AQUATIC ENVIRONMENTAL RISK ASSESSMENT OF MANGANESE

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1 AQUATIC ENVIRONMENTAL RISK ASSESSMENT OF MANGANESE PROPOSAL FROM WCA ENVIRONMENT LIMITED AND PARAMETRIX INC TO THE ENVIRONMENT AGENCY OF ENGLAND & WALES AND THE INTERNATIONAL MANGANESE INSTITUTE August 2008 Graham Merrington wca environment 23 London Street Faringdon Oxfordshire SN7 7AG, UK Tel: +44 (0) William Stubblefield Parametrix, Inc Texas Street SW Albany, OR USA Tel: Fax:

2 1. AIMS AND OBJECTIVES This research proposal describes the technical approach to be employed in developing a freshwater aquatic predicted no effect concentration for Mn. In undertaking this task a number of key needs of the International Manganese Institute and Environment Agency of England and Wales will be met. The aims of this project are to: Derive a robust evidence-based metric by which to assess the environmental risks of Mn across Europe and North America; Develop a transparent, user-friendly methodology by which local physicochemical conditions can be related to observed Mn toxicity in aquatic organisms, specifically a validated biotic ligand model for Mn; and Deliver an internationally relevant approach to assess and implement Mn compliance for freshwater monitoring data for regulators and the regulated community. This project will deliver the requirements for Mn under REACH (Registration, Evaluation, Authorization and restriction of Chemicals), the European Water Framework Directive (EC 2000) and US national ambient water quality criteria (AWQC; USEPA 2007). 2. INTRODUCTION Metals present some unique implementation challenges to all regulators when compared to synthetic organic chemicals. These challenges can arise from variation in background concentrations, the existence of different chemical species, and changes in this speciation in response to local physicochemical conditions. Such challenges can be significantly reduced in magnitude by accounting for both natural backgrounds and physicochemical conditions of the water column that may affect bioavailability. Accounting for metal bioavailability in compliance assessment provides the most relevant metric for assessing environmental risk and resolves many of the implementation difficulties encountered by regulatory agencies and dischargers of metals to the environment. This proposal is submitted jointly by Parametrix and wca environment (wca). We believe that the regulatory experience and technical knowledge of the combined Parametrix/wca project team will provide the International Manganese Institute (IMnI) and the Environment Agency with the strongest and most cost-effective approach to address the issues associated with the evaluation of potential environmental risks posed by manganese and manganese compounds. Additionally, the Parametrix/wca team is very familiar with all of the extant effects data available for manganese, with Parametrix having generated much of the data in their laboratory. The Parametrix/wca teaming approach to this project offers a number of advantages for IMnI and the Environment Agency: Familiarity with all of the available environmental fate and effects data for manganese;

3 A clear understanding of the regulatory strategies in place in both Europe and North America and a proven ability to work with regulatory authorities in both regions; and A core group of renowned environmental scientists and toxicologists who have been intimately involved in the research and development that has led to the current mechanism-based approach to effects assessment and ecological risk assessment. Due to their familiarity with the fate and effects data, the judicious use of knowledgeable scientists from both firms, and the ability to address environmental concerns from both Europe and North America simultaneously the Parametrix/wca team offers IMnI and the Environment Agency a cost-effective approach to assess the environmental aquatic risks of manganese. 3. BACKGROUND Predicted no effect concentrations (PNECs) are widely used to protect the environment from chemicals or other agents released by human activity. Although most PNECs apply in the receiving environment (soil, water, or air), others apply to industrial or waste treatment processes, or to discharges at the point of emission to the environment. Generally speaking, PNECs relate to doses or concentrations in the environment for specific substances below which unacceptable effects are not expected to occur. In the EU, the Water Framework Directive (WFD; EC 2000) places a requirement on Member States to ensure that all inland and coastal waters achieve good status by This will be achieved through a range of measures, including the use of Environmental Quality Standards (EQSs), which are effectively PNECs, for selected chemicals. The most polluting chemicals have been identified under Annex X of the Directive as Priority Substances or Priority Hazardous Substances for which standards will be set at an EU level. In addition to these Substances, Annex VIII of the WFD also requires that Member States identify other pollutants that are discharged to water in significant quantities. These are referred to as Annex VIII substances and the WFD requires that Member States develop their own standards for these substances. In the UK, and many other Member States, this list of Annex VIII substances includes Mn. Some other developed countries have also prioritized Mn in aquatic standard setting programmes, but few, if any, have been able to develop a scientifically robust and practically useable Mn EQS. The methodology used to derive both Annex X and Annex VIII EQSs under the WFD was developed by Lepper (2005) and is largely based on the EU Technical Guidance Document (TGD; EC 2003), as is also the case for REACH. The TGD was originally developed for the assessment of risks associated with high production volume chemicals - primarily organic substances. The limitation of this methodology for the derivation of PNECs, especially for metals, is widely recognized and has led to the development of alternative guidance (Crane and Babut 2007; ICMM 2007). Nevertheless, using the methodology outlined in the TGD, a Mn PNEC of 7 μg Mn l -1 is derived with an assessment factor of 50 (Bruce Brown pers. comm.). The FOREGS Geochemical Baseline Mapping program ( produced a median Mn

4 concentration for pristine waters across the EU of 15.9 μg l -1 concentrations in the UK ranging between about 4 and 91 μg l -1. (n = 807) with The EU approach to PNEC and EQS development differs somewhat from that in the US Briefly, calculation of national AWQC requires chemical-specific toxicity data from both acute laboratory toxicity tests (i.e., short-term toxicity tests (e.g., 48 or 96 hours) with survival or immobility as the end-point.) and chronic laboratory toxicity tests (i.e., longterm tests conducted to evaluate both lethal and sub-lethal effects, e.g., growth or reproduction). Based on the assembled database, final toxicity values (acute and chronic) are first determined and then used in calculating a chemical criterion value. A Final Acute Value (FAV) is calculated from the acute test database as the concentration of the material corresponding to a cumulative probability of effect of 0.05, using a log triangular distribution model. Based on the distribution of toxicity endpoints determined from the testing guidelines, the FAV thus is intended to protect 95 percent of a diverse group of aquatic genera. Regulators will often use either total or dissolved measures of metal to assess environmental risk in freshwaters, yet neither are entirely accurate predictors of aquatic ecotoxicity. Through an understanding of metal- and organism-specific bioavailability it is possible to provide an appropriate metric of environment risk (ICMM 2007). Bioavailability can be considered as a combination of the physicochemical factors governing metal behaviour and the biological receptor - its specific pathophysiological characteristics (such as route of entry, duration and frequency of exposure; Drexler et al. 2003). Currently, there is no robust or accepted way to account for Mn (bio)availability. The key problems in assessing aquatic environmental risks for Mn using a PNEC based on currently available data and methods are: The provisional proposed value is below ambient background concentrations of Mn for much of the UK, Western Europe and the U.S; The limited set of high quality chronic ecotoxicity data for Mn results in significant remaining uncertainty when using the EU TGD methodology, which is accounted for in deriving the PNEC for REACH and the Water Framework Directive through the use of an assessment factor of 50; Unlike Cu, Ni and Zn, there is currently no speciation-based method available for Mn to account for the influence of physicochemical conditions. 4. PROJECT/MANAGEMENT TEAM The project management team comprises staff from Parametrix/wca (Dr Bill Stubblefield and Dr Graham Merrington), IMnI (Dr. Louise Assem) and the Environment Agency (Bruce Brown), as shown in Figure 1. wca environment limited ( is an independent research and consultancy company established in 2005 by highly experienced chemical risk assessors. It provides assistance to industry and governmental agencies in the field of environmental toxicology and risk assessment and its scientific services are embedded in the experience of the core project team. Since its establishment, wca environment has

5 widened and deepened its services by recruiting expertise in Environmental Impact Assessment, socio-econometrics and marine ecosystems. The wca environment team currently consists of 14 experienced professionals holding advanced degrees in many areas including toxicology, biochemistry, hydrobiology, environmental technology and statistics. wca environment is accredited to ISO 9001 and will manage all components of the project on which it leads within that quality system. All outputs from the project will be peer reviewed by at least one other member of the project team (i.e. Parametrix outputs will be reviewed by wca environment and vice versa) before being submitted to Louise Assem and Bruce Brown. wca environment also operates an Environmental Management System accredited to ISO Project management Team Bill Stubblefield, Project Executive (Parametrix) Graham Merrington, Project Manager (wca environment) Bruce Brown (Environment Agency) Louise Assem (IMnI) Parametrix Core Project Team wca environment William Stubblefield - Expert in the conduct and evaluation of aquatic toxicity data. - Expert in the development of Environmental Quality Standards Robert Gensemer - Expert in toxicity reference value determination and plant toxicity evaluation Graham Merrington - Expert in regulatory affairs - Expert in the development of Environmental Quality Standards Adam Peters - Expert in Biotic Ligand Model and development of EU-based environmental standards Mark Crane - Expert in SSD development and the use of ecotoxicity data Figure 1: Schematic overview of project organization and key people involved in the project team Parametrix is a 100-percent employee-owned firm dedicated to providing quality engineering, environmental sciences, planning and architecture with superior client

6 service. Parametrix's philosophy is to guide clients through the decision-making processes required to achieve practical, cost-effective solutions for each project. We achieve this objective by maintaining a staff of some of the most talented engineers, scientists, and project managers in the business. The foundation of our success is quality staff; our employee-owners are committed to consistently providing products and services that reflect our clients' needs and expectations. Graham Merrington will be overall Project Manager with daily responsibility for ensuring project delivery to time, quality and budget. He will proactively liaise with all project staff at wca environment and Parametrix and will organise and minute monthly teleconferences between client representatives and relevant project staff. Bill Stubblefield will be Project Executive, with responsibility for the strategic direction of the project and joint responsibility with the Project Manager for liaison with client representatives. It is noteworthy that both wca and Parametrix have been involved in similar projects for ongoing risk assessments (e.g., European Copper Institute (ECI), the Nickel Producers Environmental Research Association (NiPERA), the Chromium Development Institute (ICdA) and the Lead Development Association International (LDAI)). The assessment of risks associated with metals in the environment is an evolving discipline and the approach proposed by the Parametrix/wca team reflects current processes followed when implementing EU legislation and incorporates the current state-of-the-science for conducting metal-specific approaches in risk assessments (e.g. the MERAG project). MERAG (Metals Environmental Risk Assessment Guidance Document) is an innovative and collaborative project that seeks to introduce specific hazard or risk assessment guidance to address the specific properties of metals and other natural occurring inorganic substances. This comprehensive project was launched in partnership with key members of the scientific and regulatory communities, Eurometaux and ICMM. The UK Government, through the Department of Environment, Food and Rural Affairs (Defra), provided political support for the project within the European Union and the Organisation for Economic Co-operation and Development (OECD). Pen portraits of the team member s expertise and full curricula vitae are given in Annex I at the end of this proposal. 5. METHODOLOGY The schematic below illustrates the interrelationship between the Tasks in this proposal. While each Task has a distinct output, each will feed into the following task to deliver an implementable aquatic Mn PNEC. REACH Task 1. Compile existing effects data

7 REACH/EQS Task 2. Update existing effects data with new additional data from research programs REACH/EQS Task 3. Develop a biotic ligand model to relate local physicochemical conditions to observed Mn toxicity in aquatic organisms. REACH/EQS Task 4. BLM validation REACH/EQS Task 5. Derive bioavailable PNEC water Collate data on ambient background concentrations Task 6. Deliver an implementable Mn aquatic PNEC EQS Collate monitoring data Figure 2: Schematic overview of the stepwise approach proposed in the proposal and the five key tasks to be undertaken. The balance between REACH related and EQS development related tasks are indicated in the blue boxes. Figure 2 also provides an indication of the balance between REACH related and EQS development related effort for each of the Tasks. However, the value of the deliverables from a number the tasks is similar for both REACH and EQS development. Task 6 is the delivery of the implementation package, which for Europe will require input of spatially referenced monitoring data from the Environment Agency along with access to recently collated data on ambient background concentrations for Mn. These data will be made readily available to the Project team. Further, these data will also be available for use by IMnI for any further REACH related work. The following subsections outline the details of the Tasks to be undertaken in this proposal and illustrate which organisation will lead. Task 1. Literature Identification and Retrieval (Parametrix) As a starting point, previously compiled effects data for manganese will be assembled to characterize the potential environmental hazards to organisms in the aquatic

8 environment, including sediments. PNEC data from long-term ecotoxicity studies of manganese effects will be used, as available, to predict effects on the various environmental compartments. Stubblefield et al. (1997) and Parametrix (2005) presented the results of an extensive search and collection of literature on manganese effects data for organisms from different environmental compartments. However, additional effects data have become available since then from different long-term research studies currently in progress on the effects and bioavailability of manganese in aquatic compartments. Manganese toxicity studies conducted since 2004 will be collected from all available primary and "grey" literature sources. Common sources and databases will be searched (e.g., USEPA s toxicity database: AQUIRE/ECOTOX; the primary scientific literature and CD- ROM database searches, etc.), and references obtained for review. Parametrix staff have extensive experience in conducting toxicity literature reviews, including several recent projects updating toxicity databases for cadmium, zinc, and lead that were used in deriving PNECs or USEPA ambient water quality criteria. Estimated costs include time to conduct a literature search, review the results of the search, and retrieve applicable studies to include in the subsequent data analyses. It is assumed that approximately 50 new ecological studies will be identified and retrieved during this effort. The Task, though useful in the context of EQS development (as it will allow for the development of an SSD) will largely serve the purpose of the REACH requirements. Task Deliverable The outputs from this task will be a spreadsheet and electronic literature database (EndNote format) of the reliable chronic NOEC/EC 10 values for the water column and sediment compartments that will be incorporated in the effects assessment (Task 5). The current effects database will be revised to reflect the inclusion of new data as it becomes available. Such an exercise is essential in order to capture all relevant and recent speciation and effects data for the proceeding tasks. The output of this Task will be included in the interim report delivered at the end of Task 2. Task 2: Literature review and evaluation (Parametrix) The studies identified in the above task and in the previous literature reviews will be evaluated for data relevance and reliability. All toxicity literature will be evaluated to ensure that only those studies that are of the highest quality and technical accuracy will be used in the derivation of a PNEC. Several evaluation schemes are available, but many share the common approach that scientific studies should be evaluated with respect to both suitability (is the study appropriate to help fill a particular need?) and scientific quality (are the conclusions technically defensible?). Critical to both levels of evaluation is that the study report or publication provides sufficient detail with which to evaluate suitability and quality. For this project, we propose to use a scheme that was previously developed, applied, and accepted by the regulatory authorities in the evaluation of the EU environmental risk assessments for zinc, nickel, and lead. Briefly, this approach

9 states that a study is reviewed first to see if it is suited to the goals of the investigation, with tests being rejected if they cannot be used for derivation of a PNEC (e.g., unacceptable test methods were used, etc.). Second, studies are reviewed for data quality, and ranked according to how well experimental details were reported, and whether the toxicity values reported are reliable and accurate (e.g., were exposure concentrations measured, was control mortality within specifications?). Prior to evaluating the manganese toxicity literature, ranking schemes will be developed. Worksheets will be prepared to assist reviewers in conducting consistent evaluations, and will be based on those recently used in evaluating the toxicity databases for zinc, nickel, and lead. All applicable studies will be rated for data reliability using the Klimisch et al. (1997) scoring system. Studies will be scored as follows: 1 Valid without restrictions 2 Valid with restrictions 3 Invalid 4 Not assignable Only studies achieving ranks of 1 or 2 will be considered suitable for inclusion in PNEC derivation. These would represent, at a minimum, studies for which there is moderate confidence that the same result would be obtained in a different laboratory, although there may be minor problems with conduct of the test or availability of sufficient information. In particular, only studies that analytically confirm exposure concentrations will be retained. Estimated costs assume that approximately 200 studies will need to be reviewed for manganese. This assumes approximately 45 minutes per study. The number of studies that need to be reviewed may be an overestimate and costs will be adjusted based on the number of studies actually reviewed and the time required to conduct the reviews. This Task, like Task 1 would provide valuable information for the development of a Mn EQS, yet can be considered as largely serving the purpose of meeting REACH requirements. Task Deliverable The outputs from this task will be the identification of suitable valid studies which are appropriate for use in the derivation of PNECs for manganese for both the water column and sediment compartments. This task builds upon work performed by wca when deriving provisional Annex VIII PNECs for the Environment Agency. In that analysis, insufficient data were available to construct Species Sensitivity Distributions (SSDs), so only the most sensitive, critical data were subjected to full quality review. It is likely that now there are sufficient data for construction of at least a freshwater SSD, so all data used in that SSD will require a quality review. An interim project report will be delivered on completion of this Task, combining the outputs of Tasks 1 and 2. This report will summaries the findings from these tasks, but also provide context in regard to data use, speciation issues and potential information shortfalls for the forthcoming tasks.

10 Task 3: BLM Development (wca environment) Biotic Ligand Models relate local physicochemical conditions to observed toxicity in aquatic organisms. This requires detailed understanding of both the behaviour of manganese in the environment and its interactions with organisms. BLMs are typically developed from a series of univariate ecotoxicity experiments to assess the effects of solution chemistry on toxicity (e.g. Heijerick et al. 2002). Experiments to assess the effects of varying ph, DOC and major ions (e.g., Ca, Mg and Na) on chronic manganese toxicity would be required for each of the species for which a BLM is to be developed. European regulators would require that BLMs were developed for at least one species from each of three trophic levels (i.e., fish, Daphnia and algae). Where indications exist that particular species may be sensitive, undertaking the BLM development for these species may provide greater regulatory confidence in the outputs. Indications from the development of BLMs for other metals suggest that there may be differences between the response of algae and other aquatic organisms to the effects of metal toxicity. It is also necessary for a robust model of the speciation of manganese to be available, and for the development of some BLMs (e.g. Ni) a refinement of the currently available models has been necessary. This may also be the case for manganese as this metal has been much less extensively studied than many of those for which BLMs are available. BLMs have not previously been developed for redox active metals and a consideration of redox conditions may be important in the development of a BLM for manganese. Step by step development of a BLM for Mn 1. The first stage in the development of a BLM is the calculation of manganese speciation in all of the test systems used, as a function of the water chemistry (Figure 3). This must be performed separately for each individual species due to differences in the chemistry of the standard test media. This can be performed using speciation models such as WHAM 6, WinHumicV, PHREEQC and MINTEQA2. Some of these models allow the precipitation of solid phases to be taken into account, whilst others are able to provide improved descriptions of metal binding to dissolved organic matter such as humic substances. Both of these may be of importance for a redox active metal such as manganese. The interactions between manganese and humic substances have been shown to be potentially important in controlling the transport of manganese in peat rich catchments (e.g. Graham et al. 2002), although the association between manganese and dissolved organic carbon is relatively weak when compared to other metals (Tipping 1998). There is relatively little information on the binding of manganese with humic and fulvic acids, although a small number of data sets do exist (e.g. Van Dijk 1971, Schnitzer & Skinner 1967). A study of the speciation of manganese in natural lake waters found that only between 12 and 22 percent of total dissolved manganese was present as Mn 2+ (Corsini et al. 1987). 2. The next stage in BLM development is developing an understanding of any potentially important competitive interactions between manganese and other ions at the assumed site of uptake or toxicity (e.g. Playle et al. 1993a & b). The site

11 of toxic action for metals is generally considered to be the gills of gill-breathing organisms and the cell surfaces of algae. Recent studies have shown that some competing ions can affect the toxicity of manganese.f. For example, Stubblefield et al. (1997) showed that hardness can slightly reduce the toxicity of manganese to brown trout (Salmo trutta), whereas Topperwien et al. (2007) have observed that manganese has only a minimal effect on Cd uptake by a freshwater alga (Scenedesmus vacuolatus). Figure 3. Steps to be taken in the development of a Mn BLM. 3. The classical approach towards BLM development assumes that uptake of metals occurs at a biotic ligand, and that competitive effects between different ions can affect the uptake and consequently the metal toxicity. An alternative approach simply aims to describe the observed toxicity to different aquatic organisms as a function of the water chemistry conditions in a more empirical manner. The former approach can tend to imply a greater degree of mechanistic realism, without necessarily being any more realistic. Both of these approaches have been adopted in the development of previous BLMs. 4. A BLM is then developed for each studied organism by combining the abiotic speciation of manganese with the competitive effects at the hypothetical biotic ligand. This can be done either by including an additional ligand within an existing or modified chemical speciation model (the classical BLM approach) or by relating the toxicity to the manganese speciation (e.g. the free Mn 2+ ion concentration) in a less mechanistic manner. Without review the dataset for Mn and establishing the relationships between physico-chemical parameters and

12 aquatic ecotoxicity data the most appropriate methodology for Mn will not be known. 5. The scientifically preferred option for implementing BLMs is to undertake a correction of the toxicity to each of the individual species which are represented in an SSD to derive an SSD which is specific to the particular water chemistry conditions. This requires recalculating all of the data in the SSD database so that they relate to the conditions of the water in question, then recalculating the SSD in order to derive the site-specific PNEC. In order for this approach to be taken it is necessary to apply BLMs to species other than those for which they were developed (Figure 4). Indications from other metals suggest that other kinds of organisms respond to metals in a similar way, but may have different levels of sensitivity. Any test organism which does not respond in a predictable manner would raise potentially serious questions about the validity of this approach, although as far as we are aware this has not been found to be the case in any such tests undertaken to date. The need to undertake spot checking on a minimum of three species for which BLMs have not been developed also provides an opportunity to undertake testing for additional species which may be used in the SSD. This would demonstrate that the derived BLMs can be applied to organisms such as insects, molluscs, amphibians and higher plants, which would provide confidence in application of the BLMs to the entire ecosystem. Previous spot checking exercises, such as that undertaken for Ni (Denmark 2008) have performed the testing in a variety of natural waters, although this may not be necessary provided that adequate ranges of water conditions can be established in synthetic waters. Figure 4. Spot checking of the Ni BLMs for crustacean species with other organisms (snails and rotifers) in natural waters (from Denmark 2008). The BLMs require validation in a series of ecotoxicity tests on natural waters which cover a sufficiently wide range of conditions for the most important parameters when defining toxicity (typically ph, DOC and Ca). For application in Europe, the ranges of conditions for the waters used in the validation should cover at least the 10 th to the 90 th percentiles of European surface water conditions. A wider range of conditions may need to be

13 considered for global acceptance. Validation of the BLMs developed in this Task will be addressed in Task 4. The different NOEC-values that are compiled in the effects database used for the derivation of the PNEC value have been generated in test media with varying physicochemical characteristics which alter manganese bioavailability and toxicity (e.g.; ph, hardness, and dissolved organic matter for water). Therefore, in order to reduce the uncertainty related to the derivation of ecologically relevant PNEC values, it is proposed to normalise the chronic effects data with the developed chronic bioavailability models (e.g. chronic BLMs), where there is adequate justification to do so. In that regard, each of the individual NOEC-values will be normalised to a predefined, environmentally relevant standard medium (bioavailability translation), representative of EU surface waters, soils or sediments, thereby producing a generic normalised PNEC. The following data should be compiled before normalisation of the toxicity data: Often the abiotic factors driving the bioavailability of manganese for water in the toxicity tests are not reported. In that case, these values should be estimated from existing databases. Alternatively, default values will be used. To define the abiotic factors representative of EU surface waters it is proposed to use the Environment Agency monitoring data, Scottish Environment Protection Monitoring Data and the SWAD database routinely used in EU Risk Assessments, plus Parametrix monitoring databases to calculate appropriate percentiles for the different abiotic factors. Once these abiotic factors are compiled for the different toxicity tests/environmental compartments, all individual toxicity data will be normalised using the bioavailability models developed in the long term research programmes. The aim is to develop a model which is capable of predicting the toxic responses of test organisms to changes in the speciation of Mn (Figures 5 and 6) and competitive effects from other ions at the Biotic Ligand. This will be performed by using knowledge of the specific water chemistry conditions during the tests, particularly the free manganese ion concentrations, and comparing this to the responses of the different test organisms.

14 [Mn2+] TOT = μm -4 H + Mn 2+ OH Mn(OH) 2 Log Conc MnOH + Mn 2 (OH) Mn 2 OH ph Figure 5. Manganese speciation as a function of ph in a simple system [Mn2+] TOT = μm [Cit 3 ] TOT = 1.00 mm -4 H + H 3 (Cit) Cit 3 H 2 (Cit) H(Cit)2-5 Mn 2+ Mn(Cit) OH Mn(HCit) Log Conc Mn(H 2 Cit)+ -8 Mn(OH) 2 Mn 2 (Cit) 2 (OH) ph Figure 6. Manganese speciation as a function of ph with a simple ligand (citrate) The derivation of bioavailability corrections will be undertaken in collaboration with Dr Steve Lofts (CEH, Lancaster), who has considerable experience in the development of fit for purpose models of both the speciation and toxicity of trace metals (e.g. Lofts et al. 2004, Bass et al. 2008). Dr Lofts has been closely involved in the development of the speciation model WHAM, which has been used for all previously developed BLMs. He has also developed approaches for addressing critical loads of metal deposition to soils and is

15 currently involved in addressing metal bioavailability in soils as a function of soil properties (e.g. Lofts et al & 2005). He has also developed a model which describes effects on benthic invertebrate communities in response to metal mixtures in upland streams (Bass et al. 2008). Two main approaches have previously been taken towards making bioavailability corrections in PNEC derivation for specific water quality conditions. The first of these is to make bioavailability corrections for individual species and to correct a generic PNEC on the basis of the most sensitive organism. The second approach is to correct the whole of the chronic effects database to derive an SSD which is specific to the conditions of interest, and to use the recalculated SSD to derive a site specific PNEC. Both of these approaches have been used for EQS derivation, although the latter is generally viewed as being the more scientifically robust. The bioavailability model will be developed to protect the whole ecosystem, either by consideration of the entire effects database, or by consideration of the most sensitive species which will be determined earlier in the Task. If the latter approach is taken then it will be necessary to consider whether a single species is expected to be the most sensitive over the entire range of conditions covered by the model. Again this can only be determined following consideration of the outputs from the previous tasks. Throughout the process the need to provide a simple tool which can be readily integrated into regulatory systems will be taken into account. The model will therefore use the minimum set of input parameters which is consistent with an acceptable predictive capability to describe the variation in the PNEC as a result of water quality conditions. An example for copper is shown in Figure 7. Figure 7. Variation of the PNEC for Cu as a function of ph and DOC concentration

16 This Task is equally important to both REACH and EQS development. Task Deliverable The output from this task will be a chronic BLM for Mn which allows predictions of long term manganese ecotoxicity over a wide range of water quality conditions, using a minimal set of input parameters. The deliverable will comprise the functioning software, and release and guidance notes for the use and operation of the MnBLM. Task 4: BLM Validation (Parametrix) The goal of this task is to validate the BLMs developed in Task 3 using a series of natural waters exhibiting a range of physicochemical characteristics typical of waters throughout the EU. The natural waters selected for testing should typically cover a variety of different water types, such as both soft/acidic and hard/alkaline waters and waters with differing concentrations of dissolved organic matter. It is not usually practical to cover the entire range of possible water conditions within such a validation exercise, although it is important to demonstrate that the BLMs developed are capable of correctly predicting the different responses of test organisms to changes in the abiotic water conditions. Combinations of water quality conditions which are particularly important in terms of manganese ecotoxicity will be considered: the identification of such conditions will be aided by the ecotoxicity test data and BLM predictions. Previous research in our laboratory has led to the identification of several water sources that meet the needs of this validation effort. Physicochemical parameters for these waters are provided in Table 1. In conducting this program, five natural waters will be chosen based on the range of bioavailability expected in natural systems. Following identification of these waters, samples will be collected in the field and shipped to the lab where they will be stored (4 C in the dark) until use in toxicity tests. The chronic toxicity of manganese to a fish (Pimephales promelas), cladoceran (Ceriodaphnia dubia), and algae (Pseudokirchneriella subcapitata) will be determined in each of the natural waters using standard chronic testing procedures (OECD or ASTM). Results from the empirical tests will be compared with BLM-predicted values based on the characteristics of the test waters. Task Deliverable The output from this task will be a report that will examine the validity of the chronic Mn BLMs for predicting long-term manganese toxicity over a wide range of natural water quality conditions.

17 Table 1. Site locations and average water quality of waters used in current study. Site Location Hardness Alkalinity Ca Mg Na K Cl SO 4 DOC 1 ph mg/l as CaCO 3 mg/l Calapooia River Albany, OR S. Platte River Denver, CO S. Platte River (ph-amended) Denver, CO S. Santiam River Cascadia, OR Zollner Creek Mt. Angel, OR DOC = Dissolved organic carbon

18 Task 5: PNEC/AWQC/EQS Derivation (Parametrix for AWQC and wca for EQS) Following completion of the above tasks, the Parametrix/wca team will work to derive scientifically-sound REACH compliant PNECs from which a WFD-specific Mn EQS and a USEPA Ambient Water Quality Criterion (AWQC) for Mn will be developed. wca environment and Parametrix have experience in both the EU and North America in developing water quality, sediment and terrestrial soil standards acceptable to regulatory authorities. wca environment have previously derived a draft Mn EQS on behalf of the Environment Agency, using existing data from the open literature for the fulfillment of requirements under Annex VIII of the Water Framework Directive. Therefore, wca would lead on the derivation of an EU Water Framework Directive compliant EQS. This will be performed using the guidelines outlined in the TGD and the recommendations formulated by the Expert Consultation group on Statistical Extrapolation Techniques (EC 2003). Mark Crane, a Director at wca, was a member of that expert group and has published extensively on the derivation and use of SSDs. The REACH compliant PNEC and the WFD-specific Mn EQS will not differ in regard to the numerical value on which they are based, but an EQS comprises more than just a PNEC (RCEP 1998). Specific procedures have been developed for deriving AWQC and these have been used in deriving or revising dozens of US EPA AWQC since Currently, no AWQC or Sediment Quality Criteria exist for manganese in the US Parametrix has experience of working cooperatively with USEPA regulatory authorities and therefore will lead on the development of an AWQC for Mn. Parametrix have had experience of producing AWQCs for other materials (e.g., methyl tertiary-butyl ether (MTBE)) and we propose to use the same procedures to develop an acceptable criterion value in the US and the production of a draft AWQC document that can be submitted for consideration to the USEPA. This Task will initially deliver a REACH compliant PNEC for the aquatic compartment. However, the majority of effort outlined above will be in relation to EQS development both in the EU and North America. Task Deliverable The outputs from this Task will be scientifically robust PNECs for the assessment of the freshwater aquatic risks of Mn. The deliverable will be in three distinct written forms: A report detailing the derivation of the REACH compliant Mn aquatic PNEC. A report detailing the derivation of a Mn EQS fulfilling the requirements of Annex VIII of the Water Framework Directive. A document on the derivation of a Mn AWQC that can be submitted for consideration by the USEPA. Task 6. Implementation and embedding of AWQC/ EQS and compliance framework (wca). The derivation of a numerical limit value, either an AWQC or EQS, is only one stage in producing a useable standard for the assessment of potential Mn aquatic risks (RCEP 1998). As highlighted in the Introduction to this proposal, metals present a number of unique implementation challenges when compared to synthetic organic chemicals. Therefore, the initial part of this Task will be a reality check of the proposed tools and values produced in Tasks 3 and 5 by practical application and comparison with ambient background concentrations in freshwaters from the US and EU through the use of data sources from

19 FOREGS, the Environment Agency, the Scottish Environment Protection Agency and SWAD. Biological essentiality levels for manganese will also be considered (as was undertaken in the Cu VRA; ECI 2007). The Environment Agency will provide significant technical input and compliance systems know how to this part of the task through the involvement of Bruce Brown and the WFD Technical Advisory Group in terms of delivering this regulatory reality check for the derived Mn EQS. Having established the level of environmental realism of the suggested aquatic limits there will still be a requirement to deliver the MnBLM to regulators (and the regulated community) in a form which allows them to implement the speciation-based approach described in Task 3 in a simple and resource-neutral way. Recent experiences with UK regulators suggest that they require a BLM-based tool which is simple and can be implemented efficiently, with minimal data requirements and in ways which fit with their current and likely future working practices. Some existing BLMs are overly complex and time consuming to use and will not be readily accepted by regulators, principally due to the increased costs of implementing them. The required level of simplification of the MnBLM developed in Task 3 in order to fit with regulatory systems will not be known until the completion of Task 3. The overriding aim is to ensure that any BLM-based tool closely mimics or replicates the outputs of the version developed in Task 3. wca have recently produced a simplified version of the Cu BLM for use by UK regulators in implementing an EQS based on the BLM (Environment Agency 2008). This was required because o the perceived difficulties in implementing the Cu BLM, which requires detailed water chemistry input data and is time-consuming to use. UK regulators are currently proposing revisions to the Cu and Zn EQSs to take account of bioavailability because appropriate tools are already available for both of these metals. Whilst a BLM already exists for Ni, it is not currently in a format which would be suitable for integration into UK regulatory systems for assessing compliance against an EQS. Any requirement for the development of simpler bioavailability prediction methods will depend on the complexity and format of the BLM developed during Task 3. As a result of the requirement for automated reporting of metal bioavailability, there may be less scope for complexity in the required bioavailability prediction tool than in a separate BLM application. This may require use of a simplified relationship between manganese toxicity and the solution conditions. Any such simplified tools will be fully tested against the manganese BLM and the limitations carefully considered. It is envisaged that a bioavailability correction factor, for application to a dissolved manganese concentration, may be the required output for regulatory compliance assessment. In contrast to the Cu BLM, which recalculates the entire SSD for specific water conditions, the simplified Cu BLM provides an estimate of the resulting PNEC from Cu BLM calculations on the basis of the ph, DOC and Ca conditions alone. Whilst this results in some reduction in the accuracy of the derived PNEC the benefits in terms of reduced input requirements and processing time are considered to outweigh this slight reduction in accuracy. A comparison between the two models is shown in Figure 7.

20 Figure 7. Comparison of Cu PNECs predicted by the Cu BLM (observed PNEC) and the draft version of the simplified Cu PNEC (estimated PNEC) for 786 natural waters. The red line represents a 1:1 relationship between observations and predictions; data within the blue dashed lines are within a factor of 2 of the Cu BLM prediction (Environment Agency 2008). This type of simplified model is not a replacement for the full BLM developed in Task 3, but is suitable for use as an earlier screen within a tiered risk assessment framework (Comber et al. 2008). Furthermore, such a tool has the advantage of minimising the resource requirements relative to current systems, as it is readily automated within existing laboratory information management systems. This means that when the relevant supporting parameters are reported the bioavailability correction factors for the relevant metals will also be reported. This can then allow a comparison to be made between the measured dissolved metal concentration and the EQS for that metal. This integration of BLMs into automated reporting systems requires that the BLMs are simple tools which can be made compatible with the necessary systems. This task will deliver such a system for Mn, informed through understanding and collaborative working with the UK Regulatory Agencies and their partners in other member states. Throughout this Task the Environment Agency will share the findings and approaches adopted to implement a robust, relevant Mn EQS with regulatory colleagues in Germany, The Netherlands and France under an existing arrangement on the derivation and use of Annex VIII EQSs. This Task is not REACH related and is solely concerned with the development and subsequent provision of an implementable Mn EQS. Task Deliverable This task would deliver an implementable EQS compliance assessment framework for manganese, which can be readily applied within regulatory systems. The framework would also be made applicable to North America, through the experience of Parametrix. Such a framework has already been developed by wca in collaboration with the Environment Agency for Cu and Zn. Specifically the deliverables of this task would be:

21 - A relatively simple MnBLM estimator software program that would closely mimic the MnBLM and be readily integrated into automated compliance assessment systems. - A written report providing: Conclusions on the need to take ambient background concentrations of manganese into account within a compliance assessment framework, and proposals for their implementation; A provisional compliance assessment for manganese using available monitoring data; A pragmatic system of implementation and compliance assessment for Mn which regulators and the regulated could readily use without the need for significant resources; An assessment of compliance with a Mn EQS and how that compliance is positively affected by the use of the speciation-based approaches.

22 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese 6. PROJECT PHASES Table 2 outlines the timing of the tasks and the organisations within the project team responsible for delivery. The development of the BLM will clearly take the greatest amount of project time, but it is envisaged that this will begin immediately upon completion of Tasks 1 and 2. Although the PNEC derivation in Task 5 will not start until Q3 in 2009 we envisage that draft PNECs will be calculated from Q Each Task will deliver a written output which will be peer reviewed before being distributed to the clients. Feedback and comments will be incorporated before finalisation. Monthly teleconference calls and three face to face meeting are planned to discuss progress. 9/24/

23 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Table 2. Tasks, timings and lead organisations for delivery of Aquatic Environmental Risk Assessment of Manganese. Scheduled face to face meetings are shown in brackets Research phase Q3 Q4 Q1 Q2 Q3 Q4 Task 1. Literature Identification and Retrieval Deliverable by the 15 th of October 2008 Task 2. Literature Review and Evaluation Deliverable by the 31 st of December 2008 Task 3. BLM Development Deliverable by the 15 th of October 2009 Task 4. BLM Validation Deliverable by the 15 th of October 2009 Task 5. PNEC/AWQC/EQS * Derivation Deliverable by the 31 st of December 2009 Task 6. Implementation and embedding of AWQC/ EQS and compliance framework Deliverable by the 31 st of January 2010 Parametrix (Face to face project start up) A spreadsheet of the reliable chronic NOEC/EC10 values for the water column and sediment compartments Parametrix An interim project report on the identification of suitable valid studies appropriate for use in the derivation of PNECs. wca wca wca (face to wca and face meeting) Parametrix Functioning software, and release and guidance notes for the use and operation of the MnBLM Parametrix Parametrix wca and Parametrix report on the validity of the chronic Mn BLMs for predicting long-term manganese toxicity. Parametrix and wca Parametrix and wca Reports detailing the PNEC, EQS and AWQC derivation. wca wca (face to face meeting) A report detailing an implementable EQS compliance assessment framework for Mn. *wca responsible for derivation of EU PNEC/EQS and Parametrix responsible for AWQC. 9/24/

24 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese 7. BUDGET The requested funding for the project is estimated to be 160,258 (EURO excl. VAT). It includes costs for all tasks, including subcontractors, and all administrative, literature and travel expenses (three meetings with the sponsors at the offices of wca environment in the United Kingdom). Project expenses Costs project ( )* Task 1 (Primarily REACH related) 4,500 PMX Sub total Task 2 (Primarily REACH related) PMX Sub total Task 3 (Both REACH and EQS development related) wca environment Lancaster University (Steve Lofts) PMX Sub total Task 4 (Both REACH and EQS development related) PMX Sub total Tasks 5 (Both REACH and EQS development related) wca environment PMX Sub total Task 6 (Primarily EQS development related) wca environment PMX 4,500 13,062 13,062 52,660 6,000 2,760 61,420 48,267 48, , Sub total 13,640 TOTAL ( EXCL. VAT) 160,258 *Rate of conversion from GBP to Euro 1.24, Costs include peer-review of all tasks produced by partner organisation.

25 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese References Bass, Blust, Clarke, Corbin, Davison, de Schamphelaere, Janssen, Kalis, Kelly, Kneebone, Lawlor, Lofts, Temminghoff, Thacker, Tipping, Vincent, Warnken, Zhang Environmental Quality Standards for trace metals in the aquatic environment. Environment Agency, Bristol, UK. (SC030194). Comber SDW, Merrington G, Sturdy L, Delbeke K, van Assche F Copper and zinc water quality standards under the EU Water Framework Directive: The use of a tiered approach to estimate the levels of failure. Science of the Total Environment (In Press) Corsini A, Wade G, Wan C, Prasad S (1987) Speciation of soluble manganese in lakewater with Chelex-100 and polyacrylate resin, XAD-7. Can. J. Chem. 65, Crane M, Babut M Environmental quality standards for Water Framework Directive Priority Substances: Challenges and opportunities. Integrated Environmental Assessment and Management 3: Denmark European Union Risk Assessment Report on Nickel and Nickel Compounds (Draft) European Chemicals Bureau, Ispra, Italy. Drexler J, Fisher N, Henningsen G, Lanno R, McGreer J, Sappington KG Issue paper on the bioavailability and bioaccumulation of metals. US EPA Risk Assessment Forum, Washington. EC (European Commission) Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for community action in the field of water policy. Official Journal of the European Communities L327/1 22 December EC (European Commission), 2003 Technical Guidance Document on Risk Assessment in Support of Commission Directive 93/67/EEC on Risk Assessment for New Notified Substances and Commission Regulation (EC) No 1488/94 on Risk Assessment for Existing Substances and Directive 98/8/EC of the European Parliament and of the Council Concerning the placing of biocidal products on the market. Ispra. Italy. ECI European Union Risk Assessment Report on Copper, copper(ii)sulphate pentahydrate, copper(i)oxide, copper(ii)oxide, dicopper chloride trihydroxide. Voluntary risk assessment, draft February European Copper Institute. Environment Agency, Using Biotic Ligand Models to help implement Environmental Quality Standards for metals under the Water Framework Directive. Environment Agency, Bristol, UK. (in press) Graham M, Gavin K, Farmer J, Kirika A, Britton A (2002) Processes controlling the retention and release of manganese in the organic rich catchment of Loch Bradan, SW Scotland. Applied Geochemistry 17, Heijerick, De Schamphelaere, Janssen Biotic Ligand Model development predicting Zn toxicity to the alga Pseudokirchneriella subcapitata: possibilities and limitations. Comp. Biochem. Physiol. 133C: ICMM Metals Environmental Risk Assessment Guidance. International Council on Mining and Metals, London, UK. Klimisch H-J, Andreaea M, Tillmann U A systematic approach for evaluating the quality of experimental toxicological and ecotoxicological data. Regulatory Toxicology and Pharmacology. 25: 1-5. Lepper P Manual on the methodological framework to derive environmental quality standards for priority substances in accordance with Article 16 of the Water Framework Directive (2000/60/EC). Schmallenberg (DE): Fraunhofer-Institute Molecular Biology and Applied Ecology. Lofts S, Spurgeon DJ, Svendsen C, Tipping E Deriving soil critical limits for Cu, Zn, Cd, and Pb: a method based on free ion concentrations. Environmental Science & Technology 38: Lofts S, Spurgeon DJ, Svendsen C, Tipping E Fractions affected and probabilistic risk assessment of Cu, Zn, Cd and Pb, in soils using the free ion approach. Environmental Science & Technology 39: Parametrix Manganese Water/Sediment/Soil Quality Criteria Database: Review of Existing Data and Recommendations. Prepared by Parametrix, Albany, Oregon. December Playle, R.C., D.G. Dixon and K. Burnison (1993a) Copper and cadmium binding to fish gills: Estimates of metal-gill stability constants and modeling of metal accumulation. Can. J. Fish. Aquat. Sci. 50(12): Playle, R.C., D.G. Dixon and K. Burnison (1993b) Copper and cadmium binding to fish gills: Modification by dissolved organic carbon and synthetic ligands. Can. J. Fish. Aquat. Sci. 50(12): RCEP Royal Commission on Environmental Pollution, 21st Report Setting Environmental Standards. HMSO, London, UK. Schnitzer M, Skinner S (1967) Organo-metallic interactions in soils:5. Stability constants of Pb2+, Ni2+, Mn2+, Co2+, Ca2+ and Mg2+ fulvic acid complexes. Soil Sci. 103, Stubblefiled W, Brinkman S, Davies P, Garrison T, Hockett J, McIntyre M (1997) Effects of water hardness on the toxicity of manganese to developing brown trout (Salmo trutta). Environ. Toxicol. Chem. 16, Tipping E (1998) Humic ion binding model VI: an improved description of the interactions of protons and metal ions with humic substances. Aquatic Geochemistry 4, 3-48.

26 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Topperwien S, Behra R, Sigg L (2007) Competition among zinc, manganese and cadmium in the freshwater alga Scenedesmus vacuolatus. Environ. Toxicol. Chem. 26, US EPA Aquatic life ambient freshwater quality criteria copper. EPA-822-R Office of Water 4304T, Washington DC, USA. Van Dijk (1971) Cation binding of humic acids. Geoderma 5,

27 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Annex I Expertise Graham Merrington, PhD is a Director at wca environment and an environmental scientist with over 14 years of experience in environmental consultancy, environmental regulation and academia. He represented the UK at Expert Groups for the Water Framework Directive, and was a regular attendee as an expert for metals-related issues at European Commission TCNES. He has considerable experience in the environmental risk assessment of trace metals and has been closely involved in the Existing Substances Regulations metals risk assessments, in the development of Environmental Quality Standards for metals and the preparation of the Metals Environmental Risk Assessment Guidance (MERAG). Graham has recently worked with regulatory colleagues on REACH Implementation Project Expert Working Groups to define appropriate ecotoxicity testing approaches under the REACH regulations. His main areas of expertise are in the assessment of environmental fate and behaviour of chemicals, especially metals; soil chemistry and chemical bioavailability; bioaccumulation and biomagnification through food chains; environmental management frameworks; and project management. Adam Peters, PhD is a Principal Scientist at wca environment and an environmental chemist with over 9 years of experience in environmental consultancy, environmental regulation and academia. He has been responsible for management of environmental aspects of the Notification of New Substances scheme and the Existing Substances Regulations in the UK, and has recently been a regular attendee as an expert for metalsrelated issues at European Commission TCNES. He has been closely involved with the development of Environmental Quality Standards for metals and the preparation of the Metals Environmental Risk Assessment Guidance (MERAG). Adam s main areas of expertise are in the assessment of environmental fate, behaviour, bioavailability and effects of trace metals in relation to the use of biotic ligand models; environmental risk assessment of industrial chemicals; assessment of persistent, bioaccumulative and toxic (PBT) substances; Hazard assessment of waste materials and their recovery; and development and validation of environmental quality standards for metals and metalloids. Mark Crane, PhD, is a Director at wca environment and an environmental toxicologist with over 20 years of experience in environmental consultancy and academia. Mark has extensive experience in assessing ecotoxicology data for government and commercial clients for the OECD HPV programme and under the Existing Substances Regulations. Specifically, Mark will use his experience in the development and critical review of the species sensitivity distributions for Mn. Bill Stubblefield, PhD, is the technical director of aquatic toxicology for Parametrix s Toxicology Division. His areas of expertise include aquatic and wildlife toxicology as well as site-specific assessments and surveys. He has conducted a variety of research programs for the metals and mining industry that involved environmental issues resulting from the discharge of mine-associated waters and tailings, and the toxicity of metals and byproducts of metal mining. He has considerable experience in the oil and gas industry working on issues associated with the evaluation of impacts to aquatic and terrestrial species as a result of oil spills, refinery effluents, and the toxicity of petroleum products and process streams. He has authored more than 50 peer-reviewed publications and technical presentations. He has served as an invited participant at a number of scientific

28 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese and regulatory conferences and serves as technical reviewer for several scientific publications. Bill also serves as a courtesy faculty member in the Departments of Environmental and Molecular Toxicology at Oregon State University. Bob Gensemer, PhD., is a senior ecotoxicologist and office manager of the Parametrix Environmental Research Laboratory (PERL) with experience as an aquatic ecologist and ecotoxicologist in both the academic and industrial sectors. Bob has worked on or managed projects for a variety of industrial and government clients. His consulting project experience includes reviewing and conducting site-specific water quality criteria modifications (chiefly for metals), the development of new ambient water quality criteria [e.g., methyl-t-butyl ether (MTBE) and cyanide], aquatic plant toxicology, and ecological risk assessments for both aquatic and terrestrial habitats. Much of his applied scientific research has focused on predicting the impacts of water quality factors on the toxicity of chemicals to aquatic organisms, with a particular focus on metals in water with elevated hardness. Bob is particularly interested in the development or modification of ambient water quality criteria for protection of aquatic life in effluent-dependent and ephemeral waters in arid western regions of the U.S. Steve Lofts, Ph.D, is a Senior Researcher with the Centre for Ecology and Hydrology with over 12 years of experience in the measurement and modelling of the fate, behaviour and toxicity of trace metals in the aquatic and terrestrial environments. Steve has been closely involved in the development of a method for calculating critical limits for metals in soils which are dependent upon the soil chemistry, and in the development of a model which describes the response of benthic invertebrates to mixtures of metals and acidity in mining impacted upland streams. Specifically, Steve will be closely involved in the development of the BLM for manganese in order to ensure that it is robust and scientifically defensible.

29 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Europass Curriculum Vitae Personal information First name(s) / Graham MERRINGTON Surname(s) Address(es) wca environment limited, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Telephone(s) Mobile: Graham.merrington@wca-environment.co.uk Nationality British Date of birth Gender Desired employment / Occupational field Male ENVIRONMENTAL CONSULTANT (ENVIRONMENTAL CHEMISTRY) Work experience Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector April Present Principal Consultant Technical responsibilities include direct work on, and supervision of, environmental consultancy projects on soils, sediments and waters. Managerial responsibilities include project management on technical projects. wca environment limited, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Environmental consultancy Occupation or position held Main activities and responsibilities Dates September 2002 March 2007 Principle Scientist Technical responsibilities included direct work on risk assessment and quality standard derivation and use. Managerial responsibilities include staff and project management on technical projects.

30 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Name and address of employer Type of business or sector Environment Agency, Almonsbury West, Bristol, UK Environmental Regulation Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Dates August 1998 June 2002 Lecturer in Soil Chemistry Teaching and research in soil chemistry, environmental chemistry and soil science. Department of Soil and Water, Adelaide University, Waite Campus, Glen Osmond, South Australia, 5064, Australia Higher Education Dates August 1994 July 1998 Occupation or position held Lecturer in Environmental Chemistry Main activities and Teaching and research in environmental chemistry, contaminated land and soil science. responsibilities Name and address of employer Type of business or sector School of Conservation Science, Bournemouth University, Talbot Campus, Fern Barrow, Poole, Dorset, BH12 5BB, UK. Higher Education Dates Sept1993 July 1994 Occupation or position held Postdoctoral Research Fellow Main activities and Research in fate and behaviour of metals in contaminated soils. responsibilities Name and address of employer Type of business or sector Education and training Title of qualification awarded Principal subjects/occupational skills covered Name and type of organisation providing education and training Level in national or international classification Department of Soil Science, University of Reading, Whitekinghts, Reading, Berks, UK. Higher Education Dates PhD Thesis title: Transfer and fate of heavy metals at historic metalliferous mine sites Queen Mary and Westfield College, University of London, UK ISCED 6 Title of qualification awarded Principal subjects/occupational skills covered Dates BSc (2:i hons) Environmental Science Soil Science, Environmental Pollution, Hydrology

31 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Name and type of organisation providing education and training Level in national or international classification Queen Mary and Westfield College, University of London, UK ISCED 5 Personal skills and competences Mother tongue(s) English Other language(s) Self-assessment Understanding Speaking W r i t i n g European level (*) Listening Reading Spoken interaction Spoken production Language Language (*) Common European Framework of Reference for Languages Social skills and competences Organisational skills and competences Technical skills and competences Interpersonal skills developed through presentation of research seminars, papers at international conferences. Teaching undergraduates and MSc. and presenting research material to school groups, members of the public, growers groups and agricultural bureau staff, potential industrial funders and senior Regulatory and Industry staff. Supervision of seven postgraduate students at Adelaide. Programme management in my previous Regulatory role two high profile areas of work with significant cross-disciplinary involvement within the Environment Agency and externally with other governmental agencies and industry groups. These programmes specifically require reputation, budget, resource and people management to ensure the delivery of robust, useable and accepted outputs. Laboratory Manager in the School of Conservation Sciences, responsible for the laboratory analytical facilities and the everyday running of the teaching laboratories including the management of 9 technical staff. Successfully completed Team Leader Development Programme in Environment Agency, including residential courses on People and Performance, Project Management, Time Management and Leadership. Formerly secretary of South Australian Branch of the Australian Soil Science Society, member SETAC and elected to UK Council as publicity Officer, elected to the Committee for International Society for Trace Element Biochemistry for Member of the British Society of Soil Science. Regular referee for technical papers and grant applications Direct experience in use of a range inorganic analytical tools, as well as routine chemical, mineralogical, pedological and other laboratory techniques including isotope dilution. Field based projects and glasshouse trials, setting up of field trials assessing the impact of contaminants on plant growth and other indicators of soil and environmental health. Risk based tools and techniques for chemicals, including assessment of ecotoxicology data and risk characterisation. Computer skills and competences MS Word, Excel

32 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Driving licence Additional information Full driving licence for cars Publications Only the most recent papers and reports are listed here: Merrington, G. and Smernik, R.J. (2004) Cadmium sorption in biosolids amended soils: results from a field trial. Science of the Total Environment. 327, Oliver, I.W., Merrington, G. and McLaughlin, M.J. (2004) Australian biosolids: Characterisation and determination of available copper. Environmental Chemistry. 1, Van Zwieten L., Rust, J., Kingston, T., Merrington, G. and Morris, S. (2004) Influence of copper fungicide residues on occurrence of earthworms in avocado orchard soils. Science of the Total Environment. 329, Oliver, W., Hass, A., Merrington, G., Fine, P. and McLaughlin, M.J. (2005) Copper Availability in Seven Israeli Soils Incubated with and without Biosolids. Journal of Environmental Quality. 34, 508- Oliver, I.W., McLaughlin, M.J. and Merrington, G. (2005) Temporal trends of total and potentially available element concentrations in sewage biosolids: a comparison of biosolid surveys conducted 18 years apart. Science of the Total Environment, 337, Oliver, I.W., Merrington, G. and McLaughlin, M.J. (2006) Copper Partitioning Among Mineral and Organic Fractions in Biosolids. Environmental Chemistry, 3, Merrington, G (2006) The development and use of soil quality indicators for assessing the role of soil in environmental interactions. Environment Agency, Rio House, Bristol. 249pp. Science Report SC Grosso, A., Fishwick, S. and Merrington, G. (2007) United Kingdom Report on Soil Screening Values. Chapter in: Carlon, C. (Ed.) (2007) Derivation methods of soil screening values in Europe. A review and evaluation of national procedures towards harmonisation. European Commission, Joint Research Centre, Ispra. EU EN, pp Special Issue of metals risk assessment in soils. Gorsuch, J., Merrington, G., Welp, G., Dwyer, R., Hennelly, M. and Schoeters. I. (2006) Assessing risks of metals added to soils in Europe and North America. Environmental Toxicology and Chemistry, 25, Merrington, G., Fishwick, S. and Brooke, D. (2006) The derivation and use of soil screening values for metals for the ecological risk assessment of contaminated land: a regulatory perspective. Land Contamination and Reclamation, 14, F. J. Zhao, McGrath, S. P. and Merrington, G. (2007) Estimates of ambient background concentrations of trace metals in soils for risk assessment. Environmental Pollution, 148: Full CV available from:

33 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Europass Curriculum Vitae Personal information First name(s) / Surname(s) Adam PETERS Address(es) wca environment limited, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Telephone(s) ( ) Mobile: Fax(es) ( ) adam.peters@wca-environment.com Nationality British Date of birth Gender Desired employment / Occupational field Male ENVIRONMENTAL CONSULTANT (ENVIRONMENTAL CHEMISTRY) Work experience Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector September Present Principal Consultant Technical responsibilities include direct work on environmental chemistry, risk assessment and environmental quality standards. wca environment limited, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Environmental consultancy Occupation or position held Main activities and responsibilities Name and address of employer Dates January 2004 August 2007 Principal Environmental Chemist (Position held at date of leaving) Provision of expert advice on chemical hazard and risk assessment, EQS development, chemical prioritization, behaviour and effects of trace metals and hazardous waste classification, project management and development and delivery of training materials. Scottish Environment Protection Agency, 5, Redwood Crescent, East Kilbride, G74 5PP

34 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Type of business or sector Environmental Regulator Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Dates November 2001 December 2003 Principal Chemicals Assessment Scientist management of environmental aspects of the Notification of New Substances scheme and the Existing Substances Regulations in the UK. Representation of the UK at EU technical meetings for New Substances, Existing Substances and Classification and Labelling (Environmental Effects). Environment Agency, Evenlode House, Howbery Park, Wallingford, OX10 8BD Environmental Regulator Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Education and training Title of qualification awarded Principal subjects/occupational skills covered Name and type of organisation providing education and training Level in national or international classification Dates February 2001 November 2001 Post Doctoral Research Associate Researching the development of two dimensional QSARs to take account of both chemical properties and soil conditions in contaminated land assessment. Department of Geological Sciences, University of Durham, Durham, UK Research Dates PhD Thesis title: A study of the binding of trace metals and radionuclides by humic substances Institute for Environmental and Natural Sciences, University of Lancaster, Lancaster, UK ISCED 6 Title of qualification awarded Principal subjects/occupational skills covered Name and type of organisation providing education and training Level in national or international classification Dates BSc (Hons) 2.1 Environmental Chemistry Environmental Chemistry, analytical chemistry Environmental Science Department, University of Lancaster, Lancaster, UK ISCED 5 Personal skills and competences Mother tongue(s) English Other language(s) Self-assessment Understanding Speaking Writing European level (*) Listening Reading Spoken interaction Spoken production

35 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese French A2 Basic user A2 Basic user A2 Basic user A2 Basic user A2 (*) Common European Framework of Reference for Languages Social skills and competences Teamwork: I have worked in teams for most of my professional life; Presentation skills: I have made many oral presentations at national and international conferences and workshops to both technical and lay audiences. Chairing & negotiating skills: I have chaired sessions at expert workshops scientific meetings Technical skills and competences Environmental Chemistry and Risk Assessment: expertise gained from formal training, and practical experience as an environmental regulator. Computer skills and competences Driving licence MS Word, Excel, Access; Use of models for chemical speciation, risk assessment and data estimation. Full driving licence for cars.

36 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Additional information PUBLICATIONS Crane M., Fisher B., Leake C., Nathail P. Peters A., Stubblefield W. and Warn T (2007) How should an environmental standard be implemented? SETAC, Pensacola, USA (in preparation). MacGregor K. and Peters A. (2007) Distribution of Persistent Organic Pollutants (POP) in Eels (Anguilla anguilla) across Scotland. Scottish Environment Protection Agency, Stirling, UK. Peters A.(Rapporteur), Adams W, Diamond M., Davison W., DiToro D., Doyle P., Mackay D., Nriagu J., Ptacek C., Skeaff J., Tipping E., Waeterschoot H. (2006) Integrated Approach for Hazard Assessment of Metals and Inorganic Metal Substances: The Unit World Model Approach. in Assessing the Hazard of Metals and Inorganic Metal Substances in Aquatic and Terrestrial Systems. Adams W. and Chapman P. (Eds.) SETAC, Pensacola, USA. Peters A. (Chair), Smolders E., Allen H., Beauchemin S., Buvé L., Checkai R., Garett B., Groenenberg B. (Rapporteur), Hendershot W., Kwong J., Marsh M., Paktunc D., Rencz A., Sauvé S. (2005) The dynamics and long term fate of metals-in-soils: the role of geochemistry. In McGeer J., Skeaf J. & Rowsome S. Final Report from the International Workshop on Metals-in-Soils: Science Gaps and Regulatory Needs, Natural Resources Canada, Ottawa, Canada Peters, A., Zhang, H. and Davison, W. (2003) Investigation of the application of DGT devices for measurement of trace metals in low ionic strength freshwaters. Anal. Chim. Acta., 478, Peters A., Tipping E. and Hamilton Taylor (2001) Americium binding to humic acid. Environ. Sci. Technol. 35, Peters A. (1999) Trace metal binding by humic acid. Ph.D. Thesis, Lancaster University, Lancaster, UK. Lead J., Hamilton-Taylor J., Peters A., Reiner S and Tipping E. (1998) Europium binding by fulvic acids. Analytica Chimica Acta, Vol. 369, pp KEY RECENT PROFESSIONAL EXPERIENCE Implementation of Biotic Ligand Models for Cu and Zn in the compliance assessment of Environmental Quality Standards in the UK Provision of training in chemical risk assessment to the Malaysian Department of the Environment, and provision of training in environmental chemistry to the Scottish Environment Protection Agency Environmental risk assessment, EQS development, implementation and validation for trace metals, including UK representation under existing substances regulations and member of the Metals Environmental Risk Assessment Guidance (MERAG) Science Review Panel. A UK representative at EU technical meetings on environmental risk assessment under the notification of new substances and existing substance regulations (Directive 98/8/EC). Risk assessment of industrial chemicals in accordance with the EU technical guidance document. Development and review of environmental quality standards for the protection of freshwater and marine ecosystems in accordance with current European guidance. Hazard assessment and classification of waste materials and assessment of the recovery of resources from waste materials. Full cv available at

37 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Europass Curriculum Vitae Personal information First name(s) / Mark CRANE Surname(s) Address(es) wca environment limited, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Telephone(s) ( ) Mobile: Fax(es) ( ) mark.crane@wca-environment.com Nationality British Date of birth Gender Desired employment / Occupational field Male ENVIRONMENTAL CONSULTANT (ENVIRONMENTAL TOXICOLOGY) Work experience Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector May Present Director Technical responsibilities include direct work on, and supervision of, ecotoxicity and environmental consultancy projects. Managerial responsibilities include staff and project management on technical projects. wca environment limited, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Environmental consultancy Occupation or position held Main activities and responsibilities Dates January 1998 April 2005 Managing Partner Technical work on environmental toxicology and chemistry; project management; training and workshop facilitation.

38 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Name and address of employer Type of business or sector Crane Consultants, 23 London Street, Faringdon, Oxfordshire, SN7 7AG, UK Environmental consultancy Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Dates April 1994 December 2001 Senior Lecturer in Biological Sciences Teaching and research in environmental toxicology and chemistry, and limnology. School of Biological Sciences, Royal Holloway, University of London, Egham, Surrey, TW20 0EX, UK Higher Education Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Education and training Title of qualification awarded Principal subjects/occupationa l skills covered Name and type of organisation providing education and training Level in national or international classification Dates December 1988 March 1994 Research Scientist Research into the effects of contaminants on fish, aquatic invertebrates and plants using laboratory tests, mesocosms and field survey techniques; desk-based consultancy on environmental toxicology and chemistry for government and commercial clients. WRc plc, Henley Road, Medmenham, Buckinghamshire, SL7 2HD, UK Environmental research and consultancy Dates Diploma in Management Management of staff, projects and budgets Institute of Leadership and Management ISCED 5 Title of qualification awarded Principal subjects/occupationa l skills covered Dates PhD Thesis title: Effects of Pollution on the Freshwater Shrimp Gammarus pulex L.

39 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Name and type of organisation providing education and training Level in national or international classification University of Reading, UK ISCED 6 Title of qualification awarded Principal subjects/occupationa l skills covered Name and type of organisation providing education and training Level in national or international classification Dates Postgraduate Certificate in Education (Pass with Credit) Secondary school teaching theory and practice; specialist subjects: biology and chemistry University of East Anglia, Norwich, UK ISCED 5 Title of qualification awarded Principal subjects/occupationa l skills covered Name and type of organisation providing education and training Level in national or international classification Personal skills and competences Dates BSc (1 st Class Hons.) Ecology Plant and animal biology and ecology; statistics, behavioural ecology, limnology. University of East Anglia ISCED 5 Mother tongue(s) English Other language(s) Self-assessment Understanding Speaking Writing European level (*) Listening Reading Spoken interaction Spoken production French Spanish A2 A2 Basic user Basic user A2 A2 Basic user Basic user (*) Common European Framework of Reference for Languages A2 Basic user A2 A2 Basic user A2 Basic user Basic user A2 A2 Basic user Basic user

40 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Social skills and competences Teamwork: I have managed or worked in teams for most of my professional life; I have contributed to committee work for government and professional societies (e.g., Veterinary Products Committee, Environmental Panel of the Advisory Committee on Pesticides, SETAC Europe Council). I have also undertaken voluntary work in teams in a hostel for homeless men and in youth clubs. Presentation skills: I have made many oral presentations at national and international conferences and workshops to both technical and lay audiences. Chairing & negotiating skills: I have chaired seminars for government and commercial clients; I taught negotiation skills to MSc students at the University of London. Organisational skills and competences Technical skills and competences I am currently Managing Director of wca environment limited, responsible for organising budgets, staff and workloads. I managed a team of 16 postgraduate and postdoctoral staff when I was a Senior Lecturer at the University of London. I have set up and run several technical consortia to meet client needs. Environmental toxicology and chemistry: expertise gained from formal PhD training, and research and consultancy experience over a 20 year period. Environmental risk assessment: expertise gained from consultancy experience over a 20 year period. Computer skills and competences Driving licence MS Word, Excel, Access; Probabilistic modelling with Crystal Ball. Full driving licence for cars and motorbikes.

41 KEY RECENT PROFESSIONAL EXPERIENCE Assessment of REACH strategic issues for Water UK. Use of QSAR and read across for developing Environmental Quality Standards for the European Commission. Support of a tiered approach to evaluate endocrine effects in aquatic organisms for CEFIC. Statistical analysis of fish lifecycle studies for OECD. Development of an alternative sample analysis for FEPA licensing for Defra. Assessment of water quality components of Environmental Statements for various clients Assessment of regulatory testing strategies and methods for characterizing the ecotoxicological hazards of nanomaterials for Defra. Assessment of environmental toxicology laboratory compliance with ISO for the United Kingdom Accreditation Service. Development of alternatives to animal testing for risk assessment to meet the requirements of new chemicals legislation for Defra. Desk based review of current knowledge on pharmaceuticals in drinking water and estimation of potential levels for Defra. Case study to develop tools and methodologies to deliver an ecosystem-based approach PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Additional information PUBLICATIONS Co-editor of 5 books on environmental toxicology and chemistry, >50 reports for clients, and >120 peer-reviewed papers on environmental toxicology and chemistry. The most recent and relevant papers and reports for this project are listed here: 1. Leung KMY, Morritt D, Wheeler JR, Whitehouse P, Sorokin N, Toy R, Holt M, Crane M Can saltwater toxicity be predicted from freshwater data? Marine Pollution Bulletin 42: Crane M, Sorokin N, Wheeler J, Grosso A, Whitehouse P, Morritt D European approaches to coastal and estuarine risk assessment. In, Newman MC, Roberts MH Jr., Hale RH (eds.) Coastal and Estuarine Risk Assessment, Lewis Publishers, Boca Raton, FL. pp Newman MC, Crane M Introduction to time to event methods. In, Risk Assessment with Time to Event Models, edited by Crane M, Chapman P, Fenlon J, Newman M. CRC/Lewis Press, Boca Raton, FL., pp Crane M, Chapman P, Fenlon J, Newman M Risk Assessment with Time to Event Models. CRC/Lewis Press, Boca Raton, FL. 175 pp. 5. Grist EPM, Leung KMY, Wheeler JR, Crane M Better bootstrap estimation of hazardous concentration thresholds to protect biological assemblages. Environmental Toxicology and Chemistry 21: Wheeler JR, Grist EPM, Leung KMY, Morritt D, Crane M Species sensitivity distributions: data and model choice. Marine Pollution Bulletin 45: Wheeler JR, Leung KMY, Morritt D, Whitehouse P, Sorokin N, Toy R, Holt M, Crane M Freshwater to saltwater toxicity extrapolation using species sensitivity distributions. Environmental Toxicology and Chemistry 21: Grist M, Crane M, Jones C, Whitehouse P Estimation of demographic toxicity through the double bootstrap. Water Research 37: Crane M Summary of European Union laws and regulations. In, Newman MC, Ungar M, Fundamentals of Environmental Toxicology, Lewis Publishers, Boca Raton, FL. 10. Crane M Proposed development of sediment environmental quality standards under the European Water Framework Directive: A critique. Toxicology Letters 142/3: Reproduced in Advances in Pharmacology 52: Leung KMY, Ibrahim H, Dewhurst RE, Morley NJ, Crane M, Lewis JW Concentrations of metallothionein-like proteins and heavy metals in the freshwater snail Lymnaea stagnalis exposed to different levels of waterborne cadmium. Bulletin of Environmental Toxicology and Chemistry 71: Grist EPM, O'Hagan A, Crane M, Sorokin N, Sims I, Whitehouse P Bayesian and time-independent species sensitivity distributions for risk assessment of chemicals. Environmental Science and Technology 40: Kwok KWH, Leung KMY, Lui GSG, Chu VKH, Lam PKS, Morritt D, Maltby L, Brock TCM, Van den Brink PJ, Warne M St J, Crane M Comparison of tropical and temperate freshwater animal species acute sensitivities to chemicals: implications for deriving safe extrapolation factor. Integrated Environmental Assessment and Management 3: Crane M, Babut M Environmental Quality Standards for Water Framework Directive Priority Substances: Challenges and Opportunities. Integrated Environmental Assessment and Management 3: Crane M, Kwok KWH, Wells C, Whitehouse P, Lui GCS Use of field data to support European Water Framework Directive quality standards for dissolved metals. Environmental Science & Technology 41:

42 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Europass Curriculum Vitae Personal information First name(s) / Surname(s) William A. Stubblefield, Ph.D Address(es) Texas Street SW, Albany, OR 97321, USA Telephone(s) ( ) Fax(es) ( ) bstubblefield@parametrix.com Nationality USA Date of birth 8 November 1955 Gender Occupational field Male Toxicology Work experience Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector 2002 present Technical Director Responsible for technical direction of environmental toxicology laboratory and consulting staff Parametrix Environmental Research Laboratory (PERL), Texas Street SW, Albany, OR 97321, Consulting 2002 present Courtesy Faculty, Department of Environmental and Molecular Toxicology Teaching and guidance of graduate students Oregon State University, Corvallis, OR Academia Dates Occupation or position held Affiliate Faculty, Department of Environmental Health Main activities and responsibilities Teaching and guidance of graduate students Name and address of employer Colorado State University Type of business or sector Academia

43 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Education and training Title of qualification awarded Principal subjects/occupational skills covered Name and type of organisation providing education and training Title of qualification awarded Principal subjects/occupational skills covered Name and type of organisation providing education and training Title of qualification awarded Dates Affiliate Faculty, Department of Fisheries and Wildlife Biology Teaching and guidance of graduate students Colorado State University Academia Dates Technical Director Responsible for technical direction of environmental toxicology laboratory and consulting staff ENSR Consulting and Engineering Consulting Dates Staff toxicologist Responsible for oversight and conduct of aquatic and wildlife toxicity studies Mobay Corporation; Health, Environment, and Safety Division Industry Dates Student Research assistant University of Wyoming, Fish Physiology and Toxicology Laboratory Academia Dates Staff Toxicologist Responsible for providing support to industry product lines on regulatory and technical concerns Exxon Corporation, Research and Environmental Health Division Industry Dates 1987 Ph.D. Dates 1979 Aquatic Toxicology University of Wyoming M.S. Dates 1977 Toxicology/Toxicodynamics University of Kentucky M.S.

44 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Principal subjects/occupational skills covered Name and type of organisation providing education and training Biological Sciences/Chemistry) Eastern Kentucky University Personal skills and competences Mother tongue(s) Driving licence English Oregon USA Private Vehicle

45 PARAMETRIX/wca environment Aquatic Environmental Risk Assessment of Manganese Additional information Recent Publications Smith C, W Stubblefield, A Fairbrother, H Allen, I Schoeters, and R Dwyer Distribution of soil bioavailability parameters throughout Europe and development of t- BLM based metalloregions. Society of Environmental Toxicology and Chemistry European Annual Meeting. Lille, France. May Phipps T, S Currie, W Stubblefield, C Farr, S Murphy, R Costlow, and M Thompson Aquatic toxicity of mono- and dialkyltin chlorides to freshwater fish, daphnia, and algae. Society of Environmental Toxicology and Chemistry European Annual Meeting. Lille, France. May Phipps T, S Currie, W Stubblefield, C Farr, S Murphy, R Costlow, and M Thompson Aquatic ecotoxicity of mono- and di-organotin stabilizers to freshwater organisms. Society of Environmental Toxicology and Chemistry European Annual Meeting. Lille, France. May Stubblefield W, J Oris, C Smith, and A Maki Relationship of water quality characteristics, solar radiation, and photo-induced toxicity of PAHs in Prince William Sounds (PWS),Alaska. Society of Environmental Toxicology and Chemistry European Annual Meeting. The Hague, Netherlands. May Van Genderen E, W Stubblefield, T Brock, and R Welton Preliminary investigations into the aquatic toxicity of cobalt to freshwater biota. Society of Environmental Toxicology and Chemistry European Annual Meeting. The Hague, Netherlands. May Oris J, A Roberts, W Stubblefield, and A Maki Gene expression in caged juvenile Coho Salmon (Oncorhynchys kisutch) exposed to the waters of Prince William Sound, Alaska (USA). Society of Environmental Toxicology and Chemistry European Annual Meeting. The Hague, Netherlands. May Wirtz, J.R. and W Stubblefield Manganese Water/Sediment/Soil Quality Criteria Database: Review of Existing Data and Recommendations. Society of Environmental Toxicology and Chemistry Annual Meeting. Montreal, Canada. November Smith, C., E Van Genderen, W Stubblefield, T Brock, and R Welton Preliminary investigations into the aquatic toxicity of cobalt to freshwater biota. Society of Environmental Toxicology and Chemistry Annual Meeting. Montreal, Canada. November Stubblefield, W, T Brock, K De Schamphelaere, D Heijerick, C Janssen, E Van Genderen, P Van Sprang, and R Welton Cobalt: Application of an International Approach for Developing Environmental Criteria/Guidelines/Standards for Metals.Society of Environmental Toxicology and Chemistry Annual Meeting. Porto, Portugal. May Van Genderen EJ, W Stubblefield, KA De Schamphelaere, CE Schlekat Validation of nickel Biotic Ligand Model predictions for selected non-standard organisms. Society of Environmental Toxicology and Chemistry Annual Meeting. Milwaukee, WI. November Stubblefield WA, EJ Van Genderen, TR Brock Cobalt: Application of an International Approach for Developing Environmental Criteria/Guidelines/Standards for Metals. Society of Environmental Toxicology and Chemistry Annual Meeting. Milwaukee, WI. November Redman A, J McGrath, W Stubblefield, A Maki, D DiToro Quantifying the concentration of crude oil microdroplets in oil-water preparations. Society of Environmental Toxicology and Chemistry Annual Meeting. Milwaukee, WI. November Stubblefield WA, EJ Van Genderen, CE Schlekat Effects of nickel to marine organisms: Compilation of available data and derivation of a marine PNEC. Society of Environmental Toxicology and Chemistry Annual Meeting. Milwaukee, WI. November 2007.

46 Steve Lofts Curriculum Vitae Centre for Ecology & Hydrology, Lancaster Environment Centre, Library Avenue, Bailrigg, Lancaster, LA1 4AP Tel: Direct line: M. Sc. Pollution and Environmental Control, University of Manchester Ph. D. Chemical speciation in natural environments, University of Lancaster Main current areas of research: Incorporating bioavailability into methods for assessing risks of metals to terrestrial organisms. Conventionally, the risk to organisms due to a toxic chemical is expressed using a 'threshold concentration' (usually termed a quality standard or critical limit) above which there is considered to be a potential risk to the environment. In the past such concentrations have not incorporated any knowledge of how the chemistry of the medium (i.e. the soil or water) influences the toxicity. In conjunction with colleagues David Spurgeon, Claus Svendsen and Ed Tipping, we have developed a method for calculating critical limits that are dependent upon soil chemistry. This method has been done for the metals nickel, copper, zinc, cadmium and lead, and will shortly (2008) be extended to mercury. This work has been carried out for Defra as part of larger projects to calculate critical loads of atmospherically deposited metals for the UK. The methodology has also been adopted to calculate critical loads of cadmium and lead for Europe. Related publications Lofts, S., Spurgeon, D., Svendsen, C. Fractions Affected and Probabilistic Risk Assessment of Cu, Zn, Cd and Pb in Soils Using the Free Ion Approach. Environmental Science & Technology, 39(21), (2005). Lofts, S., Spurgeon, D., Svendsen, C., Tipping, E. Deriving Soil Critical Limits for Cu, Zn, Cd, and Pb: A Method Based on Free Ion Concentrations. Environmental Science & Technology, 38(13), (2004).

47 Refining and testing models of chemical speciation. The Windermere Humic Aqueous Model (WHAM) is the main model developed and used by my research group to model chemical speciation in waters. The model simulates acid-base chemistry and metal binding equilibria of natural organic matter and mineral oxides of iron, aluminium, manganese and silicon. I am currently involved in work to update the parameterisation of the submodel for organic matter, using the latest available data from the literature. The model will then be updated to allow uncertainty in its predictions to be quantified, and will be tested against available literature field data. This work will be highly significant in advancing understanding of surface water chemistry and will be of great importance for the many users of WHAM worldwide. Behaviour of manufactured nanoparticles in surface waters. I will be assessing how manufactured titanium oxide nanoparticles partition between solution and suspended matter in a variety of UK waters, including estuaries. This work will contribute to performing better risk assessments of the ecological risks due to nanoparticles in freshwaters. Other recent publications Ermakov, I.V., Koptsik, S.V., Koptsik, G.N., Lofts, S. Transport and accumulation of heavy metals in undisturbed soil columns. Global NEST Journal, 9(3), (2007). Lofts, S., Chapman, P.M., Dwyer, R., McLaughlin, M.J., Schoeters, I., Sheppard, S.C., and 33 others. Critical Loads of Metals and Other Trace Elements to Terrestrial Environments. Environmental Science & Technology, 41(18), (2007). Pampura, T., Groenenberg, J. E., Lofts, S., Priputina, I. Validation of Transfer Functions Predicting Cd and Pb Free Metal Ion Activity in Soil Solution as a Function of Soil Characteristics and Reactive Metal Content. Water, Air & Soil Pollution, 184(1 4), (2007). de Vries, W., Lofts, S., Tipping, E., Meili, M., Groenenberg, J. E., Schütze, G. Impact of Soil Properties on Critical Concentrations of Cadmium, Lead, Copper, Zinc, and Mercury n Soil and Soil Solution in View of Ecotoxicological Effects. Reviews of Environmental Contamination and Toxicology, 191, (2007). Lofts, S. Predicting cadmium adsorption on soils using WHAM VI. Chemosphere, 69(4), (2007)..Ålmas, A. R., Lofts, S., Mulder, J., and Tipping, E., Solubility of major cations and Cu, Zn and Cd in soil extracts of some contaminated agricultural soils near a zinc smelter in Norway: modelling with a multisurface extension of WHAM. European Journal of Soil Science, 58(5), (2007).

48 Tipping, E., Lawlor, A.J., Lofts, S. Simulating the long-term chemistry of an upland UK catchment: Major solutes. Environmental Pollution, 141(1), (2006). Tipping, E., Lawlor, A.J., Lofts, S., Shotbolt, L. Simulating the long-term chemistry of an upland UK catchment: Heavy metals. Environmental Pollution, 141(1), (2006). Hall, J. R., Ashmore, M., Fawehinmi, J., Jordan, C., Lofts, S., Shotbolt, L., Spurgeon, D. J., Svendsen, C., Tipping, E. Developing a critical load approach for national risk assessments of atmospheric metal deposition. Environmental Toxicology & Chemistry, 25(3), (2006). Spurgeon, D.J., Lofts, S., Hankard, P.K., Toal, M., McLellan, D., Fishwick, S., Svendsen, C. Effect of ph on metal speciation and resulting metal uptake and toxicity for earthworms. Environmental Toxicology & Chemistry, 25(7):

49 Europass Curriculum Vitae Personal information First name(s) / Surname(s) Robert W. Gensemer, Ph.D. Address(es) Texas Street SW, Albany, OR 97321, USA Telephone(s) ( ) Fax(es) ( ) bgensemer@parametrix.com Nationality American Date of birth 05 June 1960 Gender Occupational field Male Aquatic Toxicology, Ecological Risk Assessment Work experience Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector Dates Occupation or position held Main activities and responsibilities Name and address of employer Type of business or sector 2002 present Senior Toxicologist and Toxicology Division Manager Toxicology Research Scientist, Consultant, Administrative Manager Parametrix Environmental Research Laboratory (PERL), Texas Street SW, Albany, OR 97321, USA Ecotoxicology, Ecological Risk Assessment 2007 present Affiliate Faculty, Department of Fisheries and Wildlife Teaching/Instruction Oregon State University, Corvallis, OR University Dates 2002 Occupation or position held Assistant Department Manager Main activities and responsibilities Administration, Management Name and address of employer ENSR International, Fort Collins, CO Type of business or sector Environmental Toxicology Laboratory