working group on marine sediments in relation to pollution

ICES Marine Habitat Committee ICES CM 2004/E:02 Ref. ACME

Report of the Working Group on Marine Sediments in Relation to Pollution (WGMS)

1–5 March 2004 Stockholm, Sweden

This report is not to be quoted without prior consultation with the General Secretary. The document is a report of an Expert Group under the auspices of the International Council for the Exploration of the Sea and does not necessarily represent the views of the Council.

International Council for the Exploration of the Sea

Conseil International pour l’Exploration de la Mer

Palægade 2–4 DK–1261 Copenhagen K Denmark Telephone + 45 33 15 42 25 · Telefax +45 33 93 42 15

www.ices.dk · [email protected]

Contents

1 Opening of the meeting .............................................................................................................................................. 5 2 Adoption of the agenda .............................................................................................................................................. 5 3 (Bio)availability of contaminants in sediments .......................................................................................................... 6 4 Sediment dynamics in monitoring.............................................................................................................................. 7 5 Development of indicators of sediment contamination .............................................................................................. 8 6 Collaboration with WGBEC ...................................................................................................................................... 9 7 Use of SPM in monitoring programmes................................................................................................................... 10 8 Workshop on Integrated Chemical and Biological Effect Monitoring..................................................................... 13 9 Support REGNS ....................................................................................................................................................... 15 10 Collaboration with WGSAEM ................................................................................................................................. 16 11 Any other business ................................................................................................................................................... 17

11.1 Sednet progress ............................................................................................................................................. 17 11.2 Review the outcome of the 2004 OSPAR/ICES Workshop in The Hague on BCs and EACs in relation to

contaminants in sediments ............................................................................................................................ 18 11.3 Review of BDC documents........................................................................................................................... 18

12 Background concentrations ...................................................................................................................................... 19 12.1 Background values for metals in sediments.................................................................................................. 19 12.2 Background values for PAHs sediments....................................................................................................... 22

13 Election of a new Chair ............................................................................................................................................ 23 14 Recommendations and action list............................................................................................................................. 24 15 Date and venue of the next meeting ......................................................................................................................... 24 16 Closure of the meeting ............................................................................................................................................. 24

Annex 1 Agenda of the 2004 WGMS meeting in Stockholm .......................................................................... 25 Annex 2 Terms of Reference for the 2004 WGMS meeting ............................................................................ 26 Annex 4 DGT Passive sampling of metal ions in water by DGT-technology.................................................. 30 Annex 5 Joint research of The Netherlands and Belgium on (bio)availablity.................................................. 33 Annex 6 Development of indicators for sediment contamination .................................................................... 42 Annex 7 SPM monitoring in the Netherlands .................................................................................................. 51 Annex 8 OSPAR/MON working schedule....................................................................................................... 64 Annex 9 Data description and evaluation for BCs of metals............................................................................ 66 Annex 10 Grafical Overview of data used to estimate BCs for PAHs ............................................................... 79 Annex 11 Recommendations.............................................................................................................................. 85 Annex 12 Action list .......................................................................................................................................... 86 Annex 13 Draft resolutions ................................................................................................................................ 87

ICES WGMS Report 2004 3

1 OPENING OF THE MEETING

The 2004 meeting of the Working Group on Marine Sediments in Relation to Pollution (WGMS) started on 1 March 2004. Thirteen members were present representing eleven countries.

Per Jonsson from the Swedish Environmental Protection Agency welcomed the Working Group to Stockholm and introduced Dr Sverker Evans, who gave an opening speech. He addressed the importance of the work of the group and mentioned that WGMS could also play a role in the adjustment and implementation of Water Framework Directive for sediments. He welcomed the group to the Swedish Environmental Protection Agency and wished them a pleasant and productive meeting.

Further information on logistics arrangements and the social programme for the meeting were given by Per Jonsson. On Tuesday afternoon the group went on a guided tour at the Wasa Museum, Beckholmen. The social tour was concluded by a dinner sponsored by the Swedish EPA in Gamla Stan.

2 ADOPTION OF THE AGENDA

After the opening of the meeting the group went briefly through the agenda items to identify the priority, workload, and actions required. In addition, an inventory was made of presentations by the participants. A major point added to the agenda was the establishment of Background Concentrations of metals and PAH in sediments. Under Agenda Item 12, Any Other Business, the Chair provisionally included a discussion on the work of the OSPAR/ICES Workshop on evaluation of BRC-EAC values in The Hague (8–13 February 2004). However it appeared that much work was needed additional to what was done at the workshop. It was the recommendation of the workshop that WGMS would evaluate the data collected at the workshop and define BC values from that BC values for sediment:

“the ICES Working Group on Marine Sediments in Relation to Pollution (WGMS) and Working Group on Statistical Aspects of Environmental Monitoring (WGSAEM) (1–5 March 2004) should be invited to work in collaboration, to carry out a further scrutiny of the BC data set and to construct draft background concentrations and background assessment concentrations for metals and PAHs in sediments”.

This resulted in a formal request from OSPAR to ICES and, consequently, this was taken up by the group. Some participants felt they were not sufficiently prepared to perform this task but, considering the importance, the group decided to do whatever was possible. The task was added as Agenda Item 12.

Furthermore, ICES requested WGMS to review a set of documents from the OSPAR Biodiversity Committee. This was added as Agenda Item 11.3.

Rapporteurs were appointed for the different agenda items and the sections of the summary record were collected and combined by the Chair. On Friday, the summary record, based on the notes of the Rapporteurs and the produced annexes, was discussed as far as possible. Final comments were processed by written procedure.

The final agenda is attached as Annex 1 and the Terms of Reference as Annex 2. The participants and their contact details are listed in Annex 3.

Presentations

Participant Agenda item

Title

Kristoffer Naes 3 DGT use in Norway

Foppe Smedes, Partick Roose

3 Measuring availability of hydrophobic contaminants in sediments of the Western Scheldt using SPS

Ruth Parker, Linda Tyrell

5 Brief feedback on general issues concerning indicators and developments of indicators in the European Environmental Agency

Per Jonsson 5 Fraction anoxity of an area as an indicator for eutrophication

Maria Jesus Belzunce 5 A proposal for the use of benthos in ecological quality objectives: the development of a Marine Biotic Index

Birgit Schubert 7 Monitoring of contaminants in SPM collected by sedimentation traps in estuaries


Participant Agenda item

Title

Jean-Louis Gozalez 7 Metals in SPM collected in Gironde and Seine estuary

Kristoffer Naes 7 SPM contents in Skagerrak increases as result of climate change?

Patrick Roose 7 PAH in SPM from Scheldt Estuary

Foppe Smedes 7 Contaminants in suspended matter in marine areas of the Netherlands; overview of 15 years of monitoring

3 (BIO)AVAILABILITY OF CONTAMINANTS IN SEDIMENTS (TOR A)

Measurement of the potential (bio)availability of contaminants in sediment; evaluate the work in the Western Scheldt intersessionally done by Belgium and the Netherlands. Report on the use of DGT in estimating availability of metals in sediments.

Use of DGT Kristoffer Næs gave a presentation on the use of the passive sampler DGT (Diffusive Gradients in Thin films) for determination of metal ions in water. The DGT technique depends on the diffusion of labile ions through a gel whereafter they are bound by a Chelex absorbent (attached as Annex 4). It can be used for sampling dissolved metals in the water mass (in a form of a small disk) or for sampling metals in the pore waters of sediments (by inserting a DGT probe into the sediments). Application area and limitations are listed in the table below.

The DGT technique was developed by William Davison and Hao Zhang at Lancaster University, UK, and first published in Nature 1994. By end of 2002, there were about 50 publications in the literature on the use of DGTs.

Some metals are not absorbed by the sampler. However, the DGT sampler with Chelex absorbent collects about 30 metal ions in water at pHs from 4.7–6. Measured diffusion coefficients in the gel are close to those for ions in water. Diffusion gel resistance is about 10–15%. There is a good sensitivity, with LODs (depending on the detection technique used) in the range 0.001–1 ppb (µg/L) at exposure times as short as 24 h and a sampling precision of 10–20% (which is comparable to some other methods).

As the technique measures the freely diffusing metals, probably therefore the dissolved ions, the method may be used to assess the actual bio-available fraction of these metals in seawater or pore water. The DGT sampler may therefore provide a new tool for assessment of reactive metal ions in water and be particularly relevant for integrated use with biological effects measurements.

The technique functions under a range of environmental conditions:

Environmental factor Possible problem?

pH No (4.5–9 is OK - Covers most waters)

Salinity No (10–4M – 1M, i.e., from freshwater to full seawater)

Turbulence No (No DBL at flow > 0.1 m/sec)

Pressure No (D independent of P < 100 atm)

Temperature Yes (2.5% per ºC correction)

Biofouling Yes (problem at long deployment times)

Diffusive boundary layer (DBL) Yes (DBL estimation a problem at low flow velocity < 0.01 m/sec)

Availability of hydrophobic contaminants in sediment Foppe Smedes gave an overview on the theory and practice of the use of solid phase samplers (SPS) in the investigation of availability of hydrophobic contaminants from sediments. In addition the results of a Belgian/Dutch survey in the Scheldt that applied SPS were presented (paper attached as Annex 5). The principle behind the use of SPS is the equilibrium between the reference phase and the aqueous environment.


For the experiment SPS made from silicon rubber were shaken with sediment and water and allowed to equilibrate. Different SPS to sediment ratios were used, to allow calculation of the concentration in the water phase and the maximum amount of contaminant that can be extracted from the sediment through the water phase. The latter can be compared to total sediment concentrations as obtained from Soxhlet extraction. Unfortunately, these results were not available as yet. From previous experiments, it was shown that approximately 50% of the PAHs in sediment were available for extraction with the SPS, whereas 100% of the PCBs were released. For PAHs this means that part of the contaminants cannot be extracted through the water phase and are therefore unlikely to be available for organisms.

Previous experiments showed that the method has a good reproducibility (10–20%), is rather robust, universally applicable, and allows determining several contaminants simultaneously. The drawbacks are that it is labour intensive and that equilibrium times are long (too long for Kow > 7.5).

In this survey, sediment samples were shaken for two weeks at different SPS:sediment ratios and some of the samples were even shaken for several months. The results of the study are promising. Some of the deviating results could be explained by both analytical problems and insufficient equilibrium times. Amongst other results, a clear gradient for both PAHs and PCBs was shown in the Scheldt. The gradient is very similar to the one found in sediments when normalised by sieving and/or OC.

During the discussion, Foppe Smedes confirmed that no special consideration was given to whether the sediments were reduced or not. Only surface sediments were used and the experiment took place in closed bottles. Also, the redox potential of the sediment is unlikely to change the outcome.

For the survey 0.5 mm silicone sheets were used, but for future experiments a new methodology using of bottles coated with 30 µm silicone rubber is under development. This will result in faster equilibrium or/and extend the Kow range.

It was deemed that it is a promising method to determine the “hottest” area, i.e., the most contaminated sites in an area or region in terms of availability.

Considering the way forward the method should prove to be a very useful tool for monitoring the fraction of contaminants available for extraction to the water phase. This could be of particular importance to food web studies. Linked to this, it could also be used to expose small organisms to sheets containing known concentrations of contaminants, providing a constant and easily calculated concentration in the water phase.

The method can potentially be used as a sort of universal “thermometer” measuring the pollution level in sediments. Such a goal would require only one measurement.

There is a lot of support and enthusiasm in the group to carry this work forward. Currently the RIKZ is in a reorganisation process and the situation is such that funding for further work is limited and insufficient to rapidly develop the method further for routine application. A collective effort or project involving several parties around the table seems the way forward. WGMS members agreed to inquire in their home institutes about the possibilities of participating/contributing in such a collaborative effort with corresponding funding. They are to report back to Foppe Smedes by 15 April 2004. Following this, the next step in this collaboration and intersessional work will be considered.

4 SEDIMENT DYNAMICS IN MONITORING (TOR B)

Finalize Annex to the sediment monitoring guidelines, Guidance on the interpretation of trend monitoring data, taking into account sediment dynamics.

The Working Group was asked by ICES to finalize the work on an annex to the sediment monitoring guidelines that provides guidance on the interpretation of sediment trend monitoring data, taking into account sediment dynamics. A sub-group consisting of Maria Jesus Belzunce, Ruth Parker, Birgit Schubert, Jean Louis Gonzalez and Per Jonsson discussed the progress since the last WGMS meeting. The sub-group considered two papers presented by Maria Jesus Belzunce, one on water dynamics and one on sediment characteristics of the Cantabrian Sea. It was agreed that they provide a good basis for a chapter to be included in the Annex on sediment dynamics, though it was still necessary to reshape this document before it may be included. Furthermore, Birgit Schubert volunteered to be the coordinator for a chapter on sediment dynamics in estuaries to be written by Birgit Schubert, Carla Palma, Ruth Parker, Jean Louis Gonzalez, and Jesus Maria Belzunce. Other contributions are also warmly welcomed.

Taking into consideration that there has been no comments on the draft document since the 2003 WGMS meeting, the working group agreed that the chapters on the offshore North Sea and the offshore Baltic Sea should be considered


finalised for now. Concerning the chapter on estuaries it was decided that it would be finalised intersessionally with the aim to present it to the 2004 ACME meeting. Agreement on this would then follow a written procedure. ACME can then review the outcome and decide on whether the entire paper on sediment dynamics can be added as an Annex to the sediment guidelines or not.

5 DEVELOPMENT OF INDICATORS OF SEDIMENT CONTAMINATION (TOR C)

Development of practical indicators for sediment quality is of paramount importance to display the results of environmental assessments to the general public. The group should continue to develop such indicators and, where possible, demonstrate and evaluate some presently applied procedures.

Development of practical indicators of sediment contamination is important in communicating the results from environmental assessments to the general public. It is also important in terms of describing contaminant levels in sediments in terms so that temporal trends in monitoring information are capable of showing/indicating improvement, which can be linked to a management response. Although WGMS represents a good medium for developing and discussing such indicators, over the past year there has been little advance in the development of indicators of this type within the wider European scientific community, which would allow further assessment of techniques.

Brief presentations were made by Ruth Parker and Linda Tyrrell on indicator issues in general, the development of indicators within the European Environment Agency (EEA) and how these guidelines have been applied by the UK to develop indicators of seabed disturbance (disposal of dredge material, aggregate extraction, fisheries and near-shore disturbance) with examples relevant to sediment contamination. A summary of these findings is presented in Annex 6. In addition, examples of indicator development relevant to eutrophication in the Baltic and development of a Marine Biotic Index (AMBI) were presented by Per Jonsson and Maria Belzunce, respectively.

Per Jonsson presented a model for monitoring the eutrophication status by counting both the down–core and surface distribution of laminated sediments in cores taken in a gradient from shallow to deeper water. This method has been applied in the Baltic particularly in the archipelago of Stockholm.

Maria Belzunce presented a biological index method based on 2,700 bottom fauna species. The species were grouped in five groups (sensitive, indifferent, tolerant, opportunistic, and very opportunistic organisms). Based on the relative distribution between these groups the sediment environment could be divided into four classes related to the environmental status (normal, unbalanced, polluted, and very polluted). As is the case with the toxicity tests, the biotic index method cannot easily be related to the contamination level of the sediment as other natural factors can be unfavourable to the organisms.

A summary of these two reports appears in Annex 6.

The Working Group discussed and evaluated the present knowledge of indicators of sediment contamination. At present, there is no simple indicator that allows a judgement of the quality of the environment or the sediment status. Up to now, these conditions are in general drawn from concentration data of various elements and organic micropollutants, e.g., heavy metals, PAHs, PCBs and pesticides, or from toxicity tests of the sediment. This means an extensive and time-consuming amount of work in laboratories. The use of concentration data is limited to the number of elements and substances that can be analysed for different reasons.

At present, the following methods are used to state the quality of the sediment:

1) National sediment quality criteria (SQCs) based on concentration data of sediment. This method requires analyses of one or several of the elements or substances that have been given criteria.

2) Enrichment factors based on the ratio between surface sediment concentration and the local background concentration. However, these can only be applied for stable elements.

3) Toxicity-test on selected organisms or embryos. The problem with the toxicity tests are that the results can not in a simple way be related to the contaminants of the sediment as other natural factors can be unfavourable to the organisms.

The criteria (for an example see ICES(2003)) above can be used as interim indicators in their own right and are reported at present as part of many monitoring programmes. For each method, collation of data is a considerable task but under monitoring programmes some element of trend analysis should be possible.


It was thought that an overall aim would be to try and distil many concentrations or values derived from the methods above into an overall assessment of sediment contamination. However, although this could be done using absolute contaminant concentrations, it would be a very difficult exercise to come up with scores that were meaningful in terms of all contaminants, geographical areas and without introducing bias into the end indicator. It is not possible to simply sum contaminant concentrations as each compound has different risk levels in relation to biology. A method (similar to enrichment factors) which compares a measured concentration to a set of quality criteria (e.g., Background Concentrations (BCs)) and then sums the differences into one indicator value can lead to bias in terms of presence/absence of data for a given contaminant. Also, the overall score can change depending on the ratio of contaminant levels which are above or below the assessment concentration. This approach would be difficult from a toxicological point of view. The WG concluded that despite this desired objective, at present there is no single measurement that can be used as an indicator of sediment contamination.

It was thought that an index, not of what is in the sediment, but of what biological organisms would see in terms of impact (bioavailability) would perhaps be more useful. In this way an indicator which links sediment contamination to bioavailability and biological effects would be more novel and more powerful. To some extent this is already reported within the Sediment Quality Criteria (SQCs) (for full discussion of SQCs see ICES(2003)) and this reporting mechanism could be used until something more directly linked to biological effects can be developed.

Monitoring data of total sediment concentrations of contaminants can be used as preliminary indicators in comparison to BCs and EACs (Ecotoxicological/Environmental Assessment Criteria) and in association with SQCs. Together, these sediment contamination criteria and assessment concentrations can provide a suite of indicators of sediment contamination and potential impact.

Development of an integrated indicator of sediment contamination in terms of concentration and biological impact is still some way off but some novel ideas such as approaches which utilise contaminant fugacity (a reference phase type approach) or scoring in terms of dioxin toxicity equivalents or endocrine disrupter potency were discussed. The application of solid phase passive samplers such as the silicone rubber technique presented by Foppe Smedes and DGTs was also mentioned (Agenda Item 3). It was decided that if the development of sediment contamination indicators has not come much further in a year and until significant progress is made in terms of bioavailability and toxicity, discussion of this agenda item should be continued within WGMS when sufficient information becomes available.

An ICES Symposium on marine environmental indicators (Marine Environmental Indicators: Utility in Meeting Regulatory Needs) is scheduled for 2007 and will involve assessment of indicators under both OSPAR and EU initiatives. This will provide an opportunity to revisit this subject and input to this symposium by WGMS will be considered at a future meeting.

References

ICES. 2003. Inventory of sediment quality criteria and how they derived. In Report of the Working Group on Marine Sediments in Relation to Pollution. ICES CM 2003/E:4: 18-47.

6 COLLABORATION WITH WGBEC (TOR D)

Further investigate the possibilities of integrated chemical and biological effect monitoring and evaluate where the knowledge on chemical sediment monitoring can contribute to application and interpretation of biological effects monitoring (with WGBEC). Especially biological effects monitoring techniques that include sample preparation, extraction and separations may benefit from evaluation by WGMS.

In 2003 two relevant members of WGMS joined the WGBEC meeting for two days. The work that WGMS had done in the week before on (bio)availability, mostly related to biological effect matters, was presented to the group. Due to a heavily loaded agenda of the WGBEC it was not possible to discuss and investigate how that could lead to collaborative work. Another subject to which WGMS could contribute was Toxicity Identification Evaluation (TIE). However, for the same reasons as above it also had not been possible to schedule the TIE work in the period during which the two WGMS representatives were present.

To carry on with the work, it was decided that WGMS would try to evaluate BEC procedures and try to identify matters where the knowledge within WGMS could be useful. Under this agenda item, it was intended to further investigate the possibilities of integrated chemical and biological effect monitoring and evaluate where the knowledge on chemical sediment monitoring can contribute to application and interpretation of biological effects monitoring (with WGBEC).


Communicating with the Chair of the WGBEC indicated several issues for discussion:

• (bio)availability through passive samplers or organisms;

• extraction techniques for screening assays (organic extraction, porewater);

• Practical considerations: effects of freezing/thawing sediment, homogenisation, redox-changes (time scales).

The ideas of WGMS to evaluate some existing procedures, which include such issues, could not be carried out for two reasons. Identifying these procedures and getting them to the working group meeting was not feasible within the available time frame. Secondly, the extra work on BCs under Agenda Item 12 would not have allowed the necessary time for the subject to receive the attention it would need.

Furthermore, these are typically issues to be discussed at the Workshop on Integrated Monitoring of Contaminants and their Effects in Coastal and Open-Sea Areas (WKIMON) to be held in January 2005. Most likely there will be more time then.

7 USE OF SPM IN MONITORING PROGRAMMES (TOR E)

Investigate and report on the possibilities and present use of suspended matter as a matrix for monitoring programmes.

In 2003, WGMS agreed to investigate the current and possible use of suspended particulate matter (SPM) in monitoring programmes. Accordingly, several presentations on the use of suspended particulate matter were given at the present meeting.

Jean-Louis Gonzalez presented two examples of the use of SPM 1. Within IFREMER, suspended matter is collected "outside" monitoring programme, for mass balance and flux calculations (mainly in estuaries), and for the investigation of geochemical processes controlling the behaviour of contaminants in coastal waters. The principal conclusions of two papers were presented, as examples of the possible uses of trace metal concentrations in SPM, (Boutier et al., 2000; Chiffoleau et al., 2001), together with some results obtained in the estuaries of the Gironde (BIOMET cruises results provided by B. Boutier) and the Seine (Cossa et al., 1994).

The Gironde results (Boutier et al., 2000) show that particulate cadmium concentrations on the continental shelf (Bay of Biscay) are quite variable (0.5 and 4.5 µg/g), although some very high results (> 3 µg/g) should be regarded with caution, because they were obtained from very low amounts of SPM (which are difficult to weigh accurately). The lowest particulate Cd concentrations are associated with low chlorophyll a concentrations. These results are confirmed by two cruises (BIOMET, B. Boutier personal communication) carried out in winter and spring 1998.

In the Seine estuary (Chiffoleau et al., 2001), changes in Cd concentrations in mussels living at the mouth of the estuary are related to changes in inputs to this area of phosphogypsum (a calcium sulphate that is a by-product of the phosphate fertilizer industry, that is naturally enriched with Cd). The monitoring of Cd concentrations in SPM as well as in the dissolved phase at several key estuary sites shows a very marked trend toward decreased contamination.

Another example in the Seine estuary (Cossa et al., 1994), indicates that high temporal variations of Cd in SPM at the upper limit of the Seine estuary (28 months monitoring) are not explained by the variations in runoff, SPM concentrations, Al, POC or Fe concentrations in particles.

1 References

Boutier, B., Chiffoleau, J.-F., Gonzalez, J-L., Lazure, P., Auger, D., and Truquet, I. 2000. Influence of the Gironde estuary outputs on cadmium concentrations in the coastal waters: consequences on the Marennes-Oléron bay (France). Oceanologica Acta, 23(7): 745–757.

Chiffoleau J.-F., Auger, D., Chartier, E., Michel, P., Truquet, I., Ficht, A., Gonzalez, J.-L., and Romana, L.-A. 2001. Spatiotemporal Changes in Cadmium Contamination in the Seine Estuary (France). Estuaries, 24(6B): 1029–1040.

Cossa, D., M. Meybeck, Z. Idlafkih, and B. Bombled (1994). Etude pilote des apports en contaminants par la Seine. Rapport IFREMER, DEL 94–13. Nantes.

Gonzalez, J.L., Thouvenin B., Dange C., Fiandrino A., and Chiffoleau, J.F. 2001. Modeling of Cd speciation and dynamics in the Seine estuary (France). Estuaries, 24(6B): 1041–1055.


In conclusion, these results illustrate that the potential use of SPM for the monitoring of contamination in macrotidal estuaries is limited because of the natural variability of concentrations not related to changes in inputs of contaminants. This variability arises from changes in the nature of particles (primary production in spring for example), and it is not always possible to use "normalisation parameters" (Al for example) to satisfactorily reduce the variance for spatial or temporal trend analysis.

Moreover, collection (by filtration) and analysis of SPM is not easy, is time-consuming, and the very low amounts of SPM (in the outer parts of estuarine plumes for example) can induce misleading interpretation of results.

Kristoffer Næs presented information from a newly-released report that compiles the results from twelve years of monitoring data on the water quality along the southern coastline of Norway. The report was commissioned by the Norwegian Pollution Control Authority (SFT) and drawn up by the Norwegian Institute for Water Research (Norsk Institutt for Vannforskning – NIVA) and the Norwegian Institute of Marine Research (Havforskningsinstituttet). The results show that the amount of particulate matter in the waters of the Skagerrak has increased strongly over the last five to ten years. The increase in particles in the seawater is a result of mild winters, which have created conditions for increased transport of water-borne particles from the Continent to the coast of southern Norway, and also on-shore interventions that have increased the run-off from Norwegian rivers. The change in particulate transport and flux must be considered when interpreting trends in sediment contamination.

Patrick Roose presented results for PAHs in suspended matter from the Scheldt estuary. These concentrations had been monitored on a monthly basis for one year. Sampling was performed one hour after high tide with an Alfa Laval AS16 flow-through centrifuge mounted in a mobile unit. Median PAH concentrations in SPM varied between 30 and 580 µg/kg dry weight (DW) with the highest concentrations for medium condensed PAHs. Fluoranthene was the most prominent PAH, closely followed by pyrene. Measured PAH concentrations in whole water samples were clearly associated with the SPM content and more specifically with the particulate organic carbon content in the water phase.

The ratios of phenanthrene to anthracene (P/A), fluoranthene to pyrene (Fl/Py), methylphenanthrenes to phenanthrene (MP/P) were used to distinguish between pyrolytic and petrogenic sources of PAH. The samples taken during the winter period of 2000 seem to be of a pyrolytic origin whereas the samples taken in 2001 were not purely of a pyrolytic origin. A Principal Components and Classification Analysis (PCCA) was executed to study the patterns. Two factors were identified contributing to 56 % and 32% of the total variance, respectively. These factors separated the PAHs roughly into two groups consisting mostly of the lower MW PAHs on the one hand and the high MW PAHs on the other hand. A particular sample, taken on 13 November, had a considerably different pattern. This event could be linked to a period of heavy rainfall and therefore increased terrestrial run-off (source KMI). The occasion in November with heavy rainfall and therefore increased discharges definitely had a large influence on the levels of the PAHs in the suspended matter. The input of PAH-contaminated water from inland sources may have significantly increased during that period because of increased runoff and excess rain and sewage water bypassing wastewater treatment plants.

PAH patterns in the SPM were compared with those in sediments. Although the concentrations in the SPM were generally higher, the pattern was reflected in the sediment. Three of the selected PAHs (acenaphthene, acenaphthylene, and fluorene) behaved conservatively in the estuary, showing decreasing concentrations with increasing salinity.

Foppe Smedes showed results of monitoring contaminants and the co-factors OC and Al in SPM. Starting from 1988, suspended matter was collected four times per year at about eight locations in the marine area of the Netherlands. The samples were taken using a flow-through centrifuge. Detailed results are attached as Annex 7. In general, samples from locations with the highest SPM contents have the lowest OC contents and at the same time show small variability, as the SPM is dominated by material originating from bottom sediments. In contrast, OC contents in the SPM collected at open sea (NZ 10) show a very high variability. The small amounts of SPM of mineral origin are dominated by algal material, especially in quiet weather conditions. Accordingly, the highest OC contents, up to 35%, were observed in summer, and the OC content in winter samples was more constant. As a result of algal production, the Al contents in SPM decreased considerably at the open sea sampling site NZ 10 (c.f., Annex 7, Figure 4). In the Ems-Dollard (ED), the contaminants presented (Cd, Hg, Pb, CB153) seem to show a downward trend, except for PAHs (Annex 7, Figures 5–10). In more dynamic areas as the open sea (NZ 10), contaminant contents vary strongly, and no obvious trend could be observed. The time-series for TBT was shorter. The results fit well with those for other contaminants (Annex 7, Figure 11).

Seasonal variations of CB153 and OC contents demonstrate that contaminant concentrations are significantly influenced by organic matter from algal blooms (Annex 7, Figure 12). The OC content is much more constant in winter samples compared to SPM collected in warmer periods. Algal blooms result in an increase of organic matter in the SPM. No dilution of CB153 due to the increased SPM content was observed, confirming an uptake of CB153 from the water phase by organic matter from algae. In contrast, CB153 contents increased slightly, but the CB153 content in the water


phase was not sufficient to achieve the CB153/OC ratios as observed in winter samples. Consequently, CB153 contents based on the OC content of wintertime decrease considerably in summertime (Annex 7, Figure 12, open circles).

Foppe Smedes concluded that algal blooms have an adverse effect on the use of SPM for monitoring purposes, but this may be avoided by using winter samples. However, the summer results do reflect the actual contamination levels of the water phase demonstrating how rapidly SPM responds to changes in the system. The advantage of SPM measurements over those in water phase, is that contaminant concentrations in SPM are much higher and consequently can be more accurately measured.

Birgit Schubert presented the use of SPM in a monitoring programme in North Sea Estuaries. At four of the sampling sites, SPM was sampled with sedimentation traps collecting samples over a time span of 2 and 4 weeks, respectively, and analysed for trace metals, organic contaminants and TBT. She described a comparison of trace metal concentrations in the fine-grained fraction < 20 µm of SPM and sediments sampled at two neighbouring locations in the Elbe Estuary since 1999. In this area, sediments and SPM are exchanged intensively, mainly due to tidal currents. Accordingly, comparable trace metal concentrations were observed in SPM and sediments, demonstrating that SPM may be used as an alternative to sediments for monitoring.

As an example for temporal monitoring, trace metal concentrations in SPM sampled in the mixing zone of fluvial and marine sediments in the Elbe Estuary (km 642) since 1980 were presented. Data showed a large variability due to differences in river discharge resulting in SPM with varying ratios of high contaminated fluvial particulate matter and less contaminated marine solids. It was pointed out that sampling of sediments or SPM in the mixing zone of estuaries requires a higher sampling frequency compared to sampling sites downstream of this zone. In 1988, the sampling frequency was changed from 4 samples/y to 12 samples/y and 24 samples/y since 1993. Despite the large variability, a significant decrease in the concentrations of most trace metals could be observed. From the mid-1980s until today, the concentrations of Hg, for example, have decreased by a factor of about 5, of Cd by a factor of about 2, and of Pb by a factor of about 1.5. Accordingly, the input of trace metals to the estuaries (Working Committee of the Elbe) decreased by a factor of 2.5 (Cd), 20 (Hg) and 2 (Pb). For organic contaminants, the decrease of concentrations in SPM samples at the same sample location is less significant, and still has to be verified by statistical trend analysis.

Discussion Three techniques for sampling SPM were applied in the studies presented above:

• filtration; • flow-through centrifugation; • sedimentation traps.

Depending on the technique used and the variability of contamination at the sampling site, a higher sampling frequency may be required for SPM than for deposited sediment sampling. Generally, sampling of SPM should not be carried out close to the bottom sediment surface, in order to avoid sampling freshly eroded sediments.

Some characteristics of the different sampling techniques are summarised below.

When applying filtration and centrifugation techniques, SPM is collected within a short time period, and therefore the samples are sensitive to short-term variations, or positively spoken rapidly show the variations. These techniques, especially filtration, require high concentrations of SPM. Generally, only fine-grained SPM is collected, and no sieving is required prior to analysis. A high sampling frequency is required for trend monitoring. Both techniques collect fine mineral materials as well as degraded organic matter and fresh algae from recent blooms. Therefore, for (trend) monitoring purposes, sampling should be restricted to winter.

Sedimentation traps usually are operated for time periods of several days up to several months, and are therefore much less sensitive to short-term events. However, the SPM collected with traps still responds more quickly than deposited sediments to changes in contamination. As the grain size distribution of SPM from traps can vary greatly, a fine-grained fraction should be separated for analysis of contaminants. SPM sampled with traps may be less affected by algal blooms than SPM from centrifugation or filtration. Owing to long sampling periods in traps, it was suggested that degradation of organic matter may occur. It was reported that stabilising agents, such as chloroform or nitric acid, could be added to the sampling device prior to deployment. Because of the negative impact on the environment and the risk for staff performing the sampling, there was not much support for such measures. Sampling frequencies depend on the characteristics of the sampling locations and on the purpose of the studies. For example, one or two samples per year may be sufficient for trend monitoring of contaminant contents in SPM in the outer estuaries. However, sampling sites with a high variability of contaminant concentrations require more frequent sampling. Generally, sedimentation traps


can be applied in areas with low SPM concentrations. However, in areas with strong currents and gales, effective monitoring using sedimentation traps may be difficult or even impossible.

Generally, SPM represents the mobile particulate matter with the currently available contamination level. In discussion, the potential of the use of SPM for the following occasions and purposes was pointed out:

1. Studies on suspended particulate matter and on its environmental impacts:

• studies of mass balances and flux calculations; • estimation of transport of particulate matter; • evaluation of impact on growth of organisms due to a decrease of transparency; • reflection of climate changes.

2. Studies on contamination of suspended particulate matter:

• studies of short-term changes in contamination; • investigations near contaminant sources and, e.g., on the effectiveness of remediation measures; • use of SPM instead of sediments for monitoring when depositional sites are not available; • use of SPM instead of sediments for monitoring when sediments are bioturbated, and mixing of freshly

deposited and old sediments occur.

Conclusions SPM has proved to be a potential alternative to sediments for monitoring purposes in estuaries and coastal areas. However, its application may not be appropriate in areas with very low SPM contents, e.g., the outer parts of estuary plumes or the open North Sea. Very low amounts of SPM could result in less reliable data and induce misleading interpretation of results. In addition, sampling could be very difficult and time-consuming at those sites.

Care has to be taken when algal blooms provide fresh organic matter, as this may affect results. In these cases, data from samples collected in winter are preferred for trend monitoring.

It is clear that SPM cannot be sampled everywhere and therefore will not be able to replace sediment. On a local scale, SPM monitoring can support other programmes. It could be suggested to assess some data sets in a similar way as OSPAR/MON will do for sediments. A comparison could give an objective view of the usefulness of SPM in monitoring and can it be decided whether SPM could be accepted as an alternative matrix to sediments in joint monitoring programmes.

8 WORKSHOP ON INTEGRATED CHEMICAL AND BIOLOGICAL EFFECT MONITORING (TOR F)

Develop plans for the preparation of detailed background material to be used by a proposed 2005 ICES/OSPAR Workshop on Integrated Monitoring of Contaminants and their Effects in Coastal and Open-Sea Areas (WKIMON) [OSPAR 2004/2]

The question of a closer linkage between chemical and biological effect monitoring into an integrated approach has been discussed on numerous occasions. The rationale is that such an approach might support data interpretation and provide better assessment of the marine environment. WGMS will support this effort (see Agenda Item 6).

ICES and OSPAR are planning a workshop on “Integrated Monitoring of Contaminants and their Effects in Coastal and Open-Sea Areas” that is to be held in January 2005. To that end, the Chairs of the Workshop, i.e., Robin Law (MCWG) and Ketil Hylland (WGBEC), have asked the relevant working groups, including WGMS, for contributions to be used as background documents for the 2005 Workshop.


More precisely, WGMS was asked:

• Which of the JAMP issues can be effectively addressed through integrated chemical and biological effect monitoring?

WGMS could not identify which issues were meant by this question. When related to JAMP products, WGMS has the opinion that integrated monitoring can be beneficial to the assessment of hazardous substances, in particular to OSPAR assessment HA-4 and HA-5 (SIME 04/06/1-E).

• How should integrated monitoring be carried out to improve the quality of assessments?

In lack of specific guidelines for integrated monitoring, WGMS feels that, at present, this is to a great extent a question of logistics and coordination. For example, chemical and biological programmes must be coordinated in time and space and samples taken from the same batch, to the greatest extent possible.

• Are there specific issues (with focus on your field of expertise) that need to be addressed during the workshop?

WGMS will in particular draw attention the work done by Foppe Smedes using passive samplers for measuring the bioavailable fraction of organic contaminants in sediments. The group think this is a promising technique for linking chemical status of the sediments with respect to hydrophobic contaminants and biological effects. Also, at the moment there is a lot of research reported on the use of the so-called DGTs (Diffusive Gradients in Thin films) that are promising regarding metal contamination.

• Are there experts within your work area that you suggest be asked to participate in the workshop?

WGMS members are aware of numerous researchers that could contribute with relevant information to the Workshop. They are listed below:

-UK:

Results from chemical and biological effect monitoring around England, Wales, and Scotland included in the National Marine Monitoring Programme and (also case studies of Firth of Forth)(Ian Davies, FRS) and from licensing/regulatory monitoring (Kevin Thomas, Yvonne Allen, CEFAS).

-Sweden:

Sediment TBT contamination and resulting imposex in mussels (Åke Granbo), Relation between sediment contamination and egg shell thickness of seabirds (Mats Olsson).

-Norway:

Establishing cause-and-effect relationships between sediment pollutants and macrobenthic fauna structure and function (Eivind Oug, Frode Olsgard, NIVA).

-Spain:

Results from the Monitoring Programme on the Basque Littoral (North Spain). This programme integrates results on waters, sediment, benthic communities, molluscs and some fishes. Database since 1994 (Angel Borja, AZTI).

-The Netherlands:

Integrated quality assessment of dredged material (Cor Schipper, RIKZ), Measurements of the bioavailable fractions of organic contaminants in sediments (Foppe Smedes).

-Germany:

During the last couple of years, the Institute of Fishery Ecology (M. Haarich, Th. Lang, U. Kammann) has carried out investigations on contaminants and general biological effects in fishes within a monitoring programme. In addition,


selected biomarkers (EROD) are investigated, and some research has been carried out. The Federal Institute of Hydrology (K. Gruenwald, P. Heininger et al.) carried out two investigations as well on seasonal variations of contaminant concentrations and effects in blue mussels as on macrozoobenthos in 1998/1999 and 2000/2001.

• Are there other international activities that overlap with this workshop and that should be taken account of in the preparation?

WGMS is not aware of any overlapping activity.

9 SUPPORT REGNS (TOR G)

The group was asked to start preparations to summarise the status of contamination of North Sea sediments for the period 2000–2004, and any trends in contamination over recent decades. Where possible, the causes of these trends should be outlined for input to REGNS in 2006.

WGMS noted the explanation of the proposed task for ICES to undertake an integrated assessment of the trends and status of the key components of the North Sea ecosystem, including human pressures and impacts, contained in the letter circulated recently from Andrew Kenny, Bill Turrell, and Hein-Rune Skjoldal. They also noted that it was suggested that the objective could best be achieved through a set of commissioned “Chapters”, each focused on individual themes and authored by members of the relevant ICES Working Groups.

The specific tasks suggested in the letter for the Working Group meetings in 2004 are:

1) to consider this request; 2) to give feedback on how sensible it is; 3) to start specifying and collecting the various data the WG will need to do the task; 4) to nominate a person to act as the chief contact point for this work. WGMS noted that the OSPAR JAMP timetable includes the preparation of an assessment of data held in the ICES Environmental Database during the 2004–2005 period. Specifically, the implementation timetable for the JAMP requires assessments to be carried out in 2005 of CEMP data on contaminant concentrations and their biological effects, detailed below:

• HA-2a. For the substances where periodic sampling and analysis is undertaken, assessments will be made in 2005 and 2009 of temporal trends and (where relevant/feasible) spatial distribution of levels of contaminants in biota, sediments (CEMP) and the water column and relevant biological effects;

• HA-2b. An initial assessment in 2005 and a more comprehensive assessment in 2009 of biological effects of hazardous substances in general on areas of where such effects may occur because of the potential levels of contamination.

OSPAR/MON will meet to undertake these assessments in December 2004. MON plans, to the extent possible, to relate temporal trends in concentrations to trends in inputs.

It is some years since OSPAR attempted a large-scale formal assessment of contaminant monitoring data. Possibly as a consequence of this, an initial review of the data available at ICES suggested that there were significant gaps, and that possibly countries were holding data that could be supplied to the database for the assessment. The data sets on concentrations of contaminants in biota appeared to MON to be more complete than the data on concentrations of contaminants in sediments. Rather few data were available on the biological effects of contaminants (e.g., imposex, EROD, bile metabolites, etc.). OSPAR countries were encouraged to inform ICES and MON of what data they hoped to submit before the deadlines. Once the deadlines had passed, MON/MIG would review the scope of data available, and would determine the most appropriate scope of the assessment.

MON agreed that their assessment would take advantage of the full length of time-series available to them, and would also make an additional assessment of changes over the last decade (1994–2003). The assessment would concentrate on temporal trends in contaminant concentrations in biota and sediments and, where sufficient additional information was available, would also consider spatial distribution patterns. MON considered that it would be very unlikely that biological effects data would permit a useful temporal trend assessment using the techniques developed for sediments


and biota, and therefore that a spatial assessment was more likely. The timetable for the MON assessment is attached as Annex 8.

In the light of the above activities planned within OSPAR, WGMS agreed that the best strategy would be to review the output from the MON assessments at WGMS 2005.

To return to the four tasks listed above:

1) Consider this request. The WG agreed to contribute to the exercise.

2) Give feedback on how sensible it is. The WG agreed that the task was sensible. However, they were concerned that there might be rather few data on contaminants in sediments for the more offshore parts of the North Sea. The WG also asked for clarification of the boundaries of the area to be included in the North Sea Region. Would this also include estuarine and fjordic areas? (Yes, we note that this is in the Supporting Information, Annex 2) The WG had some concern that the time period 2000–2004 was quite short and did not include any large-scale coordinated sampling programme (e.g., OSPAR) for contaminants in sediments. The WG recommended that they should review the scope of data in the ICES database for the period 2000–2004 at their meeting in 2005.

3) Start specifying and collecting the various data the WG will need to do the task. The WG considered that the current requests from OSPAR for data to contribute to the 2005 MON assessments should also provide data for the ICES exercise.

ICES Secretariat staff should be asked to confirm that the deadline for receipt of data for inclusion in the REGNS 2006 exercise would be 1 August 2005. This assumes that any work that WGMS may wish to undertake on these data for REGNS 2006 would be carried out at a meeting early in 2006.

The WG considered that they should await the outcome of the MON assessments before making proposals for any additional data analysis. The WG also noted that if any additional data analysis would be necessary, they would require assistance from the ICES Secretariat staff to extract data and prepare data products.

4) Nominate a person to act as the chief contact point for this work. The WG nominated Ian Davies (UK, current chairman of MON) to act as chief contact point for WGMS for this exercise.

10 COLLABORATION WITH WGSAEM (TOR H)

Determine priorities for assistance from WGSAEM with statistical analyses and develop with WGSAEM a plan for the necessary collaboration.

During the meeting, WGMS worked with WGSAEM to develop methods for the estimation of Background Concentrations and Background Assessment Concentrations, and the outcome of these discussions is incorporated into Agenda Item 11.2. However, it will be necessary for ICES Working Groups or OSPAR Working Groups to return to this subject routinely to improve and refine the approaches and data sets that have been used so far. In addition, there are likely to be opportunities for technical developments in the statistical methods applied to the BC/BAC objectives. WGMS therefore recommended that they continue to work with WGSAEM to:

Continue analysis of contaminant data to confirm and elaborate on BCs and BACs for sediment.

Over the years, WGSAEM has developed and applied methods for assessment of the statistical power of monitoring programmes for contaminants in biota. These methods have enabled monitoring agencies to adjust their programmes so as to take best advantage of the resources available to be used on monitoring programmes for biota, through better understanding of the dominant sources of variance in their results.

These methods have not yet been applied to sediment monitoring programmes, in an international context. The clearer definition of normalisation procedures in ICES, OSPAR, and HELCOM Guidelines means that the methods can be


applied to sediment data with greater confidence that the results will have broad applicability. WGMS therefore recommended that they work with WGSAEM to:

Undertake analysis of the power of sediment monitoring programmes to detect changes in contaminant concentrations.

The OSPAR JAMP, in relation to contaminants, has dual objectives concerning temporal trends and spatial distributions of contaminants. Past experience has shown that the OSPAR programmes normally progress from initial spatial distribution studies to longer-term temporal studies. Examples include the outcome of the recent OSPAR SIME2004 meeting at which it was proposed that several “new” contaminants should initially be investigated through one-off spatial surveys. There is little guidance currently available through ICES, OSPAR or HELCOM on how such surveys should be designed (sampling locations, separation of sampling points, numbers of replicates, grid versus random, or stratified random, sampling designs, etc.). WGMS therefore recommended that they work with WGSAEM to:

Develop guidance on sampling schemes for determination of the spatial distributions of contaminants in sediments, for example in relation to the strategies proposed by OSPAR SIME2004 towards “new” contaminants.

11 ANY OTHER BUSINESS

11.1 SEDNET progress

SEDNET is a European Sediment Research Network, financially supported by the European Commission from 2001 to 2004. The main and final deliverable is to produce guidance for integrated and sustainable sediment management (SSM) from local to river basin level.

SEDNET is structured in six working groups (http://www.sednet.org/workgroups.asp) that are specialized in different aspects of contaminated sediment management from the technical to the socio-economic perspective as follows:

Working Group 1 - Site Investigation and Characterization (becoming WP3 - Quality and impact assessment)

Working Group 2 - Contaminant Behaviour and Fate (becoming WP3 - Quality and impact assessment)

Working Group 3 - Sediment Treatment (becoming (WP4 - Dredged material treatment)

Working Group 4 - Planning & Decision Making (becoming WP2 - Sediment management at the river basin scale)

Working Group 5 - Risk Management & Communication (becoming WP5)

Working Group 6 - Financial & Economic Aspects (becoming WP2 - sediment management at the river basin scale)

Since several common approaches were identified last year, a decision to keep the communication between WGMS and SEDNET was made. For this purpose, some members of WGMS have participated in different SEDNET workshops:

• Foppe Smedes joined the workshop on “Impact, bioavailability and assessment of pollutants in sediments and dredged materials under extreme hydrological conditions” in Berlin, April 2003. The objective of this workshop was to define the state-of-knowledge and to identify the role of sediments and related research needs supporting the creation of a sound knowledge base necessary for the management of the water-soil-sediment system with regard to environmental pollution, influenced by climate change.

• Maria Belzunce participated in the workshop on “Assessing toxicological and environmental risk of natural sediments from river source to coastal Delta” in Hamburg, April 2003. The objective of this workshop was to consider current methods in biogeochemical and TIE (Toxicity Identification and Evaluation) assessment of sediments.

• Maria Belzunce participated in the workshop on “Monitoring sediment quality at river basin scale: Understanding the behaviour and fate of pollutants” in Lisbon, January 2004. The objective was to integrate complementary disciplines to solve the specific problem of monitoring sediment quality at river-basin scale with the aim of understanding the chemical, physical and biological factors in order to assess sediment quality.

As a summary of the outputs coming from the discussions in the different workshops, the following key research topics have been identified: 1- Bioavailability and mobility of contaminants in sediments;

2- Effects-based analysis for understanding contaminant behaviour and fate;


http://www.sednet.org/wg1.asp






3- New strategies for monitoring of sediment quality;

ad 1.1- It is necessary to understand the factors that govern the bioavailability and mobility of contaminants in sediments and soils. This understanding is required to develop methods to measure the bioavailability of contaminants in soils and sediments and risk assessment procedures in which the true bioavailability is taken into account.

At the last workshop in Lisbon, some work was presented related to the role of organic matter on desorption and bioavailability of organic contaminants in sediments. Only two communications addressed the direct measurement of bioavailability, by Solid Phase Extraction (SPE) and CALUX DRE methods. The workshop showed that further development is needed to measure the bioavailability of contaminants.

ad 1.2- Adequate monitoring and analytical concepts are necessary. Sorption and speciation processes, changes in environmental factors, etc., must be taken in account.

ad 2.1- Chemical analysis is not enough for evaluating the sediment quality, but the effect assessment is necessary.

ad 3.1- Appropriate selection of target compounds based on persistence, bioaccumulation/adsorption, and relevance at large scale, high fluxes, and priority substances (Water Framework Directive) should be made.

ad 3.2- Monitoring of the suspended matter: substances that tend to accumulate and are transported bound to particles may be better measured in the suspended matter than in the water phase.

References

Documents, workshop summaries of Barcelona 2002, Berlin 2003, Hamburg 2003, Lisbon 2004 are available at SEDNET website: www.sednet.org.

11.2 Review the outcome of the 2004 OSPAR/ICES Workshop in The Hague on BCs and EACs in relation to contaminants in sediments

Just before the WGMS meeting, WGMS was asked to continue the work started by the workshop. It was decided to include that as an extra Agenda Item. See Agenda Item 12.

11.3 Review of BDC documents

WGMS reviewed the set of four BDC documents that had been brought to their attention by the ICES Secretariat, and made the following observations:

BDC 04/2/11-E(L) The development of the EcoQ element concerning imposex in dog whelks Nucella lapillus

WGMS felt that this document had little relevance to their work. They noted that the EAC for TBT in sediment was provisional and that proposals had been made at SIME2004 to review all EACs.

BDC 04/2/1 E Progress on EcoQOs and a draft table of contents of the overall report on EcoQOs to OSPAR 2005

WGMS felt that they had little to contribute to the report proposed in this paper, other than to provide Background Concentrations and Background Assessment Concentrations for contaminants in sediment, should they be required.

BDC 04/2/3-E(L) Ecological Quality Objectives – A Conceptual description

WGMS noted that the OSPAR Secretariat, through this document, had sought to develop the EcoQO pilot project in a manner that recognised the approaches being used under the Water Framework Directive (and possibly also under EMMA). By considering the potential environmental impacts of various human activities, the OSPAR Secretariat was able to create links to relevant EcoQOs and assessment elements. Concentrations of hazardous substances in marine environmental compartments, including sediments, are relevant to assessments of the impacts of land-based discharges of hazardous substances, and discharges from offshore installations. Assessments based on BCs/BACs and EACs should provide useful advice in relation to the consequences of these pressures.


http://www.sednet.org/

BDC 04/2/5-E Inventory of influence of human activities on EcoQOs and identification of sectors and other stakeholders

WGMS scoured this document for reference to issues concerning contamination of sediment. Brief mention was made on page 58 in relation to the need to “Restore and/or maintain habitat quality”. However, the text contained no substantive material against which WGMS could offer comment.

12 BACKGROUND CONCENTRATIONS

The ICES Working Group on Marine Sediments in Relation to Pollution (WGMS) and the Working Group on Statistical Aspects of Environmental Monitoring (WGSAEM) are invited by OSPAR/ICES workshop to work in collaboration, to carry out a further scrutiny of the integrity and relevance of the BC data set, collated by the workshop and to construct draft background concentrations for CEMP metals (Cd, Hg, Pb) and PAHs in sediments.

WGMS considered this to be an important task but due to the late request most participants had not been able to prepare themselves for this task prior to the meeting. Starting to study the collected data it appeared that participants, especially from the Scandinavian countries, could contribute with much more data than already present in the database. This also raised the question of whether the procedure for selecting participants for the Workshop on Background concentrations through the Delegates could be more adequate and focused.

Continuing on the work done by the workshop, two subgroups – one for metals and one for organic contaminants – were formed to process the new arriving data and evaluate them with the aim of deriving proposed background concentrations. The summary and the outcome of the work of the trace metal group are given in Section 12.1. A more detailed evaluation and a summary of the data can be found in Annex 9. Section 12.2 contains the report of the organics subgroup. The graphical presentation of the organics data is collected in Annex 10. The development of Background Assessment Concentrations was led by the WGSAEM. Subgroups of both working groups had a meeting by phone discussing the developments and agreeing on proposed values for BAC. The scrutiny and integrity of the data is a chemical issue and was where possible included in the evaluation of the data available.

WGMS felt that the issue of BCs, considering the time-consuming nature, should not only occasionally get attention. Of the different workshops held so far there was only little overlap in participants and the approach differed for each workshop. Therefore, WGMS recommended that OSPAR or ICES put in place a procedure whereby the data set used to derive these BCs can be reviewed and extended, and the BC values can be regularly reviewed.

12.1 Background values for metals in sediments

Introduction Prior to the meeting of WGMS, an “OSPAR workshop on the evaluation and update of Background Reference Concentrations (BRCs) and Ecotoxicological Assessment Criteria (EACs) and how these assessment tools should be used in assessing contaminants in water, sediment, and biota” was held in The Hague in February 2004. At this workshop data were collected for the establishment of background concentrations. A simple database was installed to allow the storage and handling of the data. During their 2004 meeting the participants of WGMS gathered much more data, which were processed and added to the database. The data in the database from the EAC/BRC workshop and the new data added at the WGMS meeting were utilised in the following manner for metals:

• Down-core results dated, or expected to be, from approximately 1850 and before were selected;

• Sediments in estuaries were not included, because they are affected by the catchment areas;

• Generally only fine-grained and/or sieved samples were included. Trace metal concentrations in unsieved samples were assessed by taking into account either the lithium content or grain size analyses, as in some coarse samples of glacial origin Al can be found in large quantities;

• All data were normalised to a sample with 50 g kg-1 Al or 50 mg kg-1 Li, following the rules below:

- The simple ratio method was used for samples sieved on 20 µm and/or the Li content > 40 mg kg-1; - In other cases the OSPAR guidelines were applied taking into account pivot values. However, data resulting

from an extrapolation factor of more than 3 were discarded. In case grain size/Al or Li relations showed more variation than analytically expected, the maximum extrapolation was reduced to a factor of 2;


• Data were evaluated on a regional basis, taking only minimum and median values, to disregard any high outliers. The difference between minimum and median values was taken as a rule of thumb for variability;

• The new data sets were accepted and the above rules were applied as widely as possible, but only ratio-normalisation was performed. For some of the data sets, only Li or only Al was available.

WGMS discussion

In the discussion some critical aspects of using and deriving BC values for metals were addressed:

• It was generally accepted that core analysis of pre-industrial sediments would be the best choice, as surface sediments cannot be considered as sediments without any influence of anthropogenic contaminants. But even then, there is reason for concern as metals can move within the sediments, as is known for Mn, which could give rise to lower BC values in the cores, as well as naturally increasing values of some metals in the surface sediment.

• Care should be taken especially with diagenetic elements (e.g., Mn, Fe, Cd) when dealing with anoxic sediments. E.g. Cd concentrations in sediment can be considerably high if such sediment was settled under anoxic conditions, i.e., the overlaying water was anoxic. The formation of sulphides will function as a collector of metals from the water phase. This is especially visible for Cd and a little less for Cu, Ni and the other elements, which tend to form strong sulphide complexes. Anoxic conditions do not automatically result in higher metal concentrations as it is not expected that sediment from cores originally formed in oxic environments obtain elevated concentrations when they become anoxic in a later stage.

• Also it should be noted that in estuaries, sediments could be affected by transport from the catchment areas, which could give a different natural background concentration, albeit one that is difficult to assess.

• Another aspect that had not been taken into account is the possibility of nodules, which contain raised levels of many metals (Borg and Jonsson, 1996). These were probably not present in the cores used for determining BC-values. Probably sediment with recognisable nodules is not suitable for assessment using BC-values. A suggestion could be to sieve the samples over 20 µm. If the metals present in the nodules are environmentally relevant, i.e., released to the water phase, this will also give higher concentrations in the fine fraction.

While the complications above might not be relevant in the underlying data set for estimation of BC-values, deviating conditions should be taken into account when assessing monitoring data.

General approach to estimate BCs For each data set, a range was established by taking median concentrations of each core sample in the region (where more than one individual concentration was available), after exclusion of data sets felt to be impaired by anoxic conditions or possibly anthropogenic influence (i.e., W-Norway and Biscay Bay and Iberian Coast). Metal concentrations were normalised for both Al and Li concentrations where possible, and a rounded value in the upper range was taken as the BC. Taking the upper value is quite reasonable knowing that when the QSR 2000 was prepared, only the upper limit for BRCs (now BC) were taken into account. Likewise MON 2003 decided (before the BAC were developed) to use the upper range values. Consequently, there is no merit in setting ranges and, with regard to a practical use, a single (upper) value as BC is strongly preferred. Only for Ni and As some reservation was made with respect to a general applicable value as in the Baltic area consistently lower values were found. A detailed evaluation for individual metals is given in Annex 9.

Results The background concentrations estimated from core data are listed in the upper row of Table 1. For comparison the BRC values from the 1996 workshop on BRCs (Hamburg) when recalculated to 50 g kg-1 aluminium are given. The table shows that for most elements, the proposed BC values are close to the 1996 upper range values. For Cd, Hg and Pb the proposed values are above the former upper values, but less than 10% for Cd and Pb. Turning the 1996 values into round numbers would bring them even closer.

The 1996 report also indicated a global average for shale. The data after recalculating this to 50 g kg-1 Al are given for information. In addition, the geologically established values for the content in the earth’s crust are given in Table 1 (the latter were not normalised to 50 g kg-1 Al).

As the background values were based on core data, it was also roughly investigated whether these values were far from the current content in surface sediments, using results collected in the ICES database on marine sediments. As it was not possible to normalise those data, only sediments from the fine fraction (20–90 µm) were taken into consideration. Although these samples would also require further normalisation, the compositions are close enough to reference


composition to allow a certain degree of comparison. For each metal, the lower 5% percentile was taken as a probable lowest content in surface sediments. For all metals the 5% percentile of ICES data is close to, and often even lower than, the proposed BC value. Comparing BCs with the lower 5% percentile contents in the ICES database, it can be seen that Hg and Pb in current surface sediments are generally well above the suggested background concentration, whereas the other elements are close to or below the suggested background concentration. Especially Ni is below BC. In addition, the median values are listed, showing that in general the sediments in the OSPAR Convention area are well above background level, except for Ni where the median concentration is even below the proposed BC. The number of samples for each element is given for information.

The 1996 EAC values are shown, and except for As, the background concentrations are found to fall within the ranges given, with Hg on the lower EAC value. It should be noted that for EAC values no conditions for grain size composition are prescribed for their application.

Table 1. Estimated background concentrations and corresponding former BRC, earth crust, data held in the ICES database and EACs.

Element As Cd Cr Cu Hg Ni Pb Zn

Suggested BC1) 152) 0.2 60 20 0.05 452) 25 90

1996 BRC (lower) 3) 12 0.04 52 13 0.02 26 8 51

1996 BRC (upper) 3) 26 0.17 116 33 0.04 53 23 104

1996 BRC (shale) 6 0.08 51 25 0.02 38 9 65

Earth Crust4) 5.5 0.15 51 23 35 11.5 92

ICES5)

Database

(20–90µm)

5%Perc.

Median

(n)

11

33

(1304)

0.11

0.50

(1754)

51

92

(1656)

14

28

(1858)

0.07

0.25

(1764)

18

38

(1472)

31

94

(2162)

95

200

(1866)

EAC (low)

(high)

1

10

0.1

1

10

100

5

50

0.05

5

5

50

5

50

50

500 1) The suggested normalised BC values are valid for all regions of the OSPAR Area 2) For these elements, the core data from Region II and the Baltic area suggest that a lower value could be applied for this region. 3) The Me/Al ratios were recalculated to a sample composition of 50 g kg-1 Al. 4) Data for earth crust not normalised. 5) All sieved data from the ICES data base were taken into account, and the lower 5% percentile value and median value were

taken as a guideline for content in surface sediments, with the number of data given parentheses.

Background Assessment Concentration (BAC) At the OSPAR/ICES workshop on the evaluation of BC and EAC values in February 2004 in The Hague, the problem was considered of how to test statistically whether areas are at, or near, Background value. To support the objectiveness of such a statistical test, the term Background Assessment Concentration (BAC) was introduced. The technical side of BAC determination and use is being handled by WGSAEM. The details of the BAC derivation can be found in the WGSAEM report. Table 2 shows BCs and BACs.

Table 2. Proposed Background Concentrations and associated Background Assessment Concentrations.

Element As Cd Cr Cu Hg Ni Pb Zn

BC 2004 15 0.2 60 20 0.05 45 25 90

CV% from UK monitoring

11 14 7. 14 15 14 10 8

BAC/BC with 90% power

1.4. 1.6 1.3 1.6 1.6 1.5 1.4 1.3

BAC 22 0.31 76 31 0.08 70 34 116 Notes: 1) To use these BAC values, individual sediment results have to be normalised to 50 g kg−1 Al or 50 mg kg−1 Li content, using the OSPAR normalisation guidelines. 2) The BAC is NOT a background concentration and should only be used in connection with the statistical test devised by the ICES-WGSAEM.


12.2 Background values for PAHs sediments

For the organic contaminants, BCs were only considered and discussed for the PAHs, and specifically those PAH compounds that are part of the OSPAR CEMP. Two approaches were identified that could lead to appropriate background concentrations, namely the use of data from deep cores and the use of present-day concentrations in remote (pristine) areas, i.e., distant from known sources and, therefore, probably primarily influenced by atmospheric/diffuse inputs.

The use of data from deep cores would be consistent with the recommendations from the 2004 OSPAR/ICES Workshop on BRCs and EACs that the background concentrations for synthetic substances should be zero. This is also consistent with the OSPAR Strategy for Hazardous Substances, namely “the ultimate aim of achieving concentrations in the marine environment near background values for naturally occurring substances and close to zero for man-made synthetic substances.”

In discussion, WGMS noted some difficulties in using PAH data from deep cores to define background concentrations. These included:

• Uncertainties as to the extent of environmental (habitat) change that had occurred during the period of time represented by the core. For example, core data were presented from the Netherlands, which suggested that while the cores had been collected from marine areas, the deeper parts might represent terrestrial or littoral environments;

• Uncertainties as to the rate of degradation of PAHs in sediment cores (oxic or anoxic) over periods of decades to centuries. Significant degradation could lead to observed concentrations being lower than when the sediment was initially deposited;

• Uncertainties arising from the rather incomplete coverage of the OSPAR Convention area by cores analysed for PAHs;

• The limited occurrence of stable depositional environments from which suitable cores might be obtained for subsequent analysis.

It was therefore concluded that data for present-day concentrations in surface sediments from remote (pristine) areas, i.e., areas distant from known sources and, therefore, probably primarily influenced by atmospheric/diffuse inputs would be suitable for the derivation of BCs. The BCs should reflect “consensus” values of these data, and should not be dominated by extreme high or low values.

A database of suitable data had been initiated at the 2004 OSPAR/ICES Workshop on BRCs and EACs, and further data had been made available prior to the WGMS meeting. More data were supplied during the WGMS meeting. All data were normalised to organic carbon concentrations. The data sets in the database used by WGMS are summarised in Annex 10.

In order to limit the influence of extreme values, the data sets were summarised as median values and initially visualised as histograms (Annex 10). The Background Concentrations were then estimated as the medians of the medians. The BC values for PAH compounds obtained by this procedure, normalised to 2.5% organic carbon, are shown in Table 3.

Data were also made available on PAH and organic carbon concentrations in deep sediment cores from the Stockholm archipelago and the southwest Baltic (south of Skania, Arkona Basin area). Concentrations were normalised to 2.5% organic carbon, and medians were compared to the proposed Background Concentrations (Figure 1). The data from the Baltic Sea cores are of the same order of magnitude as the proposed BC values, suggesting that the proposed BC values may also be applicable in the Baltic Sea area.


Table 3. Proposed Background Concentrations for PAH compounds in sediment.

PAH compound Calculated BC µg kg−1 OC

Proposed BC µg kg−1 OC

Proposed BC µg kg−1 normalised to 2.5% OC

Naphthalene 191 190 5 Phenanthrene 667 670 17 Anthracene 109 110 3 Fluoranthene 792 800 20 Pyrene 507 500 13 Benzo[a]anthracene 362 360 9 Chrysene 436 440 11 Benzo[a]pyrene 577 580 15 Indeno[1,2,3,c,d]pyrene 1983 2000 50 Dibenzo[a,h]anthracene 274 270 7 Benzo[g.h,i]perylene 1756 1800 45 Note: The values above for dibenzo[a,h]anthracene are based on only three data points, and therefore have particularly high uncertainty.

0

10

20

30

40

50

60

70

80

90

100

Phena

nthren

e

Anthrac

ene

Fluoran

thene

Pyrene

Benzo

[a]an

thrac

ene

Chryse

ne

Benzo

[a]py

rene

Benzo

[ghi]p

erylen

e

Inden

o[1,2,

3-cd]p

yrene

µg/k

g dw

2.5

% O

C

Stockholm Archipelago

SW Baltic

BC

Figure 1. Comparison of PAH concentrations in deep cores from the Baltic Sea with proposed Background Concentrations, all normalised to 2.5 % organic carbon.

References

Borg, H. and Jonsson, P. 1996. Large-scale metal distribution in Baltic Sea sediments. Marine Pollution Bulletin, 32: 8-21.

13 ELECTION OF A NEW CHAIR

The group unanimously recommended that the Foppe Smedes should continue as Chair of WGMS for another term of three years.


14 RECOMMENDATIONS AND ACTION LIST

Recommendations and action list are added as Annex 11 and Annex 12.

15 DATE AND VENUE OF THE NEXT MEETING

Jean-Louis Gonzales informed that WGMS would be welcome to IFREMER. The data and exact place will be confirmed later.

16 CLOSURE OF THE MEETING

WGMS thanked the organisers and hosts for the excellent arrangements and facilities. The participants were thanked for their contributions and hard work done in an excellent collegial atmosphere. The meeting was closed at 14.00 on 5 March 2004.


Annex 1 Agenda of the 2004 WGMS meeting in Stockholm, Sweden, 1–5 March 2004

1 OPENING OF THE MEETING 2 ADOPTION OF THE AGENDA 3 (BIO)AVAILABILITY OF CONTAMINANTS IN SEDIMENTS Measurement of the potential (bio)availability of contaminants in sediment; evaluate the work in the Western

Scheldt intersessionally done by Belgium and the Netherlands. Report on the use of DGT in estimating availability of metals in sediments

4 SEDIMENT DYNAMICS IN MONITORING Finalize Annex to the sediment monitoring guidelines, Guidance on the interpretation of trend monitoring data,

taking into account sediment dynamics. 5 DEVELOPMENT OF INDICATORS OF SEDIMENT CONTAMINATION Development of practical indicators for sediment quality is of paramount importance to display the results of

environmental assessments to the general public. The group should continue to develop such indicators and, where possible, demonstrate and evaluate some presently applied procedures.

6 COLLABORATION WITH WGBEC Further investigate the possibilities of integrated chemical and biological effect monitoring and evaluate where the

knowledge on chemical sediment monitoring can contribute to application and interpretation of biological effects monitoring (with WGBEC). Especially biological effects monitoring techniques that include sample preparation, extraction and separations may benefit from evaluation by WGMS.

7 USE OF SPM IN MONITORING PROGRAMMES Investigate and report on the possibilities and present use of suspended matter as a matrix for monitoring

programmes. 8 WORKSHOP ON INTEGRATED CHEMICAL AND BIOLOGICAL EFFECT MONITORING Develop plans for the preparation of detailed background material to be used by a proposed 2005 ICES/OSPAR

Workshop on Integrated Monitoring of Contaminants and their Effects in Coastal and Open-Sea Areas [OSPAR 2004/2]

9 SUPPORT REGNS The group was asked to start preparations to summarise the status of contamination of North Sea sediments for the

period 2000–2004, and any trends in contamination over recent decades. Where possible, the causes of these trends should be outlined; for input to REGNS in 2006;

10 COLLABORATION WITH THE WGSAEM Determine priorities for assistance from WGSAEM with statistical analyses and develop with WGSAEM a plan

for the necessary collaboration. 11 ANY OTHER BUSINESS

11.1 SEDNET progress 11.2 Review the outcome of the 2004 OSPAR/ICES workshop in The Hague on BCs and EACs in relation to

contaminants in sediments 11.3 Review of BDC documents

12 BACKGROUND CONCENTRATIONS The ICES Working Group On Marine Sediments in relation to pollution (WGMS) and the Working Group on

Statistical Aspects of Environmental Monitoring (WGSAEM) are invited by OSPAR/ICES workshop to work in collaboration, to carry out a further scrutiny of the integrity and relevance of the BC data set, collated by the workshop and to construct draft background concentrations for CEMP metals (Cd, Hg, Pb) and PAHs. in sediments.

12.1 Background values for metals in sediments. 12.2 Background values for PAHs sediments. 13 ELECTION OF A NEW CHAIR 14 RECOMMENDATIONS AND ACTION LIST 15 DATE AND VENUE OF THE NEXT MEETING 16 CLOSURE OF THE MEETING


Annex 2 Terms of Reference for the 2004 WGMS meeting

2EMS03 The Working Group on Marine Sediments in Relation to Pollution [WGMS] (Chair: F. Smedes, Netherlands) will meet from 1–5 March 2004 in Stockholm, Sweden to:

a) continue the work on the measurement of the potential bioavailability of contaminants in sediment and evaluate the work done in the Western Scheldt inter-sessionally by Belgium and the Netherlands;

b) finalize work on the annex to the sediment monitoring guidelines that provides guidance on the interpretation of sediment trend monitoring data, taking into account sediment dynamics and also taking into consideration additional contributions from other member countries;

c) continue work on the development of indicators of sediment contamination;

d) further investigate the possibilities of integrated chemical and biological effect monitoring and evaluate where the knowledge on chemical sediment monitoring can contribute to application and interpretation of biological effects monitoring (with the Working Group on the Biological Effects of Contaminants);

e) investigate and report on the possibilities and present use of suspended matter as a matrix for monitoring programmes;

f) develop plans for the preparation of detailed background material to be used by a proposed 2005 ICES/OSPAR Workshop on Integrated Monitoring of Contaminants and their Effects in Coastal and Open-Sea Areas [OSPAR 2004/2];

g) start preparations to summarise the status of contamination of North Sea sediments for the period 2000–2004, and any trends in contamination over recent decades. Where possible, the causes of these trends should be outlined; for input to the Regional Ecosystem Study Group for the North Sea in 2006;

h) determine priorities for assistance from the Working Group on the Statistical Aspects of Environmental Monitoring with statistical analyses and develop with this Working Group a plan for the necessary collaboration.

WGMS will report by 22 March 2004 for the attention of the Marine Habitat Committee and ACME.

Supporting information

Priority: This group handles key issues regarding monitoring and assessment of contaminants in sediments.

Scientific Justification and relation to Action Plan:

a) Present monitoring methods are based on measuring the total contaminant concentrations in sediments. The resulting data do not necessarily represent the environmental risk, due to the limited bioavailability of many contaminants in sediments. WGMS is an appropriate platform to discuss and investigate alternative methodologies for sediment assessments for future advice to ICES on taking bioavailability into account.

b) The proposed annex to the Sediment Monitoring Guidelines is an essential addition that will assist ICES in providing advice to others, e.g., OSPAR and HELCOM, on the interpretation of monitoring data with a view to detecting temporal changes in sediment quality. For this, sediment dynamics are of great importance as they affect the evolution of all sediments and a description of their influence should be included in the proposed Annex. Contributions on other areas, such as the St. Lawrence Gulf and Estuary and the Bay of Biscay will be worked with intersessionally and drafted at this meeting. Contributions also from other areas will greatly improve the paper, and are welcome.

c) Although the progress on this point is limited, development of practical indicators for sediment quality is of paramount importance to display the results of environmental assessments to the general public. Therefore the group should continue to develop such indicators and, where possible, demonstrate and evaluate some presently applied procedures.

d) Discussion on the integration of sediment and biological effects monitoring did not come much further than taking samples at the same place and time. Especially biological effects monitoring techniques that include sample preparation, extraction and separations may benefit from evaluation by WGMS. Perhaps through this route integrated guidelines can be developed. This is useful for both biological effects and chemical monitoring, to support interpretation and provide better assessment of the marine environment.

e) Several countries (e.g., Germany, The Netherlands) collect suspended matter in or outside monitoring programmes. The potential of monitoring this future or past sediment in relation to sediment monitoring is unknown. An inventory of such programmes and evaluation of the


existing results may reveal some of the above aspects.

f) This is in response to an OSPAR request;

g) This is required as the working groups input to the thematic writing panels working under the coordination of REGNS to develop an integrated assessment of the North Sea. For the purposes of this study the North Sea comprises ICES Area IV and IIIa and does not include intertidal areas. As far as possible, significant seasonal variation should be described.

h) This task will support long-term planning for WGSAEM to ensure that its expertise is available for the solution of priority problems and that appropriate data sets are available for client requested advice.

Action plan: 4.12, 2.8, 1.4.1

Resource Requirements: None required

Participants: Subjects like bioavailability and sediment quality criteria (SQC) are of mutual interest to both WGBEC and WGMS. Periodic interactions between the groups and transfer of information are essential for efficient operation of both groups.

Selected and interested members of WGMS should participate in work of the WGBEC for the interaction and information transfer on the mutual issues such as SQC and bioavailability.

Secretariat Facilities: None required

Financial: None

Linkages to Advisory Committees:

ACME

Linkages to other Committees or Groups:

WGBEC, MCWG

Linkages to other Organisations:

OSPAR, HELCOM

Cost share ICES 100 %


Annex 3 List of participants

Name Address Telephone no. Fax no. E-mail

Maria Jesus Belzunce

AZTI Oceanography and Marine Environment Department Muelle de la Herrera Recinto Portuario s/n 20110 Pasajes Spain

+34 943 00 4800 + 34 943 00 4801 [email protected]

Ingemar Cato Geological Survey of Sweden Division of Geophysics and Marine Geology PO Box 670 SE-75128 Uppsala Sweden

+46 18 179188 +46 18 179210 [email protected]

Ian Davies Fisheries Research Services Marine Laboratory 375 Victoria Road, PO Box 101 Aberdeen AB392LW United Kingdom

+44 1224 876544 +41 1224 295511 [email protected]

Jean-Louis Gonzalez

IFREMER Departement “Polluants chimiques” Z.P de Bregaillon 83507 La Seyne sur mer France

+33 494 30 48 56 +33 494 30 64 17 [email protected]

Per Jonsson

Stockholm University, Institute of Applied Environmental Research (ITMx), Laboratory for Aquatic Ecotoxicology S-106 91 Stockholm, Sweden

+46–8–674 74 72

Mobile

+46–70–520 80 57

+46–8–674 76 38 [email protected]

Martin M. Larsen

Ministry of Environment & Energy Department of Marine Ecology Frederiksborgvej 399 DK–4000 Roskilde Denmark

+45 4630 1200 +45 4630 1114 [email protected]

Kristoffer Naes

Norwegian Institute for Water Research Southern Branch Televeien 3 N–4879 Grimstad Norway

+47 37 295067 +47 37 044513 [email protected]

Carla Palma

Instituto Hidrografico Rua das Trinas 49 1249–093 Lisbon Portugal

+351 21 0943000

+351 21 0943299 [email protected]

Ruth Parker CEFAS Lowesoft Lab Pakefield Road, Lowesoft Suffolk, NR33OHT United Kingdom

+44 1502 524349 +44 1502 513865 [email protected]


mailto:[email protected]








Name Address Telephone no. Fax no. E-mail

Patrick Roose

Management Unit Mathematical Models of the North Sea – Royal Belgian Institute for Natural Sciences 3&23 Linieregimentsplein B–8400 Oostende Belgium

+32 59 700131 direct +32 59 242054

+32 59 70 49 35 [email protected]

Birgit Schubert

BundesAnstalt fur Gewasserkunde Am Mainzer Tor 1 D–50068 Koblenz Germany

+49 261 1306 312 +49 261 1306 5363 [email protected]

Foppe Smedes

(Chair)

National Institute for Coastal and Marine Manangement RWS/RIKZ P.O. Box 207 9750 AE Haren The Netherlands

+31 505 331306 +31 505 340772 [email protected]

Linda Tyrrell

Marine Institute Marine Environment & Food Safety Services Abbotstown Castleknock Dublin 15 Ireland

+ 353 1 822 8271 + 353 1 820 5078 [email protected]







Annex 4 DGT Passive sampling of metal ions in water by DGT-technology

Oddvar Røyset NIVA chemistry, NIVA Oslo, Brekkevn 19, PO Box 173 Kjelsaas 0411, OSLO, Norway. Tel +47 22 185100, Fax +47 22 185200, Email: [email protected].

Passive sampling in aquatic chemistry Passive samplers have predominantly been used in air chemistry. The high diffusion rate of gases in air makes passive sampling an attractive technique as sampling rates of litres per hour can be achieved. The performance is good, due to the low influence from environmental parameters (temperature, pressure, humidity, air velocity). Diffusion rates of metal ions in water are much slower than for gasses in air (5 orders of magnitude lower, D of 10–6 compared to 10–1 cm2/sec for gases). Thus it is more difficult to construct passive samplers for metal ions with useful sampling rates.

For passive sampling of non-polar organic compounds in water, lipid-filled membrane tubes (Semi-Permeable Membrane Devices, SPMDs) have proved useful. For the sampling of metal ions in water, the first breakthrough was the DGT-passive sampler (Diffusion Gradients in Thin films). This was the first truly diffusional passive sampler giving quantitative and not only qualitative data for common heavy metal ions in water such as Pb, Cd, Cu, Zn, Ni, Co.

The DGT passive sampler The first passive sampler for inorganic ions was described in 1994 (Davison and Zhang, 1994; Zhang and Davison, 1995). The first studies were focused on the classical divalent heavy metals (Pb, Cd, Cu, Zn, Co, Ni). Later it also showed promise for trivalent ions (Al, Fe, Mn). The DGT samplers have from 1995 found numerous applications in freshwater (more than 50 publications) and also for seawater. The diffusive properties of passive samplers have been examined by Zhang and Davison (2000) and by Garmo et al. (2003). The uptake rate estimated from diffusion theory is around 10–20 ml/24 h for a standard DGT sampler. Current status of the sampler is reviewed by Davison et al. (2000). Benefits of the DGT technique are:

1) The sampler integrates/determines labile free ions. 2) Is little affected by environmental factors (pH, pressure, salinity, temperature (2.5–3% per degree, must be

corrected for). 3) High sampling capacity (up to months without overloading. 4) High sensitivity with LOD from 0.001–0.1 µg/L per 24 h. Methods - DGT samplers and ICPMS The standard DGT DGTs are produced from DGT Research Ltd, UK. After exposure the absorbents of the samplers are extracted with acid and the collected amounts of metals are determined with ICP-MS. For accurate calculations of water concentrations of metal ions, it is necessary to perform temperature corrections of diffusion coefficients and estimate the laminar boundary layer.

DGT sediment probes A more recent developed DGT technology, the DGT sediment probe, has lately shown promise to determine high resolution profiles of metal ions in sediments. The probe is a 15 cm long DGT “stick” which can be put into the sediment surface. After deployment the stick can be separated into suitable slices to get desired space resolution (down to 1 mm), and metals determined with ICP-MS. A modelling tool (DIFS) is available to calculate pore water concentrations.

Passive samplers and metal fractionation samplers – what do they look like? NIVA have established two new metal fractionation/speciation tools, the time-integrating DGT-sampler (labile ions) and the time-resolved SCF-sampler (Three fractions: Particulate, Labile and Anionic). The SCF sampler is a complementary fractionation tool for metals in water (Al, Fe, Mn, Cu, Zn and many others).


Samplers from left:

1) Two ordinary DGT samplers 2) SCF sampler with filter 3) SCF sampler with syringe 4) Pore water extraction (CEEP) 5) DGT sediment probe

What can DGTs be used for? General purpose sampling tool for labile metal ions in water Generally most of the high priority heavy metals (Pb2+, Cd2+, Cu2+, Zn2+, Ni2+, Co2+) are quantitatively taken up in the pH range 4.5 – 9 (Davison 2000).

In a study at NIVA we found that the DGTs collect up to 30 metal ions. In the pH range 4.7 to 6 of surface waters 24 metals are quantitatively taken up by the Chelex-based DGT. An additional 8 other elements are promising, but we need more research to understand some details of uptake mechanisms (Garmo, Røyset et al., 2003).

Works well both in seawater and freshwater The DGT sampler has high selectivity for the divalent and trivalent cationic forms of metals in water. In seawater most of the transition metals are collected (Pb, Cd, Cu, Zn, Ni, Co) as well as Al, Fe and Mn, while there are selectivity/capacity limitations for elements like Ba, Sr, U and some others.

Assessment tool for prediction of biological effects of toxic metals in water Biological and toxic effects of metals are often caused by the free “labile” ions. As the DGT collects mainly labile ions, it has been considered to be a good effect prediction tool. At NIVA we have found it very useful to predict effects of reactive labile aluminium (Al) and to some extent also iron (Fe) in acid water. The DGTs predicts both gill uptake and blood plasma stress responses from aluminium.

Marine and freshwater sediments The DGT sediment probe has lately shown promise to determine high resolution profiles of metals ions in sediments. The data achieved can be used to get a profile of metals in the pore water. This can be used to predict release potential


of the metal and also to estimate flux rates of metals out of the sediment into the water phase. This information is useful when planning remedial actions of contaminated sediments.

Water covered mine tailing sediments Similar to sediments, the DGT probe has lately shown promise to determine high resolution profiles of metals ions in sediments. The data achieved can be used to get a profile of metals in the pore water. This can be used to predict release potential of the metal and also to estimate flux rates of metals out of the sediment to the water phase.

Water quality surveys in aquaculture The DGTs can be used to document water quality and assess risks for toxic effects. Presently the DGT samplers are used in NIVA’s water quality services (VK2003, VK2004) in Norwegian aquaculture.

“Sniffer” to detect sources of metals pollution in watersheds and recipients The time-integrating property of the DGT may b every useful for screening watershed areas for intermittent sources of metal pollution. It is more difficult to come around an integrating DGT sampler,

Literature references

Davison, W., and Zhang, H. 1994. In situ speciation measurements of trace components in natural waters using thin-film gels. Nature, 367, 546–548.

Davison, W., Fones, G., Harper, M., Teasdale, P., and Zhang, H. 2000. In situ environmental measurements using dialysis, DET and DGT, in In Situ Monitoring of Aquatic System - chemical analysis and speciation, Buffle, J. and Horvai, G (Eds.), IUPAC, John Wiley & Sons Ltd.

Davison, W, and Zhang, H. 2001. In situ speciation measurements using diffusive gradients in thin films (DGT) to determine inorganically and organically complexed metals. Pure and Applied Chemistry, 73: 9–15.

Garmo, Ø. 2002. Laboratoriestudium av teknikken diffusive gradients in thin films for bestemmelse av frie ioner og labile spesier. Cand. scient. thesis, Dep of Chemistry, NTNU, Trondheim.

Garmo, Ø., Røyset, O., Steinnes, E., Flaten, T.P. 2003. Performance study of diffusive gradients in thin films for 55 elements. Analytical Chemistry, 75: 3573–3580

Zhang, H. and Davison, W. 1995. Performance characteristics of the technique of diffusion gradients in thin-films (DGT) for the measurement of trace metals in aqueous solution. Analytical Chemistry, 67: 3391–3393.

Zhang, H., and Davison, W. 2000. Direct In Situ Measurements of Labile Inorganic and Organically Bound Metal Species in Synthetic Solutions and Natural Waters Using DGT. Analytical Chemistry, 72(18): 4447–4457.

Contact persons at NIVA

Oddvar Røyset, [email protected] DGT sampling, analytical issues Torstein Kristensen [email protected] Aquaculture Åse Åtland [email protected] Aquaculture, fish response Morten Schaaning [email protected] Sediment studies





Annex 5 Joint research of The Netherlands and Belgium on (bio)availablity

Estimation of availability of PCB and PAH in sediment samples from the Western Scheldt using solid phase sampling

F.Smedes, P. Roose, E. Monteyne and M. Neijts

Introduction

At present the risk of contaminated sediments is assessed using the total contaminants concentration in it. However often a considerable fraction of this concentration is not available for uptake by organisms. The concentration in the water phase, i.e., that can be released from the sediment, seems a more realistic criterion. The different available methodologies have been extensively discussed in previous meetings of WGMS.

The basic principle is that in a sediment-water mixture the concentration in the water phase in equilibrium with the sediment is determined using Solid Phase Samplers (SPS) made from silicone rubber film. The SPS is actually operating as a reference phase that is equilibrated with a sediment water mixture and accumulates the compounds from the free dissolved water phase because of the higher solubility of hydrophobic compounds in silicone rubber compared to water. After equilibrium has been obtained (time required is about 20 days) the concentration in the water phase can be calculated from the content measured at the SPS using the silicone rubber-water partition coefficient (KSPS). By equilibration of different ratios of silicone rubber and sediment, different degrees of sediment depletion (i.e., extraction) occur. By relating the concentration extracted from the sediment with the determined concentration in the water phase, a value for maximum depletion is obtained by extrapolation to zero concentration in the water phase. Extrapolation to zero sediment extraction results in the free dissolved concentration in the water phase for a non-depletive situation. Because of the high accumulation of compounds in the silicone rubber, detection limits are not relevant for the precision of the results. Free dissolved concentrations around 0.001 ng/l can be measured.

The Netherlands and Belgium offered to perform a kind of pilot exercise with sediment samples from the Western Scheldt.

Methods

Silicone rubber foils of 0.5 mm thickness were cut in pieces of 4*6 cm ( = 50 cm2) and foils were pre-extracted in a Soxhlet with ethylacetate for 100 hr2. All extracted foils were collected in a wide-mouth bottle (A) and washed twice with methanol for one hour. However foils were spiked with reference compounds; they were not further used in the exercise.

Spiking was performed adding the reference compounds to the foils while soaked in methanol, e.g. for each foil 30 ng CBs (29, 155. 204) and 100 ng for PAHs (Ant-D10, Pyr-D12, Pe-D12). The mixture is shaken for 2 hours and water is added to obtain 80% methanol followed by shaking of another 6 hours. After that water is added to get 50% methanol and again shaken overnight. Foils are stored in this way (50% methanol) prior to use3.

Sediment samples were taken in 10-liter polypropylene containers. Samples were mixed manually and sub-samples were taken in different quantities and brought in a glass jar together with a SPS. In addition in sub-samples, the dry weight was determined for each sample. Where necessary, just enough water was added to liquefy the sediment. All jars were place on a shaker and mixed during two weeks (two duplicates were exposed for a much longer time (several months). After exposure the films were recovered, rinsed with Milli-Q and wiped with a tissue. The films were then rolled and Soxhlet extracted with 25% acetone in hexane for 6 hours. In case the extracted weight of the foil was unknown, the silicone rubber films were dried to constant weight and the weight was registered4. The extract was

2 Material released by the silicon rubber films can cause a residue that only solves in hot ethylacetate and consequently contaminate the receiving flasks. Keep a set of flasks separate for pre-extraction purposes.

3 Foils are not dried to avoid contamination through absorbtion of contaminants from air.

4 Foils can be reused but pre-extraction is again required (see note 3). For recycled films with known weight or adjusted weight, weighing is not necessary and they can be reused without preextraction provide they are not exposed to air. Put them in flask with methanol.


Kurdena Danish concentrated to 1 ml followed by a clean-up with 4 gram Al2O3 (10% water, using 25 ml of hexane to pre-rinse the column) and the compounds were eluted with 25 ml hexane. The eluate is concentrated to 1 ml, internal standards for calculation were added (CB 143 and 2-methylchrysene; in amounts that were in accordance with expected end volume). After addition of 5 ml Acetonitril (ACN) the extract is Kurdena Danish evaporated on a water bath to 1 ml or less. A nitrogen flow was used for the last evaporation. The extract is then transferred to a column with 0.3 gram C18 silica that was pre-rinsed by 3 ml of ACN. After quantitative transfer of the extract, the compounds are eluted by 3 ml of acetonitril. A sub-sample is taken for PAH analyses and diluted or concentrated as was required for HPLC analysis.

To the rest of the extract, 10 ml hexane is added followed by Kurdena Danish evaporation on a water bath to 1 ml or less. This extract was subjected to a clean-up over silica gel as normally performed for the analysis of CBs in sediments. Also the step with de-sulphuration, sonification in the presence of copper powder was included.

Further analyses followed the same procedure as sediment extracts. Results are expressed as ng/g silicone foil.

With each 10 samples also one spiked film that was not exposed was analysed. The results of blank foils are used for reference of the spiked amounts of standards. Blank amounts of compounds are not subtracted as they simply contribute to the equilibrium process. Only very large amounts, more than the amount in half a gram of sediment, may have some influence. The procedural bank should anyhow be subtracted.

Spiked standards that need to be determined were

Anthracene D10, Perylene D12, CB29, CB155 and CB204

Results

Figure 1 shows the locations in the Western Scheldt where the samples were taken. In Table 1 the details of how sediment/water mixtures were composed, as well as the dry weight content and the phase ratios, are shown. The phase ratio is expressed as the weight of SPS per gram of dry sediment. In Table 2 the results for some PAHs and CBs are listed. Only a few PAH compounds are reported as the spiked reference compounds and the internal standards used interfered with each other. For CBs a similar confusion occurred for CB29 and CB155. Finally CB143 was used to calculate the final concentrations. Tables 3 and 4 are calculated from Tables 1 and 2. Table 3 shows the free dissolved concentration in the water phase (CW) calculated from the concentration on the foil and the partition coefficient, listed in the top row of Table 3. The calculation is done according to:

SPSSPS

SPSW Pm

QC

.=

where QSPS is the amount measured on the SPS, mSPS the mass of the SPS and PSPS the water-silicone rubber partition coefficient. A higher phase ratio leads to a higher extracted concentration from the sediment and consequently a lower resulting concentration on the SPS. Actually, the amount on the SPS is also the amount extracted from the sediment. This means that also the concentration extracted from the sediment (CSedEX) can be calculated for each individual phase ratio by:

Sed

SPSSedEX m

QC =

The CW is plotted versus CSedEX, as for example in Figure 2. Extrapolation of a regression line through the points to a CSedEX of 0 will give the CW that would be found when an infinitely small SPS, i.e., low phase ratio, would be used and no extraction of sediment has taken place. This value can be read from the y-axis.

The other end, where the regression line crosses the x-axis, suggests an infinitely large SPS (or infinitely small amount of sediment), the situation exists where the free dissolved concentration (CW) is zero. Consequently, the sediment has released the total amount of the compound available for water exchange and CSedEX represents the maximum water extracted concentration. Figure 2 show an example for S15. The open symbol is the result after much longer exposure time showing that two weeks seems sufficient for fluoranthene under the present conditions.


From other work it is known that the uptake rate is related to shaking intensity, suspension density, the phase ratio and the partition coefficient between water and silicone rubber. Considering that sand is a diluter and only the suspension density of the fines is relevant, the actual suspension density in the sediment water mixtures is unknown.

It is expected that compounds as CB153 are not in equilibrium for the given time period. Nevertheless, the graphs show reasonable results as shown in Figure 3. Also a number of data sets show unrealistic results (Figure 4).

Not being too critical of the data, unaffected CW values were calculated for all locations, except where an extrapolation of more than a factor of 2 was required to reach the y-axis. The free dissolved concentrations given by the sediments from the different locations are plotted in Figure 5 for pyrene and CB153. Extrapolation to obtain the maximal CSedEX generally exceeded a factor 2 and was not limited. The maximum sediment extracted concentrations are presented in Figure 6.

Figure 5 shows a logical profile for the Scheldt estuary with high concentrations near Antwerp (S22) decreasing seawards. The gradient is rather steep and therefore plotted on a log scale. The profiles for the concentrations extracted from the sediment also show a decrease but also towards Antwerp (for S22). This would mean that sediment results would suggest that the input is located more seaward! This doe not have to be true as the lower extractable concentrations for S22 are due to a grain-size effect. The samples at S22 were much more sandy than at S18 and S15.

When comparing the profiles of both Figure 5 and 6, it can be noted that the free dissolved concentration only decreases by one order of magnitude while for the sediment a decrease of three orders of magnitude can be observed. The decrease of the free dissolved concentration represents the decline of the contamination level, while for the sediment the decrease is mainly caused by a grain-size effect (two orders of magnitude) and only for one third by the decline in the contamination level (one order of magnitude).

Conclusions

Although, due to communications the measurements are not in all cases of adequate quality, the results are a strong indication that the method proposed at WGMS2003 has a strong merit to reflect the contamination level, i.e., which sediment is the “hottest”, both in terms of free dissolved concentrations that sediments are able to give to the water phase, as well as the content that can be released to the water phase.

igure 1. Sample locations in the Western Scheldt are indicated by Sxx. A circle indicates the ones used in this project.

F


Figure 2. Decrease of the dissolved concentration of fluoranthene in the water phase in relation to the extracted content from the sediment (Location S15). Open circle is duplicate exposure with much longer equilibrium time (several months instead of 2 weeks).

Figure 3. Decrease of the dissolved concentration of CB153 in the water phase in relation to the extracted content for the sediment from location S22.

Figure 4. Decrease of the dissolved concentration of CB101 in the water phase in relation to the extracted content for sediment from location S01. Relation is not very clear and large extrapolation is required to obtain a value for CW.

S15

y = -0.05x + 32

R 2 = 0.82

0

5

10

15

20

25

30

35

0 50 100 150 200

µg/kg extracted from sediment

ng/l

Fla

S15

y = -45x + 220R2 = 0.99

0

50

100

150

200

250

0 1 2 3 4


pg/l

CB153

S01

y = -1650x + 41

R 2 = 0.69

0

5

10

15

20

0 0.01 0.02 0.03


pg/l

CB101


CB153 (pg/l) obtained by extrapolation to zero sediment extraction for

tions with infinitely large SPS, i.e., low or zero free dissolved concentration. 10.

Figure 5. Free dissolved concentrations for pyrene (ng/l) and the different locations.

1S01 S04 S0

10

100

1000

7 S12 S15 S18 S22

ng/l Pyrpg/l CB153

10

Figure 6. Extrapolated values for the extracted concentraNote that the extracted CB concentrations are multiplied b

0.1

1

S01 S04 S07

100

1000

S12 S15 S18 S22

µg/kg Pyr µg/kg CB153(X10)

y


T

T mra

L

S

S

S

able 1

he ex onths. Phase tio i

oca Raw

Susp Dens.

g/g

. Composition of exposure mixtures.

posure time was two weeks except the foils in the grey-shaded rows that were exposed for severals expressed as weight of SPS per gram dry sediment.

tion Id nr SPS

weight

g

Wet

Sediment

g

Water

added

g

Dry

weight

%

Dry

Sediment

g

Phase

Ratio

030217–01 1.71 1250 80 80 1000

030217–02 1.71 500 30 80 400

030217–03 1.71 120 8 80 96

030217–04 1.71 1000 125 84 840 0.0020

030217–05 1.71 217 37 84 182

030217–06 1.71 1200 81 972

01 0.0017 0.75

0.0043 0.75

0.0178 0.75

04 0.75

0.0094 0.72

07 0.0018 0.81

030217–07 1.71 200 25 81 162 0.0105 0.72

S12 030217–08 1.65 500 40 64 320 0.0052 0.59

030217–10 1.71 100 10 64 64 0.0267

S15 030217–11 1.71 1069 50 40 428

030217–12 1.71 205 10 40 82 0.0208

030217–13 1.71 20 4 40 8

030217–14 1.71 200 10 40 80 0.0213

S18 030217–15 1.71 250 50 48 120

030217–16 1.71 430 80 48 206

030217–17 1.71 38 8 48 18

030217–18 1.71 15 8 48 7

S22 030217–19 1.71 1222 80 75 917

030217–20 1.71 231 ? 75 173

030217–21 1.65 57 ? 75 42

0.0098 0.75

0.0389 0.75

0.0083 0.40

0.0935 0.40

0.2369 0.31

0.0019 0.70

0.38

0.0142 0.40

Long

0.38

0.2133 0.33

0.0053 0.59

0.58

0.0040 0.38

320 64 40 500 1.71 030217–09 Long


Table 2. Amount in ng per SPS of the different amounts after exposure to sediment. Gray is extended exposure time.

Ratio CB52 CB101 CB118 CB138 CB153 CB180

S01 0.0017 83 238 269 7 16 19 18 47 29

Phase Ant Fla Pyr CB28

0.0043 77 114 155 7 10 14 0

0.0178 70 61 86 2 2 3 5 3

S04 0.0020 240 359 364 2 56 105 82 25 79 15

0.0094 97 130 146 5 6 10 0 8 23 0

S07 0.0018 324 375 517 5 15 33 34 35 88 49

0.0105 97 318 368 20 14 16 10 10 26 0

S12 0.0052 1026 701 1116 11 66 116 81 97 241 144

0.0053 240 1346 1395

0.0267 362 455 850 7 27 50 33 40 110 59

S15 0.0040 3543 1632 2496 128 222 160 226 525 298

0.0208 1969 1597 2445 92 168 134 184 422 268

0.2133 432 1279 1813 37 71 61 93 210 213

0.0213 526 1780 2186

S18 0.0142 4622 6977 5534 11

0.0083 4394 7285 5729 19

0.0935 1888 5118 4261 6

S22 0.0019 5784 4731 4827 130 188 211 191 423 288

0.0098 2057 4150 4457 71 112 141 123 271 216

0.0389 25 34 51 31 62 129 112


Table 3. Concentrations in the water phase calculated through the partition from the content on the SPS in Table 2. Note that PAHs are in ng/l and CBs in pg/l. Gray is extended exposure.

Ratio Pyr CB28 CB52 CB101 CB118 CB138 CB153 CB180 Phase Ant Fla

Log KSPS 4.1 4.5 4.6 5.1 5.4 5.7 5.9 6.2 6.2 6.4

ng/l pg/l

S01 0.0017 4 14 7 7 4 4 15 19 1 7

2 8 4 5

1

S04 0.002 5 9 130 3 60 9 0 11 7 12 29 3

0.009 2 24 15 3 8 4 5 2 12

S07 0.001 8 21 35 39 25 13 33 11 8 15 7

0.010 5 94 4 7 4 5 5 6 3 19 10

S12 0.005 17 54 159 0 62 37 92 35 2 49 13 14

3 11 25

0.026 13 30 64 58 24 15 41 14 7 17 8

S15 0.004 37 299 9 118 84 4 0 165 30 25 19 70

0.020 36 216 6 99 68 6 8 92 30 19 15 62

0.213 27 86 83 45 34 78 50 3 20 24

3 24 33

S18 0.014 81 26 2 215 129

0.008 84 44 3 205 135

0.093 63 15 5 88 95

S22 0.001 71 304 0 156 71 7 9 269 88 22 15 67

0.009 66 166 0 104 45 0 8 96 77 13 10 50

0.038 122 81 61 23 24 49 27 9

0.0043 4 2

0.0178 3 1 5 3 1 2 1

0.005 21

0.021 32


Table 4. Content extracted by SPS in ng per gram of sediment. Gray is extended exposure.

Phase Ant Fla Pyr CB28 CB52 CB101 CB118 CB138 CB153 CB180 Ratio

S01 0. 0.01 0.01 0.01 0 0. .00017 0.03 0.03 0.02 .01 03 0 1

0. 0.02 0.01 01 03 0 0. 0043 0. 0. .02 02

0. 0.06 0.02 0.02 0.09 0.05 0 0.01 0178 .02 0.03

S04 0. 0.02 0.01 01 0.02 0.26 0 0. 0.01 0020 0. 0.25 0.12 .02 06

0. 0.04 0.02 02 0.23 0.14 0 0. 0094 0. 0.11 .03 08

0. 0.05 0.06 06 36 0.20 .07 0 0105 0. 0.98 0. 0 .04 0.10

0053 6 0.13 0.11

0. 0.45 0.22 33 70 1.55 .64 0 0.37 0267 0. 0.81 1. 0 .40 1.09

S15 0. 0.66 0.12 15 1.19 .47 0 0.28 0040 0. 1.04 0 .33 0.77

0. 1.91 0.62 75 4.49 4.08 .06 1 1.30 0208 0. 2 .42 3.25

0. 4.29 5.06 69 18.34 1 7 16 102133 5. 17.7 9.60 .34 .54 .61

0213

S07 0.0018 0.03 0.01 0.01 0.04 0.06 0.07 0.04 0.02 0.06 0.02

S12 0.0052 0.25 0.07 0.09 0.28 0.82 0.72 0.32 0.19 0.48 0.18

0. 0.0

0. 0.52 0.70 0.69

S18 0.0142 3.06 1.84 1.16 0.38

0.0083 1.69 1.12 0.70 0.36

0.0935 8.22 8.87 5.87 1.41

S22 0.0019 0.50 0.16 0.13 0.57 0.41 0.29 0.13 0.29 0.12

0.0098 0.94 0.76 0.65 1.63 1.28 1.02 0.45 0.99 0.50

0.0389 4.73 3.15 2.38 0.91 0.92 1.92 1.05


Annex 6 Development of indicators for sediment contamination

Developm practical ind ors o viron q is n m in es m monitoring sments to the general public. It is also important in terms of describing environmental state in terms so that temporal trends in monitoring information are capable of showing/indicating improvement which can be linked to a

t respon Comm to a dicat are several p ples rele to t n iment ontaminat

Definitions of an indicator:

everal de of an indica ear the literature. An dicator can be;

• “Physical, chemical and biological or socio-economic measures that best represent the key elements of a complex ecosy en nment A ndicat emb n a l-dev oped inte retative framewo and has mean ond the measure it represents” (Ward et al. 98);

An in sed measurements one or re en nment ariabl collect at som int in ime and space which is relevant to the management goal (Nicholson and Fryer, 2001);

• Quantified information that is capable of showing environmental change over time (UK Environment Agency – DEFR 2).

eria t be d indicator:

Indicators may be developed in terms of two objectives:

) Decis por “perfo ance” catorsEnvir al s r “d tive icato .

here are ite hich ld de e a “g r but the comm n factors are listed elow (from Ward et al., 1998). Each type of indicator will have different features.

ecision S or erform ce” In ators s ould be

Monitored regularly with relative ease and cost-effectiveness; • Relevant to the decision-maker and to the decision (i.e., to policy and management needs); • Sensitive to manageable human activity; • Tightly linked to human activity; • Responsive to human activity but not to other causes of change; • Measurable over a large proportion of the target area. Environmental State or “Descriptive” Indicators should be:

• Scientifically sound and technically robust; • Simple and easy to communicate; • Capable of being monitored to provide statistically robust data that can illustrate trends over time and apply

preferably to a broad range of environmental regions; • Provide an early warning of potential problems; • Sensitive to the change that it is intended to represent; • Cost-effective. In terms of testing and evaluation, indicators should:

• Undergo a period of testing; • Be subject to a “probationary period”, during which results are treated with caution;

ent of asses

icat f en mental uality importa t in co municat g the r ults fro

managemen se. on ll in ors rinci also vant hose o sedc ion.

S finitions tor app in in

stem or viro al issue. n i or is edded i wel el rp rking bey , 19

• dex ba on of mo viro al v es ed e po t

A, 200 Crit o descri a goo

1 ion sup t or rm indi . 2) onment tate o escrip ” ind rs T many cr ria w wou scrib ood” indicato o b

D upport “P an dic h :

•


• Be tested with real data, which may need to be gathered or mined; • Use hi e b alid to ri n • Be statistically robust; • Be fit for purpose (i.e., applicable to time-series);

Be e ty mBe p ap at

• Capable of being up-dated regularly.

Overview of present EU indicators relevant to sediment contamination or approach

The section below summarises the approaches taken by the EEA (European Environment Agency) which is the lead uropean a vo n t t iro al cator al xample of an application

of this approach within the UK in terms to developing indicators of seabed disturbance.

EEA Approach

The basis of EEA Reports (EEA, 2002 and 2003) on the testing of indicators for the marine and coastal environment is SP s fra rk te fo on ur ec rin uts te (of hazardous

anc ri vir t) m (b cal ts, im . I is to develop a common set of indicators to support policy framing and implementation.

Indicators are items of quantified information that help explain how the quality of environmental changes over time or atially la al em isi sig nc vi ge rogress made on

route to sustainable development. Indicator reporting by the EEA will be based on annually updated information.

The Dangerous Substances Directive and OSPAR Convention require trend measurements. The EEA aims to use these end me ve sta ca r. Alth S as t a d t ica proach, this EEA

testing aims to show whether and how OSPAR data can be used for the EEA core set on indicators for hazardous bstanc

hese re c he ss he ts testing of pote tial ind ors f porting by means of entifica a ila da ab d ata pro ssing of a selected set of descrip ve parameters for the

policy issue hazardous substances. Testing focused on inputs of hazardous substances into the marine environment for tial tor th en ation o rd s subs nces in sedime for po ntial state indicators.

Due to the lack of reliable and comparable data, testing concentrated on the method for compiling data and the resentat n

uring testing, an in of R ata on iu concentration sed ent in astal waters, raised questions about the reliability and comparability of data. In some cases, different units were used when reporting to the

ase e e q na e. Ther so of m and tical procedures. It was concluded that reliability and comparability of the data were not sufficient using the data currently available to

evelop s r.

he usef concen rations of haz s ce se ts im w the data set on oncentr c mplete (e.g., a time-serie t l y nd ke eli an parability of the

data. An improvement in the quality of the data and the methodology used for combining the inputs is also required. erforming trend analysis within the improved data may then indicate that this parameter has indicator potential.

An example of a proposed state indicator on concentrations of hazardous substances in organisms was presented in the report. This indicator has been developed using OSPAR Background Reference Concentrations (BRC) and Ecotoxicological Assessment Criteria (EAC). For reasons of comparison, concentrations of hazardous substances in organisms can be translated into uniform and comparable units. An Ecological Reference Index (ERI) is determined by dividing the concentration of a hazardous substance in the organism by the BRC or the upper limit of the EAC range. The resulting value represents an ecological reference or a potential for environmental effects. Assuming that ecological references of a number of substances are independent (no synergistic or antagonistic effects), the sum of the individual ERIs produces an aggregated or combined ERI. This approach was tested using OSPAR data on concentrations of hazardous substances in blue mussel. A decreasing trend was observed in ERI data during the period of 1990–1996.

data w ch hav een v ated quantify their va ability a d to ensure their quality;

• of suitabl quali and no ore; • altered and/or ada ted as propri e;

E organis tion in lved i he developmen of env nment indi s and so an e

the Dsubst

IR asseses in ma

ment ne en

mewoonmen

. This and I

sting pact indi

cuses cators

Pressiologi

e (Dir effec

t/Rive e.g.,

e Inpposex)

), Stats aim

sp vary, and they p y a vit role in phas ng the nifica e of en ronmental chan and p

tr asurements to de lop a te indi to ough O PAR h not ye dopte he ind tor ap

su es.

Tid

ports destion of d

ribe tta ava

procebility,

and tta reli

resulility an

of d

n icat or EEA retice

poten pressure indica s and e conc tr f haza ou ta nt te

p ion of tre ds.

D exam ation OSPA d cadm m s in im co

datab and, ther fore, results ar uestio bl e is al a lack metadata on sa pling analy

d uch an indicato

Tc

ulness oations is

f o

t ardouss of a

ubstaneast 10

s in ears) a

dimen chec

may d for r

proveability

hen d com

P


This indicates that the ERI appears to provide a suitable indicator for concentrations of hazardous substances in organisms.

nt monitoring programmes (mainly the UK NMMP, National Marine Monitoring Programme) could be developed into indicators of seabed disturbance. The framework adopted was the DPSIR approach (as used by the EEA

arlier OECD “Pressure-State-Response” model) focusing primarily on the P, S and I indicators in terms of effects of aggregate extraction, disposal, fisheries and near-shore disturbance.

Proposed indicators were ranked into three types depending on information and data available. These were:

a) b) e AQC groups;

Seve roposed indicators linked to sediment contamination are given below in a table. These proposed indic d and validated to ensure robustness, reliability and quality before adoption, in order to ensure ffective reporting of the state of the marine environment. The full descriptions of each indicator appear at the end of

aminant indicators (including sediments) for effective impact management, indicators of effects in terms of biological response are important. This continuum links into the existing

3) and also background concentrations (BCs) and Environmental ment of sediment contamination indicators should be developed

h da item 3).

• National sediment quality criteria (SQCs) based on concentration data of sediment. This method requires analyses een given criteria.

• Enrichment factors based on the ratio between surface sediment concentration and the local background

t the results cannot in a ts in the sediment as other natural factors can be unfavourable to the

eir own right and are reported at present as part of many on a considerable task but under monitoring programmes me element of trend analysis should be possible.

Application of the DPSIR approach; UK development of indicators for seabed disturbance

A UK meeting in 2002 funded by DEFRA (Department for the Environment, Food and Rural Affairs) considered how outputs of curre

and a development of the e

Indicators that require testing and evaluation with existing data sets prior to full adoption but could be used now; Indicators that require some refinement from the National Marin

c) Indicators that require further R&D work before they can be adopted.

ral examples of pators will be teste

ethis annex.

The indicators listed here indicate that in terms of cont

frameworks of sediment quality criteria (ICES, 200Assessment Criteria (EACs). In this way the developwit bioavailability of contaminants in mind (see agen

At present the following methods are used to state the quality of the sediment:

of one or several of the elements or substances that have b

concentration. Only to be applied for stable elements. • Toxicity-tests on selected organisms or embryos. The problem with the toxicity tests are tha

simple way be related to the contaminanorganisms.

The criteria above can be used as interim indicators in thm itoring programmes. For each method, collation of data isso


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46 ICES WGMS Report 2004

At this time, examples of the development of sediment contamination indicators were not available in addition to the e approach is useful in

terms of looking ahead to improvement of sediment contamination indicators:

that eutrophication triggers a chain of effects starting with increased primary production, subsequently followed by increased sediment

r. The end-point of the chain is that the subsequent wipeout of the macrobenthic fauna leads to a turnover from bioturbated to

in e es r en diment cores, a diagram is t n percent of the accumulation bottom area.

he area of sediment which has this condition can also be plotted with time.

determine ecological quality of sediment communities

Maria Jesus Belzunce presented some work on “the use of benthos in ecological quality objectives: the development of

ro

rjwith his index, based upon sensitivity/tolerance of benthic fauna

provpresen ed some examples in which the index was validated and applied to different impact sources and

graphical areas. One of the conclusions is that change of the index is not easily related to sediment contamination as

A program to calculate and represent the index is available (free of charge) in AZTIs web page (www.azti.es)

Case studies of indicator development:

quality assessment methods listed above. Below are two examples of indicator development whos

Example of indicator development for eutrophication

Per Jonsson presented an approach to use changed distribution of anoxic/hypoxic laminated sediments as an indicator of severe changes in the soft-bottom macrobenthic fauna. The approach is based on the assumption

accumulation, increased degradation of organic material causing oxygen depletion in the near-bottom wate

lam ated sediments. After mapping the sediment distribution (erosion, transportation and accumulation bottoms) in thinv tigation area, sediment cores are taken and examined. The cores are dated assuming annual lamination and the yeawh lamination first occurs is calculated. Based on a number of such examinations of secrea ed showing the historical development of the laminated azooic area iT

During spring 2004, this approach will be further developed and suggested to become a national Swedish quality criteria related to eutrophication. It may be used to evaluate the eutrophication situation in the Baltic Sea and enclosed coastal waters of the Kattegat/Skagerrak.

In this case this indicator of extent of anoxic areas (state or impact) can be linked to other indicators of inputs (pressure/driver) to help demonstrate the effects of eutrophication or improvement of environmental quality given management actions locally or potentially in future in the Baltic.

Example of the development of a Marine Biotic Index (AMBI) to

a Marine Biotic Index”. This study shows the use of macrobenthos communities to evaluate the alteration of the marine envi nment due to different pollution sources.

Bo a et al. (2000) proposed a Marine Biotic Index (AMBI) to establish the ecological quality of sediment communities in the European estuarine and coastal environments. T

to stress gradients, classifies macrofauna species into five ecological groups. The distribution of these ecological groups ides a biotic index of five levels of pollution classification, as in the Water Framework Directive (WFD). The

tation showgeoother natural factors may be unfavourable to the organisms. However, it could be used in the establishment of the ecological status of the marine environment. Examples of the application of this method are given in Borja et al. (2003).

. The list of benthic taxa and the program are continually updated.

Way forward: General discussion

From the above summary it is apparent that there are some indicators of sediment contamination proposed at present but these are mainly limited to total concentrations. Of the indicators proposed, most are at the stage of testing and validation (UK). In relation to sediment hazardous substance indicators developed by the EEA, there is still a need for improved reliability, comparability, and quality of the data and longer time-series for the usefulness of the indicators to be assessed.

At this time, there is no new insight into novel indicators of sediment contamination and in future this will need to be revisited in the context of issues of bioavailability and biological effects. At present, it would be possible to use sediment quality criteria (SQCs) developed so far and potentially aim towards a composite contaminant indicator.

The issue of indicators identification and testing will carry on in future in terms of a new and emerging monitoring framework from OSPAR and the WFD which requires an improved reporting system based on indicators. The EEA has

adopted aapproach aindicators undata on c(BCs) an

ICES WGMS Report 2004

n indicators-based reporting system using the DPSIR (Driving force, Pressure, State, Imnd development is ongoing. The revision of the OSPAR JAMP is also likely to embrace

der a similar DPSIR-type model. Similarly, the 2005 JAMP assessment will be undertakontaminant concentrations and biological effects collected under CEMP. Revised Background Cd Environm al Assessment Criteria s) are being developed und PAR SIME and ICES and will

facilitate assessmen f sediment contaminatio d impact assessment.

In the interim, ment Quality Criteria (SQCs) in comparison with BCs and provide a good framework for sediment contamination assessments and a range of potential indicators.

References

Borja, A., Franco, J., and Perez, V. 2000. A Mari ex to establish the ecological quality of soft-bottom benthos with e European estuarine and e Pollution Bulletin, 40: 1100–1114.

Borja, A., Mu , I., and Franco, J. 2003. Th ine Biotic Index to different impact sources affecting ttom benthic communities al e Pollution Bulletin, 46: 835–845.

DEFRA. 2002. Proceedings of the seabed disturbance workshop, Essex, UK. February 2002. EEA. 2002. Testing of Indicators for the marine and coastal environment in Europe Part 2: Hazardous Substances EEA

technical report No. EEA. 2003. Part 3: Prese t State and developme f indicators for eutrophication, hazardous substances, oil and

ecological quality. EEA Technical Report . ICES. 2003. Inventory imen ality criteria and how they are derived. rt of the Working Group on

Marine Sedments on Pol tion. IC 003/E:04: 18-47. NMMP. 2001. Pr th MP i orkshop, Leith, Edinbu , 2–4 May 2001. Available on

ww arlw.mn anm

., Buari

entts o

i

(EACn an

er OS

EACs canthe Sed

ne Bio coastal env

e applicatioong E

tic Indironments. Marin

n of a Maruropean coasts. Marin

in thxikasoft-bo

85. n

of sed in reldingk/nm

nt o. 86

M 2ors w

s No

ES Cndicat

t qulu

e NMm

In Repo

rghati

s ofpr/n

oceeac.uab. mp.ht

Fryer. 2001. Manageme s, Indicators a cs. Discussi

te ohe sea

47

pact, Response) the use of such en in context of

oncentrations

Nicholso d nt Goal nd Indicator Statisti on Document for NMMP

WG eeting 11 December 2001. Ward, T utler, E., and Hill, B. 1998. Environmental indicators for national sta f the environment reporting –

est es and t . Department of the Environment, Canberra, Australia.

48 ICES WGMS Report 2004

ent contamination indicators derived for dredged material disposal (from DEFRA, 2002).

Indicator Name: D5. Individual load of specific contaminants

Full descriptions of proposed UK sedim

ACTIVITY: Disposal

Indicator Type: P S I Category: A B C

Brief description: Individual load of specific contaminants in dredged material deposited at sea, including selected OSPAR metals/organotins/PAHs/PCBs.

Unit of measure: Tonnes?

Rationale/policy relevance: Important that levels of contaminants in dredged material licensed for disposal are maintained at levels which will not harm the environment.

iments/impacts on biota.

Data sources:

agree on common approach to development of action levels. End of 2003 as a target to agree nationally on action levels

Links to other indicators: Quantities/concentration of contaminants in sed

Targets (if applicable): 100% of material has contaminant loads commensurate with agreed action levels.

Measurement/analysis/interpretation: Approach to be agreed. Methods will define numbers (digestion method, etc.) (normalising PCBs?).

Outputs/presentation: Graphics - aggregated metals/total PCBs/PAHs.

FEPA licensing authorities.

Limitations of the indicator: Limitations of methods/normalising. Not fully effective until an agreed national approach on action levels has been developed.

Follow-up actions to progress indicator: To develop indicator-related to disposed load above action levels. FEPA administrations to meet by the end of 2002 to

for at least a subset of key contaminants.

ACTIVITY: Disposal

Indicator Name: D10. Concentrations of specific organic contaminants in sediments at selected representative disposal sites


representative disposal sites in particular organotins/PCBs/PAHs.

Unit of measure:

Impo redged

Link

Sam ars.

Outputs/presentation: Simple graph – amount above reference level – then aggregated.

Data sources: Develop targeted monitoring programme at selected representative disposal sites.

Limitations of the indicator: Monitoring data not yet available – the gathering of it would impose additional costs on industry. Number of sites monitored. Source certainty?

Follow-up actions to progress indicator: Development of representative monitoring site monitoring programme if considered appropriate. Develop a programme to integrate with the Water Framework Directive monitoring requirements. Conversion of site-specific data to a UK indicator. Need to decide whether or not to normalise measurements?

Brief description: Concentrations of specific organic contaminants in sediments at selected

Normalisation? ppm/ppb.

Rationale/policy relevance: rtant to assess levels of organic contaminants present in the marine environment as a result of licensed d

material disposal.

s to other indicators: Specific contaminant loads/sediment chemistry (NMMP)/impacts on community structure.

Targets (if applicable): [(Below the limits of detection of the best available techniques for synthetics and background for PAHs.) Reach WFD requirements. Local reference sites/disposal site concentrations –] no unacceptable? Increase in concentrations above local control stations.

Measurement/analysis/interpretation: pling difficulties. Aim for around 20 representative disposal sites over two ye


http://www.marlab.ac.uk/nmpr/nmp.htm

ACTIVITY: Disposal

Indicator Name: D6. TBT-induced Imposex in Whelks


B n:

BT-induced Imposex in Whelks (as defined in accordance with OSPAR guidelines).

ce: to assess endocrine-disrupting effects of TBT remobilised as a result of licensed dredged material disposal.

Targets (if applicable):

Measurement/analysis/interpretation:

Outputs/presentation: ighly impacted than the local control stations.

Data sources: around 20 representative disposal sites with the NMMP survey data.

Limitations of the indicator: f whelks. Monitoring data not yet available – the gathering of it would impose additional costs on

:

rief descriptioT

Unit of measure: As per OSPAR guidelines.

Rationale/policy relevanImportant

Links to other indicators: Contaminant loads/levels of contaminants in sediment/impact on community structure.

As per OSPAR guidelines.

As per OSPAR guidelines.

% of the representative sites that are more h

Comparison of data from

Presence/absence oindustry.

Follow-up actions to progress indicatorDevelopment of representative site monitoring programme if considered appropriate.


Annex 7 SPM monitoring in the Netherlands

overview of fifteen years of monitoring

F. Smedes

Suspended matter in marine areas has similar properties to sediment and can be considered to be past and/or future is often reflecting the contamination history of past water pollution, the suspended matter is

ollow the contamination level of a water mass. The water phase is usually a mixture of th different uptake capacities and suspended matter is one of them. Concentrations in raw

water are often a function of the suspended matter content, but also after filtration of water samples, more dissolved bility in the water phase and consequently higher concentrations of contaminants are

he water phase are generally very low even if all compartments are sampled, let alone when a single compartment is isolated. Of all compartments in the water phase, the suspended matter shows the highest concentrations

n minants. Suspended matter is often collected by filtration. However, collection off this l can be isolated. Secondly,

adsorption of contaminants from the water phase by the filter material can lead to an overestimation of the content on ther more robust technique is the application of a flow-through centrifuge. Several cubic

is also a useful parameter for estimating the flux of contaminants.

From 1988 at about eight locations in the marine area of the Netherlands, suspended matter was collected four times a n in Figure 1. The samples were taken using a flow-through centrifuge at a capacity of 0.7–

eter of 10–12 cm. Three segments of Teflon sleeves were place in the rotor. After centrifugation, the sleeves are taken out and the material is scraped from the sleeves into a

Typically 4–25 m3 water was centrifuged resulting in samples of 30–1000 g of dry suspended matter. were homogenised by a ball mill and for analysis of organotin compounds.

o those for sediments.

e concentration profiles of the cofactors as well as the contaminants. To

diment. Consequently, OC content in the SPM collected at open Sea, NZ 10, shows a very high variation. The small amount of SPM in the water originating from the sediment is easily overruled by algae material, especially in quiet weather conditions. As a result of that algae production, the Al content in SPM decreases considerably at NZ 10, as shown in Figure 4. The trend in time of some contaminant contents in SPM is shown in Figure 5 to Figure 11. It can be visually observed that in the Ems-Dollard (ED) all contaminants shown seem to exhibit a downward trend except for PAHs. In a more dynamic area as the NZ there is no obvious trend. Perhaps there is one, but with the high variability it is not likely significant. For TBT, the time series is shorter. The results obtained fit well with those of other contaminants.

In Figure 12 the seasonal variation of CB153 is shown. The lower graph shows the variability of the OC contents. The value in the both winter samples is however much more constant over the years, with an average of a bout 3.2%. Clearly, algal growth in warmer periods dominates the suspended matter. This is confirmed by the lower aluminium contents indicating a lower contribution of the mineral fraction (see Figure 4). An algal bloom is principally an increase of the suspended matter content by mainly organic matter. This would imply a higher concentration of a compound like CB153. There is however only a slight increase and not significant in many cases (closed circles in upper graph). However the fact that the content is never decreasing because of the dilution by all that algal material means that it has taken up a considerable amount of dissolved CB153 from the water phase. The amount in the water phase is not sufficient to reach the concentration based on organic carbon that is present in wintertime. Resuspension is very limited

Contaminants in suspended matter in marine areas of the Netherlands;

Introduction

sediments. As sedimentexpected to more rapidly fdifferent compartments wi

organic matter will increase solupresent. At the same time, the filter can remove contaminants from the water phase by adsorption. Contaminant concentrations in t

of metals and hydrophobic co tacompartment by filtration is time-consuming and usually only a small amount of materia

the suspended matter. Anometres of water can be processed resulting in a sediment-like material. Consequently, analyses are performed similar to those applied for sediment. In addition to using the content of contaminants in suspended matter to evaluate the contamination level, it

Methods

year. The locations are show1 m3 per hour. Rotation speed is around 10000 rpm with a diam

glass sample jar. Samples were stored at –20°C prior to freeze-drying. After freeze-drying, samplesstored at room temperature, except a small sub-sample that was stored at –20°C All sample analyses were equal t

Discussion

The graphs in Figure 2 and further show themphasize the relation between the locations, some graphs were made with equal scales for all locations (Figure 2). In case the scales were individual for each location, the variation in time is more visible (Figure 3). In general, the locations with the highest SPM contents have the lowest OC contents and at the same time show little variability. The SPM is then dominated by material originating from the bottom se


in the quieter summer periods and diffusion from sediment to fill the gap to equilibrium with the water phase. Consequently the concentration based on organic carbon, in the figure recalculated to the winter value for OC (3.2%),

n the upper graph by the open circles.

or trend monitoring purposes the above is an adverse effect but on the other hand the outcome is expressing very ntamination levels, indicating the very rapid response of suspended matter to changes in the

quality of the water phase. The advantage is that the concentration is much higher and consequently more accurately measured.

drops considerably in summertime as can be seen i

Conclusion

Fprecisely the actual cosystem. In other words the quality of suspended matter is very well reflecting the

Figure 1. Map with sample locations. Names correspond with those in the graphs.


ED

40 OC

30

15

0

5

87 90 93 96 99 020

5

87 90 93 96 99 02

WZ West

0

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OC

NZ 10

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WS-NZ WS-V liss

10

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35

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10

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25

30

35

40OC

35

25

30

40

Figure 2. OC in % dw SPM (equal scales).

0

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25

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40OC

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35

40OC

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35


ED

6

7 OC

WZ Mid

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12

4

Figure 3. OC in % dw SPM (Variable scales).

0

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3

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87 90 93 96 99

OC

WS Hans

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02

OC


Figure 4. Al in g/kg in SPM (equal scales).

0

10

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30

40

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70

87 90 93 96 99 02

A l

0

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A l

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A l

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A l

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A l

WZ MidED


Figure 5. Cd in mg/kg SPM (variable scales).

ED

0

0.2

0.4

0.6

0.8

1

87 90 93 96 99 02

Cd

WZ Mid

0

0.2

0.4

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Cd

WZ West

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Cd

NZ 10

0

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Cd

WS-NZ

00.10.20.30.40.50.60.70.80.9

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Cd

WS-V liss

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Cd

WS Hans

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Cd


Figure 6. Hg in mg/kg SPM (Equal scales).

ED

0

0.2

0.4

0.6

0.8

1

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87 90 93 96 99 02

Hg

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Hg

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Hg

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Hg

in


Figure 7. Pb in mg/kg in SPM (Equal scales).

0

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Pb

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PCB153

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Figure 8. PCB153 in µg/kg dw suspended matter (Equal scales).


ED

90 93 96 99 02

Flu

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Figure cales).

9. Fluoranthene in µg/kg dw in SPM (Variable s

050

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Figure 10. BaP in µg/kg in SPM (Variable scales).


Figure 11.TBT in µg/kg in SPM (Equal scales).

ED

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Figure 12. Profile of PCB153. The closed symbols are raw numbers and the open values represent normalised values 3.2 % OC. The lower graph shows the corresponding OC contents.

NZ 10

0

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6

8

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1987 1990 1993 1996 1999 20020

2

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PCB153

PCB153 for 3.2 %OC

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OC

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recalculated to


Annex 8 OSPAR/MON working schedule

MON 2003 ANNEX 9 (Amended 18 02 04)

OSPAR CONVENTION FOR THE PROTECTION OF THE MARINE ENVIRONMENT OF THE NORTH-EAST ATLANTIC MEETING OF THE WORKING GROUP ON MONITORING (MON) COPENHAGEN: 16–18 DECEMBER 2003

2004 timetable for work on the 2005 assessment of CEMP data, amended to show progress with the Actions

Action Responsibility 2004 Deadline Progress to 18 February

Submit to ICES example data sets for TBT- metal- and PAH-specific biological effects as a basis for ICES to undertake a test of the data reporting format (version 3.2) with a view to ICES finalising the reporting format so that it can be made available from 30 April 2004 for Contracting Parties to submit their biological effects data.

Norway and UK 9 January Complete

Update the S-PLUS codes to take account of the discussions at MON 2003 and request relevant data sets from ICES on which to test run the revised S-PLUS codes.

UK 12 January Rescheduled for early March (WGSAEM)

Prepare a list of “stations” based on Master records, i.e., geo-position, species/sediment, monitoring year, station.

ICES 12 January Complete

Send a reminder to Contracting Parties about submission of data. Letter to include ICES latest overview for sediment (with normalising aluminium, lithium, organic carbon (TOC CORG), percentage of grain size) and biota for metals, organic metals, organics, pivot values (see annex to sediment guidelines). The reminder should request indications from MON-delegates on the data they intend to submit and the expected dates of their submissions up to 1 August 2004.

MIG Convenor 15 January Complete

Invite Contracting Parties to provide the details of those experts that will be taking part in preparing for and undertaking the assessment at the next meeting of MON.

MIG (via Secretariat)

1 February Rescheduled for March

Provide ICES and the OSPAR Secretariat with details of national OSPAR contact and data co-ordinator

Contracting Parties 1 February Partially complete

Provide sample data sets from the ICES database to the UK so that the UK can test run the revised S-PLUS codes on the sample data sets.

ICES 6 February Data sets provided

BRC/EAC workshop.

Netherlands (plus France and UK)

8 - 13 February Complete

Provide to ICES unique station names for the ICES database. Contracting Parties 15 February Partially complete

SIME meeting. 24–26 February

UK

ICES 30

ICES 1

ASMO meeting. 29 March – 2 April

Provide to ICES the final versions of the S-PLUS codes. 31 March

Latest date by which the biological effects data reporting format (version 3.2) should be finalised and made available for Contracting Parties to submit their biological effects data to ICES.

April Complete

Translate the S-PLUS codes into R or other appropriate language that will be used for ICES database applications.

May


Action bility 2004 Deadline Progress to 18 Responsi

Contracting Par

MIG 1

ICES 1

Contracting Par

MIG

MIG 1

MIG 31

MIG 31

ICES 15

MIG

ICES and MIG

ssessment report and M

nex

February

Final date for submission of data to ICES where new codes are needed and/or there are problems with the data set.

ties 1 June

Ensure that EAC/BRCs and normalising parameters are in place for the first run of the assessments on July 1.

June

First run of assessments and production of summary statistics and maps

July

Final date for delivery of screened data to ICES. ICES has the option to deny new entries after this date.

ties 1 August

Final decision on which normalising to use for sediments. 1 August

Evaluate the use of EAC/BRC, normalising, quirks in temporal nd assessment.

August

Review the OSPAR data submitted to ICES on metal- and PAH-ecific biological effects monitoring and consider whether

sufficient data is available to warrant assessment, and, if so, propose the procedure by which this data should be assessed.

August

Review the OSPAR data submitted to ICES on contaminants in sediments and the extent to which OSPAR spatial data are available, over and above temporal trend data, and whether it is

fficient to warrant further spatial distribution assessment.

August

Completion of checking and entry of data submissions for the ssessment to the ICES database.

September

Circulate to Contracting Parties for agreement the complete set of finalised tools and procedures to be applied in the ssessment.

1 October 2004

Final runs of assessment. 1 November

Prepare the assessment products for submission to the next meeting of MON in the form of a draft aAnnexes.

IG Deadline for t MON

ON meeting to assesses the data products from ICES and MIG and finalise the assessment for consideration by ASMO 2005, and to:

examine the feasibility of examining relationships between inputs and environmental concentrations and effects, taking into account the assessments being undertaken by INPUT;

should address the issues identified by SIME 2003 ting to national comments, mandatory data fields, and

variability in monitoring data.

[First week in December]

tre

sp

su

a

a

M

a.

b. rela


Annex 9 Data description and evaluation for BCs of metals

Data sets:

The data set from the BRC/EAC workshop contains cores from Regions I, II, and IV. Only three data sets from Re on I, one individual concentration from Region II, and two from Region IV were available, so it was noted that the ta sets used were very small, and probably could be expanded by finding more national data or even use data from o oceans to validate the determined background concentrations. At the 2004 WGMS meeting, further data sets were added.

New data sets included data sets from Sweden and Finland from the Baltic Sea (nine data sets including one anoxic sediment). Only sediments from before approximately 1850 were taken, and one permanently anoxic sediment is gi en for reference, but not included in the background concentration determination. From Norway, cores from Regi I (twelve data sets) and Region II (five data sets used, two from the inner Oslo fjord were disregarded). For this data et, core samples below 15 cm were used as “pre-industrial”, even though no direct age determination was available. Also, “outliers” (defined as > average +3× standard deviation) were excluded, taking out three mercury results (0.079–0.2 kg−1) and one lead result (80 mg kg−1). The Swedish Geological Survey contributed data from the bottom of 136 co s, with 84 data sets from Region I (Skagerrak and Kattegat) and 52 data sets from the Baltic and Bothnian Sea. The data were treated as individual locations. Also for this data set, some outliers was removed, and for Hg, Cu, Ni values be w the detection limit were converted to a value of half the detection limit in the data treatment. The UK and The Netherlands contributed core data from Region III (four data sets).

Table 3. Data sets collected during WGMS 2004.

OSPAR Region Element As Cd Cr Cu Hg Ni Pb Zn

gidather

von s

mgre

lo

(n = 10) 10±1

0.10

0.37 37±7 27±7

I Norway (n = 12) n.a. 0.23 n.a. 34 0.022 n.a. 21 122

II Norway (n = 7) n.a. 0.07 n.a. 24 0.018 n.a. 27 105

Skagerrak (n = 51) § 7 0,10 65 6 0,017 24 30 65

Kattegat (n = 27) § 8 0,11 60 11 0,015 24 21 60

III UK (n = 3) 10* 0,13 73* 22 0.016 36* 17 66

HELCOM Baltic SW (n = 11) § 9 0,15 61 4 0,017 29 18 67

S Bothnian Sea (n = 7) § 6 0,10 56 21 0,015 24 14 77

Stockholm (n = 27)§ 6 0,20 59 6 0,026 18 21 79

Baltic sea (n = 8) 11 0,17 56 23 0,019 32 30 80

Anoxic Baltic (n = 1) 11 1,0 52 52 0,021 43 27 99

MPB:

Baltic Proper (n = 51)

Åland Sea (n = 4)

Bothnian Sea (n = 5)

Bothnian Bay

9±3

6±5

9±2

(±0.27)

0.31

0.24

52±13

56±4

40±7

45±13

40±3

36±5

(±0.02)

0.04

0.03

0.03

0.02

39±7

39±1

36±8

32±18

25±15

26±8

24±6

4.2±2.9

120±30

155±16

132±17

71±21 *A

: only available at one station. § data from the Geological Survey of Sweden. ll mass concentration in mg kg−1 normalised to 50 g kg−1 Al, except Norway Region I normalised to 50 mg kg−1 Li, and

MPB = Marine Pollution Bulletin p.8 (32)1996, in mg kg−1 dry weight – most expected to be in fine-grained samples. For MPB, mean±SD is given, except for Hg and Cd where maximum SD is indicated in parentheses (actual values for Hg are ±0,02; ±0,00; ±0,01; ±0,01 and for Cd ±0,19; ±0,06; ±0,07; ±0,27). Data in italics are considered unsuited as background areas but given as information values. In Table 3, the median values for the new added data sets are shown. From this, it can be seen that Ni and As seem a bit lower in Region II (Skagerrak and Kattegat). This was the basis for the reservations made in Table 1 suggesting that lower background concentrations could be used for this region, as well as the HELCOM areas.


E

Ita tB isc2

A

TYPE OSPAR R LOCATION MEAN MEDIAN MIN

Core I Barents Sea

val

n th rt of each ble he ay al ed once d at the 004

rse

From vering Regi

Medi e Bay of Biscay were 4 mg k e new data kg−1 when

Comp ta was 15 m ues may b

The est

uation of the collected data for individual metals

e sections below, an overview and evaluation of the data collected are given for eight metals. The first pashows the data collected during the BRC workshop in The Hague. It can be noted that the minimum value inof Biscay is sometimes higher than the median. This is possibly because the calculation of normntration is based on mean values for each sample. The second part of each table contains the data adde

WGMS meeting.

nic

the workshop on BCs held in The Hague, six cores were available normalised to aluminium (50 g kg−1), coons I, II, and IV. Normalised to lithium, four cores were available, covering Regions I and IV.

an arsenic values for cores normalised to aluminium were between 3 mg kg−1 and 14 mg kg−1, with th and Iberian Coast being the lowest (3 mg kg−1). For Li normalisation, the values of As concentrations

g−1 up to 18 mg kg−1. Generally, the minimum values were within 30% of the median at that location. In th sets, median values for As ranged from 6 mg kg−1 to 11 mg kg−1 normalised to Al, and 8 mg kg−1 to 17 mg

normalised to Li.

aring both data sets, it can be noted that ranges overlap quite well. The 90% percentile of all core dag kg−1 As. This value in the upper range was selected as BC, being aware that in some areas lower local vale present.

imated background concentration of Arsenic is set to 15 mg kg−1.

CONTAMINANT As mg kg−1

ARTMENT Sediment

COFACTOR Al

COMP

13.1 11.3 7.1

Spitzbergen 12.6 12.9 9.5

W-Norway 4.8 4.8 4.5

II Oystergrounds 9.7

IV Bay of Biscay and Iberian Coast 3.4 3.2 1.9

SURFACE I Laptov Sea, Siberia 21.2

Added at the 2004 WGMS meeting:

CORE I Skagerrak, 51 cores 7.6 7.1 4.1

Kattegat, 27 cores 8.5 8.4 4.0

III Belfast Lough 10

HELCOM Baltic Sea 11.8 11.4 9.7

Stockholm Archipelago 6.0 5.8 2.0

SW Baltic 9.2 8.6 3.2

S Bothnian Sea 6.2 6.4 4.6


CONTAMINANT As

COFACTOR Li

TYPE OSPAR R LOCATION

Core I Barents Sea

Added a

8.2 5.3


Cadmium

Five cores were available normalised to aluminium, coveavailable covering Regions I and IV.

Median cadmium values for cores normalised to aluminiumexclusion of the anoxic W-Norway (0.86 mg kg−1) aminimum values were far from

ring Regions I and IV. Normalised to lithium, four cores were

were between 0.04 mg kg−1 and 0.16 mg kg−1, with the nd Bay of Biscay and Iberian Coast (0.38 mg kg−1). Generally, the

the median.

s not Al results were avai wedish data on agerrak) were 0.015 mg kg to 0.017 mg kg−1, with minimum values up to 50%

below median values. The 90% percentile was up to 0.13 mg kg−1 for the Skagerrak. For Region II, a median value of g kg−1 a a max 0.13 mg kg−1

values ranged between 0.10 mg kg−1 and 0.20 mg kg % percentile but ise below 0.3 The m ues from the

of the original data set.

dmium for cores normalised to lithium 0.0 0 −1, with the xclusion of the anoxic W-Norway (1.26 mg kg−1) and Bay berian Coast (0.53 mg kg−1). Generally, the inimum values were far from the median.

For the new data sets, for Region I data from Norway the median cadmium value was 0.23 mg a maximum kg−1. Swedish data from Region 1 (Kattegat/ gerrak) ranged fr .12 mg kg− o 0.13 mg kg−1, with

minimum values up to 50% below median values. The 90% percentile was up t 1 for the Skagerrak. No Li lable for Region II or Region III data. For the HELCOM area, median values of cadmium ranged

between 0.20 mg kg−1 and 0.37 mg kg−1. The 90% percentile was high for the Stockholm Archipelago (1.6 mg kg−1), but otherwise was below 0.65 mg kg−1. The median values from the new data sets are about two times above the range

kes the background concentration not only regional but local. As a on for all regions, but with the comment that locally, other values

pply in the range 0.05 mg kg−1 to 0.4 mg kg−1.

m is set to 0.2 mg kg−1.

For the new data sets, Region I data from Norway wacadmium from Region I (Kattegat/Sk

mg kg−1

COMPARTMENT Sediment

MEAN MEDIAN MIN

17.4 14.8 9.5


W-Norway 7.0 7.0 6.6



t the 2004 WGMS meeting:

CORE I Skagerrak, 51 cores


HELCOM Baltic Sea 17.3 16.9 13.9

Stockholm Archipela

9.6

go 10.6 10.1 3.5

SW Baltic 15.5 15.3 4.8

available, as no−1

lable. S

0.07 mg kg−1 was found, with a maximum of 0.08 mwas found. For the HELCOM area, median

nd for Region III, median and imum of−1. The 90

was high for the Stockholm Archipelago (0.93 mg kg−1), new data sets are about two times above the selected

otherw 4 mg kg−1. edian val

Median values of ca were between of Biscay and I

6 mg kg−1 and .21 mg kgem

kg−1, withvalue 0.46 mg Ska om 0

o 0.4 mg kg−1 t

values were avai

of the original data set.

The large range of results found in all regions maresult, it was decided to set the background concentraticould a

The estimated background concentration of Cadmiu


CONTAMINANT Cd mg kg−1


COFACTOR Al

TYPE OSPAR R LOCATION ME

Core I Barents Sea 0.23 0.16 0.04

Spitzbergen 0.04 4 0.02 0.0

IV Bay of Biscay and Iberian Coas 0.35 8 0.18 t 0.3

Biscay Bay 0.04 0.05 0.03

MONIT IV Bay of Biscay 0.12 0.05

V Rockall Bank and Rockall trough 0.23 0.14 0.03




Kattegat, 27 cores 0.13 0.10 0.07

II Norway 5 cores 0.08 0.05 0.07

HELCOM Baltic 0.17 0.17 0.15


SW Baltic 0.19 0.08 0.15


CONTAMINANT Cd mg kg−1


COFACTOR Li

TYPE OSPAR R LOCATION


MEAN DIAN MIN

W-Norway 0.86 0.86 0.84

III Belfast Lough 0.13

MEAN MEDIAN MIN

COREe I Barents Sea 0.30 0.21 0.06

W-Norway 1.26 1.26 1.23






CORE I Norway 15 cores 0.23 0.23 0.05

Skagerrak, 51 cores 0.16 0.12 0.09

Kattegat, 27 cores 0.19 0.13 0.07



SW Baltic 0.30 0.20 0.13



Chromium

n of Oysterground (73 mg kg−1). Generally, the minimum values were within 15% of the median.

For the new data sets, Swedish data on chromium from Region I (Kattegat/Skagerrak) ranged from 74 mg kg−1 to 77 −1 median values. The 90% percentile was up to 0.4 mg kg−1 for the

n II or Region III data. For the HELCOM area, median chromium values ranged between 82 mg kg−1 and 108 mg kg−1. The 90% percentile was below 150 mg kg−1. The median values

ta sets ar 0% higher than origin ata s

The estimated background concentration of Chromium is set to 60 mg kg− .

NTAMINANT Cr −1

Five cores were available normalised to aluminium, covering Regions I, II, and IV. Normalised to lithium, four cores were available covering Regions I and IV.

Median values of chromium in cores normalised to aluminium were between 45 mg kg−1 and 58 mg kg−1 with the exclusio

For the new data sets, Swedish data on chromium from Region I (Kattegat/Skagerrak) ranged from 60 mg kg−1 to 65 mg kg−1, with minimum values up to 50% below median values. The 90% percentile was up to 90 mg kg−1 for the Skagerrak. For Region II, a median value of 0.07 mg kg−1 was found, with a maximum of 0.08 mg kg−1, and for Region III a median and maximum of 0.13 mg kg−1 was found. For the HELCOM area, median chromium values ranged between 56 mg kg−1 and 65 mg kg−1. The 90% percentile was below 75 mg kg−1. The median values from the new data sets are within the original data set.

Median values of chromium in cores normalised to lithium were between 64 mg kg−1 and 71 mg kg−1. Generally, the minimum values were within 20% of the median.

mg kg , with minimum values up to 70% belowSkagerrak. No Li values were available for Regio

from the new da e about 5 the al d et.

1

CO mg kg

COMPARTMENT S ediment

COFACTOR Al

T SPAR R LOCATIO MEDIAN

CORE Sea 0 46.8 I Barents 54. 53.6

Spitzbergen 4 45.46. 46.6 1

II Oystergroun 73.3

IV Bay of nd Ibe Coast 56.0 58 4 0

English Ch l 41 33

IV Bay of Bisca 54.2 49

YPE O N MEAN MIN

W-Norway 45.0 45.0 44.9

ds

Biscay a rian .0 4.

MONIT II anne

y





Kattegat, 27 cores 58.4 59.9 30.9




SW Baltic 64.4 61.3 55.0



CONTAMINANT Cr mg kg−1


COFACTOR Li




W-Norway 66.1 66.1 65.9


MONIT II English Channel 31.7 25.6

IV Bay of Biscay 54.2 46.2





Kattegat, 27 cores 73.8 74.4 29.1



SW Baltic 102.7 101.3 60.9

S Bothnian Sea 108.9 1 100.5 08.1

Copper

the Workshop on B held i e, six cores were available no ed to inium ( kg−1), covering Regions I, II, and IV. Normalised to lithium, four cores were available, covering Regions I and IV.

edian copper values fo ores to aluminium ranged from 5– g kg− th the of Biscay and erian Coast being the lo st (5 Li-normalised values, the C centrati ns were 1 mg kg−1 up to 44

mg kg−1. The differences between the median and the minimum values were often very large, up to 80%. This was even ore true for the new da ts. T sed by anoxic situations. For Cu it etter to

lower values f deriv alue. To do so, first all cores we ected w ere the minimum value was more than half the median. Then the set could still contain cores that were enhanced due to anoxic processes

he median of the selected set, 19 mg kg−1, was taken as a basis for the Background ounding results in 0 mg k

Comparing this value with monitoring data from the ICES database shows that the proposed number is well in greement with the lower end resu ediments.

he estimated bac round conce t to 20 mg kg−1.

From Cs n The Hagu rmalis alum 50 g

M r c normalised 30 m 1, wi BayIb we mg kg−1). For u con o 5

m ta se his large range is probably cau is therefore blook at the or ing a background v re sel h

over the whole core. Therefore, tvalue. R 2 g−1 Cu as the BC.

a lts of surface s

T kg ntration of Copper is se


CONTAMINANT Cu mg kg −1


COFACTOR Al

TYPE OSPAR OCATION MEAN MEDIAN MIN

Core I Barents Sea 17.6 17.8 14.1 S pitzbergen 22.3 21.9 20.8 W -Norway 30.3 30.3 29.2


MONIT II English Channel 13 10

IV Bay of Biscay 11 8

V R ckall trough ockall Bank and Ro 35.0 28.0 15.0

SURFACE L iberia I aptov Sea, S 19.0


CORE III Belfast h Loug 15

Duich 1996 18.4 16.3

R L

IV Bay of Biscay and Iberian Coast 13.0 12.0 7.0 Biscay Bay 8.4 5.5 5.1

Loch Duich 18.6 17.2

II Norway, 5 cores 34.7 34.0 12.3

I Skagerrak, 51 cores 18.0 6.1 1.8 Kattegat, 27 cores 14.0 11.3 2.1

HELCOM Baltic, 8 cores 23.2 23 22.5 Stockholm Archipelago, 28 cores 14.9 6.3 1.5 SW Baltic, 13 cores 9.2 4.0 2.4 S Bothnian Sea, 7 cores 21.4 20.7 16.8

CONTAMINANT Cu mg kg−1


COFACTOR Li


Core I Barents Sea 23.2 23.8 18.4 Spitzbergen 30.2 30.1 28.4 W-Norway 44.5 44.5 42.8










III Oysterground 15



SW Baltic 17.3 6.3 5.7



Mercury

vaila ormalised to aluminium, covering Regions I and IV. Norm lithium four cores were available covering Regions I and IV.

of merc n cores normalised to aluminium were bet een 0.018 g kg−1 and 039 mg kg−1, with the on of the Ba oast (0.080 mg kg−1). Gene lues below 40% of

the median.

r the new data sets, R on I orway were not available, as n esults were availab edish data on ercury from Region 1 atteg k) ranged from 0.015 mg kg−1 to 7 mg k −1 ith mi values up to % below median valu Th entile was up to 0.13 mg kg−1 e Skag For R II, a median ercury value of 0.01 g kg m of 0.036 −1, and Region edian and aximum of 0.016 mg kg−1 wa the HELCOM area, median me value ed bet 0.015 mg kg−1

and 0.026 mg kg−1. The 90% percentile was high for Stockholm Archipelago (0.129 mg kg ), but otherwise was below kg−1. The me val w data sets are within the ran the orig al data se

rcury value r co ium were between 0 8 mg kg−1 0.054 g kg−1, with the f the Bay o iscay (0.100 mg kg−1). Genera y, the mi values were below 40%

For the new data sets, Region I data on mercury from Norway showed a median value of 0.022 mg kg−1, with a aximum value of 0.04 mg k from Region 1 (Kattega gerrak) ed from 20 mg kg−1 to

.026 mg kg−1, with mi um elow median values. Th perce as up 3 mg kg−1 for the Skagerrak. No Li values were available for Region II or Region III data. For the HELCOM area, median mercury

alues ranged between m 49 mg kg−1. The 90% percentile was high e Stockholm Archipelago 0.224 mg kg−1), bu e elow 0.093 mg kg−1. The median va from t data within the ange of the original data

he estimated ba ground con of Mercury is set to be 0.05 mg k r all r s.

CONTAMINANT Hg mg kg−1

Five cores were a ble n alised to

Median values ury i w m 0.exclusi y of Biscay and Iberian C rally, the minimum va were

Fo egi data from N o Al r le. Swm50

(Kes.

at/Skagerrae 90% perc

0.01for th

g , werrak.

nimumegion

m 8 m −1 was found, with a maximu mg kg for III, a mm s found. For rcury s rang

−1ween

0.055 mg dian ues from the ne ge of in t.

Median meexclusion o

s fof B

res normalised to lith and Iberian Coast

.02ll

and nimum

m

from the median.

m 7 g−1. Swedish data t/Ska rang 0.00 nim values up to 50% b e 90% ntile w to 0.1

v 0.019 g kg−1 and 0.0 for th( t otherwis was b lues he new sets are r set.

T ck centration g−1 fo egion

COMPARTMENT Sedim ent

COFACTOR Al

TYPE LOCATION


0Spitzbergen 0.039 0.039 .035

0W-Norway 0.023 0.023 .022

IV ay and Iberian Coast 0Bay of Bisc 0.080 0.080 .050

0Biscay Bay 0.018 0.018 .025

MONIT IV 0Bay of Biscay 0.053 .052

V 0Rockall Bank and Rockall trough 0.100 0.080 .030

Added at the 2004 WGMS eting me :


0.007 Kattegat, 27 cores 0.023 0.015

II Norway 3 cores 0.015 00.016 .009

III Belfast Lough 0.016

H 0.016 ELCOM Baltic 0.019 0.019

0.010 Stockholm Archipelago 0.046 0.026

SW Baltic 0.025 0.011 0.017

S Bothnian Sea 0.022 00.015 .012

OSPAR R MEAN MEDIAN MIN


CONTAMINANT Hg mg kg−1


COFACTOR Li



Spitzbergen 0.053 0.054 0.045

W-Norway 0.034 0.034 0.032





CORE I Norway 15 cores 0.024 0.022 < 0.01

Skagerrak, 51 cores 0.057 0.026 0.013

Kattegat, 27 cores 0.030 0.020 0.015

HELCOM Baltic 0.028 0.028 0.023


SW Baltic 0.039 0.025 0.017

S Bothnian Sea 0.043 0.029 0.019

ickel

ailable malised to aluminium, covering Regions I and II. Norm lithium, three cores were available covering Region I.

s of nickel i res normalised to aluminium were between 27 mg kg− and 38 m −1, with the exclusion orway (47 mg −1 r mum values were within 3 e

new data sets, Swe sh nic Region 1 (Kattegat/Skagerr ere 24 −1, w inimum values out 20% below median lues. rcentile was up to 29 mg kg− the S rak. F gion II no data ere available, and for Re ion III 36 mg kg−1 was found. Fo rea, ckel values

ranged between 18 mg kg− and 32 mg kg . The 90% percentile was below 38 mg kg . The median values from the w data sets are generally low t f the original data set.

Median nickel values for cores normalised to lithium were between 45 mg kg−1 and 53 mg kg−1, with the exclusion of ay (69 mg kg−1). erall alues were within 25% o edian.

r the new data sets, Sw ish da attegat/Sk k) ra from mg kg−1, with minimum values at around 20% of median values. The 90% percentile was up to 36 mg kg−1 for the Kattegat. No Li

available for R ion II . For the HELCOM area, median ues nged between 30 percentile was below 58 mg kg−1. The median values from the new data sets are in

the same range as those selected from the original data set.

he estimated background concen s set to 45 mg kg−1.

N

Five cores were av nor alised to

Median value n co 1 g kgof W-N kg ). Gene ally, the mini 0% of th median.

For the di kel data from ak) w mg kg ith mab va The 90% pe 1 for kager or Rew g

1 one value of

−1r the HELCOM a

−1median ni

ne be hose selected o

W-Norw Gen y, the minimum v f the m

Fo ed ta on nickel from Region 1 (K agerra nged 28–29

values were eg or Region III data nickel val ramg kg−1 and 47 mg kg−1. The 90%

T tration of nickel i


CONTAMINANT Ni −1 mg kg

TYPE

Core I Barents Sea 33.9 34.2 27.6 S 33.5 pitzbergen 38.3 38.4 W 45.6 -Norway 46.9 46.9

II O ystergrounds 27.3

MONIT E 7 13 II nglish Channel 1

IV B 19 ay of Biscay 22.0


CORE I Norway 22 cores


K 4.3 attegat, 27 cores 22.3 24.0

I Belfast II Lough 36

Duich 96 33.3 19 36

S .0 .4 24.5 W Baltic 31 29

S .2 3.7 1.7 Bothnian Sea 24 2 2


COFACTOR Al

OSPAR R LOCATION MEAN MEDIAN MIN





CONTAMINANT Ni mg kg−1


COFACTOR Li


Core I BarentsSea 44.7 44.6 36.2 Spitzbergen 52.2 53.1 43.3 W-Norway 68.9 68.9 66.9






CORE I Norway 22 cores

Skagerak, 51 cores 27.3 27.8 5.6




SW Baltic 30.1 26.4 19.8


Lead

Six cores were available normalised to aluminium, covering Regions I, II, and IV. Normalised to lithium, four cores were available, covering Regions I and IV.


Median lead value for cores normalised to aluminium were between 6.8 mg kg−1 and 9.1 mg kg−1, with the exclusion of Oystergrounds (29 mg kg−1) and the Bay of Biscay and Iberian Coast (19 mg kg−1). Generally, the minimum values

of the m .

For the new data sets, Region I data from Norway were not available, as no Al results were available. Swedish data on gion I (Katte Ska rak) ranged from 21 mg kg−1 to 29 mg kg−1, with minimum alues about 50% of the

values. The 9 44 mg kg−1 for the Skager Re median lead value of 27 −1 was found, with ax mg kg−1; for Region III, a me of 17 g−1 an aximum of 20

g kg−1 were found. For th HE edian lead values ranged bet 14 m and 3 kg−1. The 90% rcentile was below 46 mg kg an values from the new data oun e tim her than those lected from the original d ta se

edian lead values for co no en 11.2 mg k nd 12. −1, w e exclusion of e Bay of Biscay and Iber n Co ). Generally, the minimum v were w 25% edian.

w data sets, Reg I d Norway had a median val f 20 mg k 1, with ximum value 45 g kg−1. Swedish data fr e /Skagerrak) ranged from 2 5 mg kg−1 with min um values up to % below median values. The 9 kg−1 for the Skagerrak. No Li values were available for

r Region III dat For , median values of lead ra d betw 7 mg kg−1 and 44 mg kg−1. The 90% percentile was high for the Stockholm Archipelago (76 mg kg−1), but otherwise was below 67 mg kg−1. The

sets are about four times above those of the original data set.

he estimated background onc lead is set to 25 mg kg−1.

ONTAMINANT Pb mg

were within 25% edian

lead from Re gat/ ger vmedian 0% percentile was up to rak. For gion II, a mg kg a m imum of 49 dian mg k

−1d a m

mpe

e LCOM area, m−1. The medi

ween sets ar

g kgd thre

0 mg es hig

se a t.

M res rmalised to lithium were betwe−1

g−1 a 5 mg kg ith thth ia ast (30 mg kg alues ithin of the m

For the ne ion ata on lead from ue o g− a mam om R gion 1 (Kattegat 5–3 , im50 0% percentile was up to 58 mgRegion II o a. the HELCOM area nge een 2

median values from the new data

T c entration of

C kg−1


COFACTOR A l

TYPE OSPAR R LOCATION IN

CORE I Barents Sea 9.6 8.6 6.8

MEAN MEDIAN M


W-Norway 7.6 7.6 7.3

II Oy 29.0 stergrounds

IV Bay Iberian Coast .0 of Biscay and 25.0 19.0 16

Bis 0 .0 cay Bay 9. 6.8 10

MONIT II English Channel 26 32

IV Bay 1 of Biscay 33. 30

V Roc 0 .0 kall Bank and Rockall trough 14. 13 11.0


CORE I Skagerrak, 31.8 .7 14.8 51 cores 29

Kattegat, 27 cores 21.4 20.5 14.0

rway 5 cores 28 24

III Belfast .5 Lough 16

Duich .5 15.5 1996 17

HELC Baltic 29.8 27.7 OM 29.9

SW .5 13.0 Baltic 19 18.0

S B .9 .8 0.1 othnian Sea 15 13 1


II No .8 .9 15.9



CONTAMINANT Pb mg kg−1


COFACTOR Li


CORE I Barents Sea 12.8 11.2 8.8


W-Norway 11.2 11.2 10.7





SURFACE I Laptov Sea, Siberia .7 16




Kattegat, 27 cores 27.6 25.5 19.2



SW Baltic 30.1 26.4 19.8


Zinc

Six cores were available normalised to aluminium, covering regions I, II and IV. Normalised to Lithium four cores were nd .

value for alis um were between 61 mg kg−1 m −1 the of Biscay Bay (28). Generally, the minimum values were within 10% of the median.

r the new data sets, Region I orway were not available, as no ults were availab dish data on nc from Region (Kattegat/S nged from 60 mg kg−1 to 65 m −1, min values 25% below edian values. T 90% percen to 108 mg kg−1 for the Skager r Re , a m value of 105 g kg−1 was foun ith a maxi Region III, a n of 6 g−1 a um of 70 g kg−1 were fou . For the HE , median zinc values ranged bet g −1 nd 79 −1. The 90%

percentile was high for Stockholm Archipelago (147 mg kg−1), but otherwise was below 94 mg kg−1. The median values new data sets were arou r than those selected from the al data et.

Median zinc values for cores normalised to lithium were between 83 mg kg−1 and 87 mg kg−1, with the exclusion of the Generally, the minimum values were within 20% of the median.

or the new data sets, Region I rway showed a median va 122 m −1, with imum value of 154 mg kg−1. Swedish data from Region 1 (Kattegat/Skagerrak) ranged from 74–77 mg kg−1, with minimum values

p to 50% below median value rcentile was up to 173 mg r the rrak. values were vailable for Regi or Regio the HELCOM area, median zi values ra wee 07 mg kg−1 and

144 mg kg−1. The 90% percentile was high for the Stockholm Archipelago (259 mg kg−1), but otherwise was below 170 g kg−1. The med from w data sets are about 65% above tho he ori ata se

he estimated ba round conc f zinc is set to 90 mg kg−1.

available covering regions I a IV

Median cores norm ed to alumini and 69 g kg with exclusion

Fo data from N Al res le. Swezim

1 he

kagerrak) ratile was up

g kgrak. Fo

imum gion II

aboutedian

m d, w mum of 146 mg kg−1, and for media 6 mg k nd maximm nd LCOM area ween 67 m kg a mg kg

from the nd 50% highe origin s

anoxic W-Norway (102 mg kg−1).

F zinc data from No lue of g kg a max

u s. The 90% pe kg−1 fo Skage No Li a on II n III data. For nc nged bet n 1

m ian values the ne se of t ginal d t.

T ckg entration o


CONTAMINANT Zn mg kg−1


COFACTOR Al

TYPE OSPAR R LOCATION MEAN IN MEDIAN M

CORE I Barents Sea 64.1 8.3 65.2 5 Spitzbergen 6 6 58.70.8 0.8 ay 69. 69.5 68.8 W-Norw 5

ay 32. 27.7 28.8 Biscay B 2

MONIT II 100 93 English Channel

IV 96. 81 Bay of Biscay 6

V gh 63. 60.0 41.0 Rockall Bank and Rockall trou 0


Added a


62.0 58.8 Loch Duich

1996 67.8 64.5 Duich

HELCOM es 79 80 75 Baltic, 8 cor



t the 2004 WGMS meeting:

CORE I Skagerrak, 51 cores 75 65 47

Kattegat, 27 cores 61 60 48

II Norway, 5 cores 104 103 74

Stockholm Archipelago, 28 cores 94 79 43

SW Baltic, 13 cores 66 67 49

S Bothnian Sea, 7 cores 77 77 66

CONTAMINANT Zn mg kg −1


COFACTOR Li


CORE I Barents Sea 84.6 86.9 73.9 Spitzbergen 82.6 83.0 78.4 W-Norway 102.0 102.0 100.9






Added at the 2004 WGMS meeting

CORE I Norway 22 cores 126 122 104

Skagerrak, 51 cores 77 74 65

Kattegat, 27 cores 94 77 58

III Oysterground 65

HELCOM Baltic 116 117 108

Stockholm Archipelago 166 133 103

SW Baltic 105 107 82

S Bothnian Sea 149 144 133


Annex 10 Graphical Overview of data used to estimate BCs for PAHs

ate kgr concentrations for PAH compounds in sedimen

Type of sample

Data sets used to estim bac ound t.

Location

East Shetland Basin, Nor Surface sedth Sea iment

Fladen Ground, North Sea Surface sediment

Outer Moray Forth, Scotland, orth Surface sedimN Sea ent

Intermediate areas of the Mora Firth Surface sedimy , Scotland ent

Sea lochs (Scotland) and voes a Surface sedim (Shetl nd) ent

Oyster Ground, Southern North Sea Core

Bocht van wateren, Ems-Dollard, Ne Core therlands

Oslofjord, Norway Core

Biscay Bay, France Core

Arctic Ocean to Iceland Sea Surface sediment

Northem North Sea/Skagerrak Surface sediment

Tay/Forth, Scotland Surface sediment

Minches, Scotland Surface sediment

Southern North Sea Surface sediment

Northern Norway fjords Surface sediment

Barents Sea Surface sediment

Histograms of all data collected for each individual compound:

Mo Sc Ta S ter

y F

ot y/F otlirt

h dor

than

dia

teirt

hnd te

r,

et basan

din

,

Mi

Snc

hco

tes an

d

/k

Naphtalene

0

100

200

300

400

500

600

700

800

900

1000

Bis

cay

Bay

Nor

ther

nN

orw

ayO

ffsho

rera

,la

n

cIn

med

Mor

ay F

,S

cotla O

uM

urra

yFi

rth,

Flad

enG

roun

d,S

cotla

ndE

ast

Sh

l

Loch

s-vo

es,

Sco

tland

,l

IV I II III

CORE MONIT

µgg

OC


Phenanthrene

10

900

yste Bo te B

-lla

r

sca

No No

Offs ra

y

Ba

he rwa

ore irt nd ort

an

y

Gr

und

la

Sc

la

IV I II

RE

0

500

ster

grou

nds

Boc

ht v

ante

ren,

Em

s-

Bis

cay

Bay

Nor

ther

nN

orw

ayO

ffsho

reM

oray

Firt

h,Ta

y/Fo

rth,

Sco

tland

Inte

rmed

iate

Mor

ay F

irth,

ter M

urra

yth

, Sco

tland

Flad

enG

roun

d,st

She

tland

basi

n,Lo

chs-

voes

,S

cotla

ndM

inch

es,

Sco

tland

1000

1500

2000

3

5000

Oy wa Ou

Fir Ea

25003000

500

4000

4500

/kg

OC

II IV I II III

CORE MONIT

µg

Anthracene

0

0

200

300

400

500

600

700

800

Org

roun

ds

cht v

anw

are

n, E

ms

Do

d

iy rt

rn y

hM

o F

h,S

cotla

Tay/

Fh,

Sco

tld

Inte

rmed

iate

Mor

ay F

irth,

Sco

tland

Flad

eno

,S

cot

nd

Min

ches

,ot

nd

II II I

CO MONIT

µg/k

g O

C


ou va

, E ay

wa

s-

N Off

ora

rn ay e th,

th,

Ea

t San

d

Sco M

i

d s,

V I

CORE

Fluoranthene

0

2000

4000

6000

8000

10000

12000

14000

16000

Oys

terg

rnd

s

Boc

htn

tere

nm

Bis

c B

ay

orth

eN

orw

shor

My

Fir

Tay

/For

Sco

tland

Inte

rmed

iate

Mor

ay F

irth,

Out

er M

urra

yF

irth,

Sco

tland

Flad

enG

roun

d,

she

tlba

sin,

Loch

s-vo

es,

tlan

nche

Sco

tland

II I II III

MONIT

µg/k

g O

C

Pyrene

3000

5000

7000

8000

9000

ster oc

her D

o

Bis

c

OM

or Sc Ta Sc

ter

Mor Sc

nte

rh,

S

st S ba Sco

Loch

sS

c M

6000

C

4000

µg/k

g O

0

1000

2000

grou

nds

t van

en, E

ms-

llard ay

Bay

Nor

ther

nN

orw

ayffs

hore

ay F

irth,

otla

ndy/

Forth

,ot

land

med

iate

ay F

irth,

otla

d M

urra

yco

tland

Flad

enG

roun

d,S

cotla

ndhe

tland

sin,

tland -voe

s,ot

land

inch

es,

Sco

tland

Oy B

wat In Ou

Firt Ea

II IV I II III

CORE MONIT


0

15

nd an ms

Ba

wat

ern,

-

Nor fsh

ray otla

y/ cotl

me

Of

Mo S Ta S

nte

,

Eas

t S bahe si

n,

Sot

la

,

I

Chrysene

2000

2500

Offs ra

yS

cot

Tay/

Sco

term ra

yS

cot

r M Sc Fl

ore

Firt

land

Fort

tland

Mo

In M

h, h, e

Eas

Sh

asi

tlan

,d

Sco

t

II IV

µg/k

g O

CBenzo[a]anthracene

500

1000

00

2000

25003000

3500

4000

4500

5000

Oys

terg

rou

s

Boc

ht v

eE

Dol

lard

Bis

cay

y

Nor

ther

nw

ayor

e F

irth,

cnd

Forth and

Ir

diat

eM

oray

Firt

h,S

cotla

ndO

uter

Mur

ray

Firth

, Sco

tland

Flad

enG

roun

d,S

cotla

ndtla

nd

Sco

tland

Loch

s-vo

es,

cnd

Min

ches

Sco

tland

II IV II III

CORE MONIT

µg/k

g O

C

0

500

1000

1500

3000

3500

Oys

terg

roun

ds

Boc

ht v

anw

ater

en, E

ms-

Dol

lard

Bis

cay

Bay

h edia

to

Firt

h,la

nd

Out

eur

ray

Firth

,ot

land

aden

Gro

und,

Sco

tland

te

bn

Sco

tland

Loch

s-vo

es,

land

Min

ches

,S

cotla

nd

II III

CORE MONIT


0 s s- y n h,200

400

600

800

1000

1200

1400

1600O w

at

terg

rou

ade

oun

otla

G Sc

d, dE

µg/k

g O

C

350

Benzo[a]pyrene

1800

ysnd

Boc

ht v

aner

en, E

mD

olla

rd

Bis

cay

Ba

Nor

ther

Nor

way

Offs

hore

Mor

ay F

irtS

cotla

ndTa

y/F

orth

,S

cotla

ndIn

term

edia

teM

oray

Firt

h,S

cotla

ndO

uter

Mur

ray

Firth

, Sco

tland

Fln

rn

ast S

hetla

ndba

sin,

Sco

tland

Loch

s-vo

es,

Sco

tland

Min

ches

,S

cotla

nd

0

50

100

150

200

Bocht vanwateren,

Ems-Dollard

Biscay Bay NorthernNorway

OffshoreMoray Firth,

Scotland

Tay/Forth,Scotland

Minches,Scotland

II IV I II III

CORE MONIT

µg/k

g O

C

Dibenzo[ah]anthracene

250

300

II IV I II III

CORE MONIT


Benzo[ghi]perylene

0

500

1000

1500

2000

2500

3000

Oys

terg

roun

ds

Boc

ht v

anw

ater

en, E

ms-

Dol

lard

Bis

cay

Bay

Nor

ther

nN

orw

ayO

ffsho

reM

oray

Firt

h,S

cotla

ndTa

y/Fo

rth,

Sco

tland

Inte

rmed

iate

Mor

ay F

irth,

Sco

tland

Out

er M

urra

yFi

rth, S

cotla

ndFl

aden

Gro

und,

Sco

tland

Eas

t She

tland

basi

n,S

cotla

ndLo

chs-

voes

,S

cotla

nd

Min

ches

,S

cotla

nd

II IV I II III

CORE MONIT

µg/k

g O

C

Indeno[1,2,3-cd]pyrene

0

500

1000

1500

2000

2500

3000

3500

Oys

terg

roun

ds

Boc

ht v

anw

ater

en, E

ms-

Dol

lard

Bis

cay

Bay

Nor

ther

nN

orw

ayO

ffsho

reM

oray

Firt

h,S

cotla

ndTa

y/Fo

rth,

Sco

tland

Inte

rmed

iate

Mor

ay F

irth,

Sco

tland

Out

er M

urra

yFi

rth, S

cotla

ndFl

aden

Gro

und,

Sco

tland

Eas

t She

tland

basi

n,S

cotla

ndLo

chs-

voes

,S

cotla

nd

Min

ches

,S

cotla

nd

II IV I II III

CORE MONIT

µg/k

g O

C


Annex 11 Recommendations

WGMS recommends:

1) that at their next meeting they review the outcome of the OSPAR/MON assessment in relation toin the view of BCs and BACs, and in preparation for REGNS;

2) to review the possible progress of joint work on (bio)availability measurements; 3) WGMS to review the intersessional work performed by the subgroup on sediment dynamics; 4) to review any new material on indicators for sediment contamination; 5) to review the outcome of the ICES/OSPAR Workshop on Integrated Monitoring of Contaminants and t

in Coastal and Open-Sea Areas (WKIMON); 6) to further collaborate with the WGSAEM, either by meeting together or delegate participants

meeting; 7) that the report and annexes on the estimation of BCs be forwarded to OSPAR for use by MON i

assessment; 8) WGMS recommended that OSPAR or ICES put in place a procedure whereby the data set used

BCs can be reviewed and extended, and BC and BAC values can be regularly reviewed; 9) to meet in February/March ?nd –?th, 2005, at IFREMER, France; 10) that Foppe Smedes, The Netherlands, will continue as WGMS Chair for another three years.

sediments, also

heir Effects

to each other’s

n the 2004/2005

to derive these


Annex 12 Action list

1) Foppe Smedes to collect and coordinate further intersessional work on the measuremencontaminants in sediments initiated by WGMS participants;

2) Birgit Schubert to perform and coordinate intersessional work on sediment dynamics in relati3) Patrick Roose to report progress on relevant matters to WGBEC 2004; 4) Foppe Smedes to inform the project manager of SEDNET on relevant issues dealt with by W5) Maria-Jesus Belzunce to report on SEDNET progress; 6) Patrick Roose to collate and report on EMMA; 7) Ian Davies to be the contact person for matters concerning REGNS; 8) All participants to report on new relevant material on indicators for sediment contamination.

ts of availability of

on to monitoring;

GMS;


Annex 13 Draft resolutions

Proposed terms of references for the 2005 WGMS Meeting:

The Working Group on Marine Sediments in Relation to Pollution [WGMS] (Chair: F. Smedfor five days in La Seyne sur Mer, France, in February/March 2005 to:

a) review the report of the OSPAR/MON assessment in relation to sediments and in thuse of BCs and BACs;

b) review the outcome of the ICES/OSPAR Workshop on Integrated Monitoring Effects in Coastal and Open-Sea Areas (WKIMON)

c) evaluate the suggested joint work on (bio)availability measurement;

d) review the proposed work (coordinated by Germany) for the annex to the sediment provides guidance on the interpretation of sediment trend monitoring data, taking dynamics and also taking into consideration additional contributions from other mem

e) review any new information on the development of indicators of sediment contcontribution to the OSPAR/ICES workshop in indicators

f) continue preparations to summarise the status of contamination of North Sea sedim2004, and any trends in contamination over recent decades. Where possible, the causes be outlined; for input to the Regional Ecosystem Study Group for the North Sea in 20

g) continue collaboration with the Working Group on the Statistical Aspects of Environ

es, Netherlands) will meet

e view of evaluation of the

of Contaminants and their

monitoring guidelines that into account sediment

ber countries;

amination and consider a

ents for the period 2000–of these trends should

06;

mental Monitoring.

d ACME.

ent of contaminants in

WGMS will report by ?? March 2005 for the attention of the Marine Habitat Committee an

Supporting information

Priority: This group handles key issues regarding monitoring and assessmsediments.

Scientific Justification and relation to Action Plan:

Action Plan Nos 1.7, 1.10, 1.11, 2.8, and 4.12

a) review the outcome of the OSPAR/MON assessmesediments, also in the view of evaluation of BCs and BACBy the next meeting the outcome of the OSPAR-available;

b) discussion on the outcome of ICES/OSPAR workshop oof Contaminants and their Effects in Coastal and Openwill allow WGMS to define tasks for future work on thfor integrated chemical and biological effect monitoringassessments of the marine environment;

c) previously discussed methodologies for sediment(bio)availability were considered very promising. Participintersessional work that can be reviewed with view to fguidance for monitoring taking bioavailability into accou

d) the proposed annex to the Sediment Monitoring Guidproviding advice to others, e.g., OSPAR and HELCOM

nt as far as related to s (see item g), below).

MON assessment will be

n Integrated Monitoring -Sea Areas (WKIMON)

e preparation of guidelines that may provide better

assessments in terms of ants have intentions for

uture advice to ICES on nt;

elines will assist ICES in , on the interpretation of

monitoring data with a view to detecting temporal changes in sediment quality. For this, sediment dynamics are of great importance as they affect the evolution of all sediments. The proposed document containing information and guidance should be included as an Annex to the present sediment monitoring guidelines. Participants are suggested to perform intersessional work from other area types. This will be coordinated by Germany and the outcome will be reviewed at this meeting;

e) practical indicators for sediment quality are of paramount importance to display the results of environmental assessments to the general public. Therefore, the group should continue to study and evaluate developments of such indicators;


f) the working groups should give input to the thematic under the coordination of REGNS to develop an integNorth Sea. For the purposes of this study, the North Sea IV and IIIa and does not include intertidal areas. As far aseasonal variation should be described;

g) Monitoring and interpretation will benefit from the pointcollaboration with WGSAEM: continue work to confirmBACs for sediment; the analysis of power of existing prstrategies on sampling schemes for future programmes.

Resource Requirements: None required.

Participants: A subject like bioavailability is of mutual interest to bothPeriodic interactions between the groups and transfer of infoefficient operation of both groups. Selected and interested meparticipate in work of the WGBEC for the interaction and inmutual issues such as sediment quality criteria and bioavailab

A similar exchange is suggested with the WGSAEM

Secretariat Facilities: None required

Financial: None

Linkages to Advisory Committees:

ACME

writing panels working rated assessment of the

comprises ICES Areas s possible, significant

s that were identified for and elaborate BCs and ogrammes; and develop

WGBEC and WGMS. rmation are essential for mbers of WGMS should formation transfer on the ility.

Linkages to other Committees or Groups:

WGBEC, MCWG

Linkages to other Organisations:

OSPAR, HELCOM

Cost share: ICES 100%
