z., Poerschmann, J., and Pawliszyn, J. Diresct solid phase microextraction of complex aqueous samples with hollow fibre membrane protection. Analytical Communication 33, 219-221. 1996. 23 A. Segal, T. Gorecki, P. Mussche, J. Lips and J. Pawliszyn, Development of Membrane Extraction With a Sorbent InterfaceB. Micro Gas Chromatography System for Field Analysis, Journal of Chromatography a 873, pp. 13-27 (2000). 24 Litten, S., Mead, B., and Hassett, J. Application of passive samplers (PISCES) to locating a source of PCBs on the Black River, New York. Environmental Toxicology and Chemistry 12, 639-647. 1993. 25 L. Muller, T. Gorecki and J. Pawliszyn, Optimization of the Spme Device Design for Field Applications, Fresenius Journal of Analytical Chemistry 364, pp. 610-616 (1999). 26 M. Kawaguchi, K. Inoue, M. Yoshimura, R. Ito, N. Sakui, N. Okanouchi and H. Nakazawa, Determination of Bisphenol a in River Water and Body Fluid Samples by Stir Bar Sorptive Extraction With in Situ Derivatization and Thermal Desorption-Gas Chromatography-Mass Spectrometry, Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 805, pp. 41-48 (2004). 27 M. S. Garcia-Falcon, B. Cancho-Grande and J. Simal-Gandara, Stirring Bar Sorptive Extraction in the Determination of Pahs in Drinking Waters, Water Research 38, pp. 1679-1684 (2004). 28 C. Basheer, V. Suresh, R. Renu and H. K. Lee, D. Development and Application of Polymer-Coated Hollow Fiber Membrane Microextraction to the Determination of Organochlorine Pesticides in Water, E. Journal of Chromatography a 1033, pp. 213-220 (2004). 29 M. S. Garcia-Falcon, C. Perez-Lamela and J. Simal-Gandara, Strategies for the Extraction of Free and Bound Polycyclic Aromatic Hydrocarbons in Run-Off Waters Rich in Organic Matter, Analytica Chimica Acta 508, pp. 177-183 (2004).
236
Legislation and Standard (chapter 3)

1 British Standard, General requirements for the competence of testing and calibration laboratories. BS EN ISO/IEC 17025:2000. 2 Council Directive 2000/60/EC, 23rd Oct 2000 establishing a framework for Community action in the field of water policy. (The water framework directive.) 3 Cheeseman, R. V. and Wilson, A. L. (Revised by Gardner, M. J.) A Manual of Analytical Quality Control for the Water Industry (NS30), Water Research Centre, 1989, ISBN 0 902156 85 3. 4 Council Directive 98/83/EC, 3rd Nov 1998 on the quality of water intended for human consumption. (L330/32) 5 a) Water Supply (Water Quality) Regulations 2000: Statutory Instrument 2000 No 3184. b) Interim Guidance on the the Water Supply (Water Quality) Regulations 2000: Drinking Water Inspectorate September 2003. (This is an excellent guidance document on how to interpret SI No 3184.)
6 Dixon, E.M and Gardner, M.J. Specification for waste water monitoring for urban wastewater treatment implementation. WRc plc R & D Technical Report P96, 1997. 7 ENVIRONMENT AGENCY. Performance Standard for Laboratories Undertaking Chemical Testing of Soil, Environment Agency, February 2003, Version 2. 8 Drinking Water Inspectorate (2003), Standard Operating Protocol for the Monitoring of Cryptosporidium Oocysts in Treated Water Supplies to Satisfy the Water Supply (Water Quality) Regulations 2000, SI No. 3184 England and the Water Supply (Water Quality) Regulations 2001, SI No. 3911 (W.323) Wales. 9 Thompson, K. Clive and Smith, M., Cryptosporidium: The Analytical Challenge, Royal Society of Chemistry, 2001, ISBN 0 85404 840 5. 10 ISO 15705:2002 Water quality -- Determination of the chemical oxygen demand index (STCOD) -- Small-scale sealed-tube method 11 ISO/PRF 17294-1 Water quality -- Application of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of elements -- Part 1: General guidelines and basic principles (available in English only) 12 ISO 17294-2:2003 Water quality -- Application of inductively coupled plasma mass spectrometry (ICP-MS) -- Part 2: Determination of 62 elements 13 14 15 ISO 11262 Soil quality Determination of Cyanide. Drinking Water Testing Specification (DWTS) DWI Information Letter 7/93 QWAS Water Analysis (Microbiology) proficiency testing scheme results 2003
16 Calux biological detection systems for the analysis of very low levels of chemical contaminants; (estrogens; androgens; dioxins etc. (See www.biodetectionsystems.com) 17 S::CAN (on-line diode array spectrometry) http://www.s-can.at/.
18 Thompson, K. Clive and Gray, J. (Eds.) Water Contamination Emergencies: Can We Cope? Royal Society of Chemistry, 2004, ISBN 0 85404 628 3. 19 CSL-LEAP, Mystery (simulated emergency pollution water sample) proficiency scheme. (Barry May, CSL, Sand Hutton, York, YO41 1LZ; (www.fapas.com).
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20 Persoone, G., Janssen, C. and De Coen, W. New Microbiotests for routine toxicity screening and biomonitoring, Kluwer Academic / Plenum Publishers, New York 2000 (ISBN 0-306-46406-3). 21 Protocol for Carrying out Chemical and Microbiological Analysis Interlaboratory Trials Draft Technical Report CEN/TC 308/WG1 (Issue 5). Other relevant references not incorporated in the text: EN ISO 5667-3:2003 Water quality - Sampling - Part 3: Guidance on the preservation and handling of water samples (ISO 5667-3:2003) Kratochvil, B., Goewie, C. E. and Taylor, J. K., (1986) Sampling theory for environmental analysis, Trends in Analytical Chemistry, 5 (10), 253 257. Thompson, K. Clive and Nathanail, C. Paul, Chemical Analysis of Contaminated Land, Blackwell Publishing, 2003, ISBN, 1-84127-334-1. Kaiser, L. E. and Palabrica, V.S., Phototobacterium phosphoreum Toxicity data index (Microtox database) Water Poll. Res. J. Canada, 1991, No.3, 361 -431
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Sixth Framework Programme

Contract: SSPI CT 2003 - 502492

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

OVERVIEW OF THE MANUAL (for the non-specialists)

Measurement of physico-chemical parameters

Biological assessment techniques

Chemical monitoring techniques

Legislation and standards

Quality elements / Parameters

Tidal regime Physico-chemical status

Tidal regime Physico-chemical status

Groundwater level Chemical status

Quantity and dymanics of water flow

Abundance Composition Presence of sensitive taxa Diversity

River continuity Invertebrate fauna HYDROMORPHOLOGICAL Fish

Structure & substrate of the river bed

Morphological conditions BIOLOGICAL

Length/width Species composition Continuity/ground cover

SELECTION OF QEs - RIVERS

Thermal conditions Oxygenation conditions

Temperature Dissolved oxygen

Salinity SPECIFIC SYNTHETIC POLLUTANTS PHYSICO-CHEMICAL

Electrical conductivity PH Alkalinity/ANC Total phosphorus Soluble reactive phosphorus

Total nitrogen Nitrate + nitrite Ammonium

SPECIFIC NON SYNTHETIC POLLUTANTS

Suspended Solids Turbidity

Legend: Mandatory QE specified in Annex V.1.2

Figure 1. Example of selection of quality elements for rivers

Tools for ecological monitoring

Conductivity Redox conditions

Priority & emerging chemical pollutants

Immunoassays Organic matter Chemical analytical methods

Total Nitrogen OM aromaticity

EU-funded projects on samplers & (bio)sensors

Achievements Phosphate Supplementary Information

Figure 2. User-interface of this operational manual

1.2 - Lists of substances currently of direct relevance to the WFD

NONPRESCRIPTION DRUGS Acetaminophen Caffeine Cotinine Ibuprofen

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

1.4.3 Barcelona Convention: protection of the mediterranean sea

1.4.4 - International Commission For The Protection of Rhine (ICPR)

1.5 - Outline of sources of these substances

1.6 - Summary of typical levels of these identified substances in EU water bodies

Typical level in water

Link and Ref

River water Ground Sea water (ng/L) water (ng/L) (ng/L)

www.pesticideinfo.or g www.scorecard.org www.inchem.org

n/a n/a n/a

Discontinued insecticide Insecticide for wood against termites

POLYAROMATIC HYDROCARBONS (PAHS)

www.epa.gov www.epa.gov www.epa.gov www.epa.gov www.scorecard.org www.ecousa.net/toxics/naph.sht ml www.scorecard.org

1 < 50 0.3 to 25 < 50 < 100

n/a <5 0.7 to 10 < 10 nd to 100

0.01 to 0.1 n/a n/a <5 < 0.1

VOCs & SVOCs

Hexachlorobenzene (HCB) Pentachlorophenol

www.epa.gov www.epa.gov www.scorecard.org

nd to 0.04 100 to 1000

Dichloromethane Pentachlorobenzene 1,2,3-trichlorobenzene 1,2,4-trichlorobenzene 1,3,5-trichlorobenzene

100 to 743000 0.1 to 1 10 1 to 10 V

3000 n/a n/a 1 n/a

n/a n/a 1 0.3 1

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