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ICES WGMS REPORT 2013 SCICOM STEERING GROUP ON HUMAN INTERACTIONS ON ECOSYSTEMS

ICES CM 2013/SSGHIE:05

REF. SSGHIE, SCICOM, ACOM

Report of the Working Group on Marine Sedi-ments in Relation to Pollution (WGMS)

18-22 March 2013

Lowestoft, UK

International Council for the Exploration of the Sea Conseil International pour l’Exploration de la Mer

H. C. Andersens Boulevard 44–46 DK-1553 Copenhagen V Denmark Telephone (+45) 33 38 67 00 Telefax (+45) 33 93 42 15 www.ices.dk [email protected]

Recommended format for purposes of citation:

ICES. 2013. Report of the Working Group on Marine Sediments in Relation to Pollu-tion (WGMS), 18-22 March 2013, Lowestoft, UK. ICES CM 2013/SSGHIE:05. 47 pp.

For permission to reproduce material from this publication, please apply to the Gen-eral 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.

© 2013 International Council for the Exploration of the Sea

ICES WGMS REPORT 20133 | i

Contents

Executive summary ................................................................................................................ 1

1 Opening of the meeting ................................................................................................ 3

2 Adoption of the agenda ................................................................................................ 4

3 Spatial design of a regional monitoring programme for contaminants in sediments .................................................................................................................... 5

3.1 Introduction ........................................................................................................... 5 3.2 Selection of strata for the Southern North Sea .................................................. 5

3.3 Data analysis ......................................................................................................... 8

3.4 Issues and considerations .................................................................................. 14 3.4.1 Recommendations ................................................................................. 15

4 Reports on seabed integrity and radionuclides-based sediment modelling. ..................................................................................................................... 16

4.1 MSFD Descriptor 6: Seafloor Integrity ............................................................. 16 4.2 Brief overview of work studying radionuclide transport in the

Irish Sea (1960-2000) ........................................................................................... 16

5 Microplastics and associated chemical contaminants in sediments .................. 18

6 Continue collection of data and develop background concentrations for alkylated PAHs. ..................................................................................................... 19

6.1 Develop of background concentrations for alkylated PAHs in sediments ............................................................................................................. 19

References: ............................................................................................................................. 20

6.2 Develop of background concentrations for dioxins and related substances ............................................................................................................ 22

7 Passive sampling .......................................................................................................... 23

7.1 Discuss the outcome of WKPSPD and as a follow-up, on the use of passive sampling for measurements in sediments in relation to assessing the state of the marine environment. .............................................. 23

7.2 Initiate a review on the use of passive sampling for measurements in sediments ......................................................................................................... 24

7.3 Review the PS guideline .................................................................................... 25

7.4 Report on ongoing and new projects involving passive sampling .............. 25 7.4.1 Update on use of passive samplers in UK .......................................... 25

References .............................................................................................................................. 27

7.4.2 Update on use of passive samplers in Belgium ................................. 28 7.4.3 The Application of Passive Sampler (DGT) Technology for

Improved Understanding of Metal Behaviour at Marine Disposal Sites in the UK ........................................................................ 28

ii | ICES WGMS REPORT 2013

7.4.4 Automation of the passive sampling techniques (France) ............... 29

8 Provide expert knowledge and guidance to ICES Data Centre (possibly via subgroup) as requested ...................................................................... 31

9 Miscellaneous ............................................................................................................... 32

9.1 That MCWG, WGMS and WGBEC hold a concurrent meeting in 2014 with a full day joint plenary to address common areas of interest: a) To define the role of passive sampling in integrated monitoring and assessment (sampling strategy, assessment criteria, deployment alongside bio-indicator species) and use of toxicity tests on passive sampler extracts in monitoring programmes. b) Microplastics ........................................................................ 32

9.2 Deliberations about the future of WGMS ........................................................ 32

10 Recommendations and Action list ............................................................................ 33

11 Chair(s) for 2014 ........................................................................................................... 34

12 Date and venue of the next meeting ......................................................................... 35

13 Closure of the meeting ................................................................................................ 36

Annex 1: List of participants............................................................................................... 37

Annex 2: Agenda ................................................................................................................... 39

Annex 3: WGMS terms of reference for 2013 .................................................................. 40

Annex 4: Recommendations ............................................................................................... 42

Annex 5: Action list .............................................................................................................. 43

Annex 6. Review of WGMS 2013 report regarding OSPAR request ........................... 44

ICES WGMS REPORT 2013 | 1

Executive summary

The Working Group on Marine Sediments in Relation to Pollution (WGMS) met from 18 to 22 March in Lowestoft, UK. The meeting was chaired by Patrick Roose and Lu-cia Viñas and attended by 9 scientists from five countries.

The proposed agenda was accepted without modifications and arrangements were made to carry out the work. Furthermore, a number of informative and relevant presentations were given during the meeting. In particular, information on the use of passive samplers (PS) was presented through this means.

The main task at the meeting was to finish the guidance on the design of a regional monitoring programme for contaminants in sediments, an OSPAR request. WGMS reviewed the output of last years’ meeting and remained in agreement with the ap-proach outlined.

WGMS proposes a contaminant monitoring concept in sediment which is thought to fulfil the MSFD demands of assessing the good environmental status (GES) on a re-gional basis (e.g. southern North Sea) with respect to Descriptor 8 (contaminants). WGMS has worked under the assumption that GES thresholds will be defined for non-normalized concentrations in whole sediments. Hence, in the context of a spatial monitoring plan for assessing GES, non-normalized concentrations in whole sedi-ments (with >20% fines) were used.

In order to test the approach, WGMS conducted a pilot study in the Southern North Sea. Concentration data from this area in the period 2006-2011 were extracted from the ICES database for a subset of contaminants (Cd, Pb, benzo[a]pyrene (BaP), fluo-ranthene (Flu), and CB153) and supporting parameters (Al, organic carbon and silt/clay content). Additionally, GIS information from the same area, identifying the patches of fines, was collected through members of the group.

WGMS identified six areas as suitable strata for further statistical analysis. The choice of these strata was based on local expert knowledge and, although WGMS members felt these areas were sensible given their knowledge, this may need to be further re-fined in the future.

The statistical analysis of concentration data within these strata suggests coefficients of variation of about 35% and 75% for metals and organics respectively, perhaps in-creasing to about 40% and 100% in inshore areas. Considering a random stratified sampling approach within a stratum and using a one-tailed t-test at the 5% signifi-cance level that allows to demonstrate compliance with GES with a power of 90% when the average concentration is half the assessment concentration, the results show that it would require 5 samples per stratum for metals, and between 10 and 15 sam-ples per stratum for organics.

Based on this design, the status of the whole Southern North Sea could be assessed by estimating the mean concentration across the (muddy parts of the) whole Southern North Sea and to compare this to the Assessment Concentration. The power of this assessment would be greater than the power of assessing an individual stratum, be-cause more samples would be involved.

This sampling design is readily applicable to other OSPAR regions. In fact, it was fur-ther tested for the Spanish and French coast, obtaining very similar results to those for the Southern North Sea.

2 | ICES WGMS REPORT 2013

As a recurring topic, WGMS discussed the use of passive samplers for environmental monitoring. Several developments in this field were presented and discussed during the meeting. The group remains convinced of the potential the approach offers and recognizes this to be a topic on which it can constructively work together with WGBEC and MCWG.

WGMS also considered microplastics as an upcoming scientific issue for its work and a field on which it can collaborate with WGBEC and MCWG. Clearly, the current methods for separation, quantification and contaminant analysis of microplastics in sediments are not harmonized and there is merit for ICES action in this field. WGMS feels that it could significantly contribute to this given its expertise. However, WGMS is of the opinion that given the small proportion of microplastics in sediment, it prob-ably doesn’t constitute an important factor from a hazardous substances point of view.

Finally, WGMS discussed its further existence and future topics to some extent. The group was of the opinion that a continued existence is merited and that this will en-hance the scientific output of ICES. The group also recognized the benefits of work-ing closely together with WGBEC and MCWG and concluded that the independent viewpoint it brings to the common topics benefits the overall quality of that output.


1 Opening of the meeting

The 32nd meeting of the Working Group on Marine Sediments in relation to Pollu-tion was opened by Stuart Rogers, the science director of Cefas. He welcomed the WGMS and wished everybody a pleasant stay and fruitful meeting.


2 Adoption of the agenda

After briefly going through it, the agenda was accepted with minor modifications relating to information sent to the chairs by ICES. Arrangements were subsequently made to carry out the work. As last year, it was clear that agenda item 3 below consti-tuted the major task and that it would seriously impact the meeting. Given the im-portance of agenda item 3, it was decided to give it priority at the expense of the other items in the agenda.


3 Spatial design of a regional monitoring programme for contami-nants in sediments

3.1 Introduction

WGMS were requested by OSPAR (2011/1) to develop guidance on the design of a regional monitoring programme for contaminants in sediments which can explain whether good environmental status has been achieved on a larger regional scale (e.g. subregions of the OSPAR Regions) within the period 2010-2020, with the major effort in 2014-2020. The guidance should address:

1 ) the selection of areas where monitoring makes most sense, i.e.; a ) depths that are sensible to monitor (does it make sense to monitor be-

low 1000 m? 500 m? 200 m? 100 m?); b ) sediment types that are sensible to use and the implication for possible

spatial coverage; c ) ship time considerations; d ) time from changes in inputs to response in the sediment can be detect-

ed; 2 ) the required spatial resolution of sampling within these areas.

WGMS 2013 reviewed the output of the last two years’ meeting and remained in agreement with the approach outlined. In order to progress with the design task, a case-study for the Southern North Sea was completed using a GIS approach.

3.2 Selection of strata for the Southern North Sea

Considering the OSPAR request mentioned above, the broad objective consists of comparing mean concentrations across the region to Assessment Concentrations such as ERLs or EACs.

WGMS proposes a contaminant monitoring concept in sediment which is thought to fulfil the MSFD demands of assessing the good environmental status (GES) on a re-gional basis (e.g. southern North Sea) with respect to Descriptor 8 (contaminants). The current higher-level assessment tools (OSPAR Environmental Assessment Crite-ria (EACs) or US Effects Range Low (ERLs)) are based on toxicity information and make no distinction between sediment types (muddy/sandy/gravel) or composition (aluminium or TOC concentrations). Taking this as the current best approach to as-sess the contaminant specific burden in sediment against the GES, a monitoring con-cept that makes use of hydrographically and sedimentologically related strata, which are representing the general features of the assessed region, appeared to be most suitable. The current OSPAR assessment criteria system is made to assess contami-nant data from non-normalized concentrations in total sediment samples.

In reflection of last year and in response to the advice from the review group, WGMS discussed the comments of the review group and agreed that the previous advice regarding normalization for temporal monitoring still stands. However, GES thresh-olds are defined for non-normalized concentrations in whole sediments. Therefore, in the context of a spatial monitoring plan for assessing GES, non-normalized concen-trations in whole sediments (with >20% fines) should be used. In this context, it is important to note that the proposed monitoring strategy is intended to be suitable for a spatial assessment in relation to the MSFD. It is not intended to answer questions


about the relevance, or temporal development, of specific contaminant sources or pathways.

Concentration data for a subset of contaminants (Cd, Pb, benzo[a]pyrene (BaP), fluo-ranthene (Flu), and CB153) and supporting parameters (Al, organic carbon and silt/clay content) were extracted from the ICES database for the Southern North Sea for the period 2006-2011. Belgium provided a separate dataset to this. Because of pos-sible overlap/duplication of data and as this submission was more comprehensive, the ICES data from Belgium was discarded and the dataset provided from Belgium was used instead.

GIS information for the Southern North Sea with emphasis on identifying the patches of fines was collected from members. Two GIS layers describing sediment grain size were available: one being a product of Defra Sea Bed Integrity project (Stephens, D., Coggan, R., and Diesing, M. 2011. Geostatistical modelling of surficial sediment com-position in the North Sea and English Channel: using historical data to improve con-fidence in seabed habitat maps. In ICES CM 2011/G:11) for the western half of the southern North Sea and the other being a product of BSH (German Federal Hydro-graphic Agency) and Smile Consult GmbH, prepared using inter-national data from GEUS (Geological Survey of Denmark and Greenland), TNO (Netherlands) and MUMM (Belgium) and which covered the eastern half of the southern North Sea. Both these layers were merged to produce one map showing silt/clay content greater than 20% (Figure 1).

Figure 1: Merged mud map (Defra seabed integrity –west side and BSH/ Smile Consult GmbH- east side).


Looking at the muddy parts of the Southern North Sea as shown in Figure 1, one can observe that it effectively comprises several larger areas of mud, each subject to their own inputs, pressures, and hydrographic regimes and each of management and envi-ronmental interest, and some smaller, often isolated, areas of mud that are of limited interest. For monitoring and assessment purposes, it is sensible to exclude the smaller areas of mud from consideration, and to apportion the larger areas into distinct stra-ta, which can then be monitored using some form of stratified sampling. The patches of mud within a stratum do not have to be contiguous, but a stratum should have hydrographic coherence.

WGMS members identified six areas as suitable strata for further analysis being: Oys-ter Ground, German Bight, Weisse Bank, North Frisian coast, Wadden Sea and Flem-ish Banks (Figure 2). The choice of these strata was based on local expert knowledge. However, although WGMS members felt these areas were sensible given their knowledge, this may need to be further refined in the future.

Figure 2: Strata identified for the Southern North Sea


3.3 Data analysis

Concentration data from sampling sites within the modelled silt/clay (%) zones in each of the areas were extracted and evaluated (Figure 3). The data were restricted to the years 2006-2011 (the most recent six-year period corresponding to the MSFD re-porting cycle) and to the contaminants mentioned earlier (Cd, Pb, Flu, BaP and CB153). Concentrations measured in sieved (<63 μm) sediments were multiplied by 0.3 to convert them to total sediment equivalents. (This approach is ad-hoc, but has some justification based on a limited number of measurements made in both sieved and unsieved samples – it effectively assumes that all the contaminants are in the fines, and there are 30% fines.) Although the data were not collected for regional as-sessments, in the absence of more targeted information they can be used to get a crude estimate of the variability of contaminant concentrations within each stratum.

In practice, the coefficients of variation will be both contaminant and stratum specific. In particular, they will generally increase with the size of the stratum and are likely to be greater in inshore strata where there are more localized influences. However, the available data weren’t collected with this in mind, and are based on few degrees of freedom, so the estimates above must be treated with much caution. For design pur-poses, they suggest a coefficient of variation of about 35% and 75% is appropriate to metals and organics respectively, perhaps increasing to about 40% and 100% in in-shore areas.

Figure 3: Sampling points extracted from ICES database– red sampling locations in muddy areas


Table 3.1 shows the number of locations sampled each year, the mean concentration, and the coefficient of variation in concentration for each contaminant / stratum com-bination. (Combinations with one or less locations sampled each year are omitted.) The corresponding ERL or EAC is also shown.

Table 3.1.

Oyster Ground

Weisse Bank

German Bight Wadden

Flemish Banks

ERL / EAC

Cd n 2 15 6 6 4

(mg/kg) mean 0.03 0.05 0.28 0.14 0.09 1.2

(%) cv 7 30 52 38 33

Pb n 2 17 6 6 4

(mg/kg) mean 14 21 25 15 9 47

(%) cv 33 13 19 43 26

Flu n 2 2 3 6 2

(μg/kg) mean 32 28 59 37 10 600

(%) cv 37 59 76 125 57

BaP n 2 2 3 6 2

(μg/kg) mean 21 16 25 16 10 430

(%) cv 32 68 75 86 141

CB153 n 2 3 6 4

(μg/kg) mean 0.10 0.78 0.49 0.40 40

(%) cv 81 72 62 114

Probably the simplest form of sampling design, given the stratification of the region, is to conduct simple random sampling within each stratum (i.e. random stratified sampling). To choose an appropriate number of samples within each stratum, we as-sume that we want to test, within each stratum, the hypothesis

H0: μ ≥ AC vs H1: μ < AC

using a one-tailed t-test at the 5% significance level. Here, μ is the true mean concen-tration and AC is the Assessment Concentration. Further, we want to have 90% pow-er for rejecting the null hypothesis (demonstrating acceptable status) when μ = AC / 2. This target is arbitrary, and could easily be modified, but it is useful for illustrative purposes, is meaningful environmentally (all strata are of management interest in their own right, and any with a mean concentration less than half the AC is likely to end up with acceptable status), without demanding unrealistic resources (see below).

Figure 4 shows how the power of the test increases with sample size for a coefficient of variation of 40% (blue), 75% (pink) and 100% (green). It suggests that we require 5 samples per stratum for metals, and between 10 and 15 samples per stratum for or-ganics. Since MSFD will require assessment of both metals and organics, this means taking between 10 and 15 samples per stratum, and hence between 60 and 90 samples for the whole Southern North Sea.


Figure 4. Power as a function of sample size for a coefficient of variation of 40% (blue), 75% (pink) and 100% (green).

Based on this design, the status of the whole Southern North Sea could be assessed in several ways. One option would be to use the individual assessments for each stra-tum, perhaps insisting that the Southern North Sea can have acceptable status only if each stratum has acceptable status. An alternative would be to use the data from each stratum to estimate the mean concentration across the (muddy parts of the) whole Southern North Sea and to compare this to the Assessment Concentration. The over-all mean would be a weighted average of the stratum means, where the weights are proportional to the area of the strata (and would thus be dominated by any large are-as of mud). The power of this assessment would be greater than the power of an in-dividual stratum assessment, because more samples would be involved. For example, suppose there are 6 strata, all of equal area, all with a mean concentration of μ, and all sampled with 15 samples, and suppose the within-stratum coefficient of variation is 100%. Then, in an individual stratum, we would have 90% power for rejecting the null hypothesis when μ = AC / 2, but in the Southern North Sea, we would have 90% power when μ = 3 AC / 4.

The design above could be easily refined as more data become available. For exam-ple, stratum specific coefficients of variation could be used to reduce sampling effort in more homogeneous strata. Also, sampling effort could be reduced in those strata where concentrations are expected to be ‘very low’ (i.e. well below AC / 2). Finally, if some strata have strong spatial gradients (more likely in inshore strata), then they could be further stratified to reduce sampling effort / increase power.

As illustrated below, this design approach is readily applicable to other OSPAR re-gions. However, there may be other (practical and/or logistical) limitations that re-quire consideration. For example, it is not possible to routinely collect undisturbed surface sediment samples from very deep water (e.g. >500 m) and, given that concen-trations will be low and so few samples required, it would also be very costly to sample distant areas.

n

pow

er

0.2

0.4

0.6

0.8

1.0

5 10 15 20


Design approach applied to Spain

For the Spanish area, a similar approach was applied. Three strata were identified taking into account the available information on the sediment composition of the area (http://mapserver.ieo.es/website/WMS_IEO/viewer.htm): Eastern Bay of Biscay, Gali-cia and Gulf of Cadiz (Figure 5).

Figure 5. Sediment composition and strata identified in the Spanish coast.

Sampling point concentration data from within the silt/clay zones in each of the areas was extracted and evaluated. The data were restricted to 2010 (the most recent spatial sampling in the area) and to the same suite of contaminants. As per previous case study, although the data were not collected for regional assessments, in the absence of more targeted information they can be used to get a crude estimate of the variabil-ity of contaminant concentrations in each stratum.

Table 3.2 shows the number of locations sampled in each stratum, the mean concen-tration, and the coefficient of variation in concentration for each contaminant / stra-tum combination. The corresponding ERL or EAC is also shown.

http://mapserver.ieo.es/website/WMS_IEO/viewer.htm


Table 3.2.

Eastern Bay of Biscay Galicia Gulf of Biscay ERL / EAC

Cd n 10 16 13

(mg/kg) mean 0.18 0.06 0.17 1.2

(%) cv 50 44 15

Pb n 11 16 13

(mg/kg) mean 47.6 22.0 56.2 47

(%) cv 53 28 45

Flu n 11 16 13

(μg/kg) mean 287 8.2 8.6 600

(%) cv 77 111 49

BaP n 11 16 13

(μg/kg) mean 148 4.5 4.2 430

(%) cv 77 129 44

CB153 n 11 2 7

(μg/kg) mean 2.30 0.17 0.81 40

(%) cv 74 9.2 77

These results suggest that the proposed coefficients of variation of about 35-40% and 75-100% for metals and organics respectively are also appropriate to this area and that this approach could also be applied in this region. Therefore, by using the same power analysis as in the previous case study, it is suggested that between 10 and 15 samples are to be collected at each stratum for Spain.

Design approach applied to France

For the French area, the same approach was used. Nine strata were identified taking into account the available information on the sediment composition of the area (http://wwz.ifremer.fr/dcsmm; Figure 6) and expert knowledge: North Picardy, Seine Bay, North Brittany, South Brittany, Rochebonne, Grande Vasiere Area, Pertuis Cha-rente-Gironde, Arcachon Basin and Basque Country. Although these proposed areas seemed sensible given the expert knowledge, they may need to be further refined in the future.

http://wwz.ifremer.fr/dcsmm


Figure 6. Sediment composition and strata identified along the French coasts (sources SHOM, IGN).


Sampling point concentration data from the silt/clay zones (silt/clay content greater than 20%) in each of the strata was extracted and evaluated. The available data (sources Ifremer, Quadrige 2) corresponded to the period 1998-2003 and to the con-taminants suite previously mentioned (i.e. Cd, Pb, Flu, BaP and CB153). Within this period, each stratum was sampled once at different sampling sites. Although the data were not collected for regional assessments, in the absence of more targeted infor-mation they can be used to get a crude estimate of the variability of contaminant con-centrations in each stratum. No data were available for stratum 9 (Grande Vasière Area).

Table 3.3 presents the number of locations sampled in each stratum, the mean con-centration, and the coefficient of variation in concentration for each contaminant / stratum combination. The corresponding ERL or EAC are also shown.

Table 3.3

1- North Picardy

2- Seine Bay

3- North Brittany

4- South Brittany

5- Roche-bonne

6- Pertuis Charente -Gironde

7- Arcachon Basin

8- Basque Country

ERL-EAC

Cd n 14 38 52 45 2 10 4 4

(mg/kg) mean 0.39 0.25 0.23 0.16 0.09 0.19 0.11 0.13 1.2

(%) cv 64 68 108 48 8 66 48 72

Pb n 14 38 52 45 2 10 4 4

(mg/kg) mean 16 23 34 37 21 36 17 63 47

(%) cv 47 40 114 46 23 17 26 57

Flu n 14 38 52 45 2 10 4 4

(μg/kg) mean 170 69 49 84 7 57 326 275 600

(%) cv 112 105 128 132 49 140 102 111

BaP n 14 38 52 45 2 10 4 4

(μg/kg) mean 65 68 21 40 2,5 35 148 72 430

(%) cv 86 100 118 114 79 165 115 160

CB 153 n 14 38 52 45 2 10 4 4

(μg/kg) mean 0.9 2.2 0.97 0.76 0.15 0.49 0.25 2.5 40

(%) cv 102 87 142 82 47 58 52 75

For the eight proposed strata, the coefficients of variation ranged from 8 to 114% and from 47 to 165% for metals and organics respectively. Higher coefficients of variation were observed for larger and inshore strata where there are more localized influ-ences. The proposed design approach seems to be applicable to the French regions also.

3.4 Issues and considerations

In order to get a good definition of the strata it is important to have high-resolution GIS layers of sediment type.

For practical purposes, the depth should be limited to <500m given the difficulties associated with sampling in deeper waters.


Spatial monitoring in MSFD is not expected to replace ongoing monitoring plans de-signed to examine temporal trends, or local issues.

If when sampling, any of the samples are not composed of muddy sediments, then the sampling will need to adapt by discarding such samples and collect alternative material at other, randomly selected, locations.

The group considers that this monitoring strategy would also be applicable for a pas-sive sampling-based monitoring programme.

3.4.1 Recommendations

WGMS recommends that OSPAR coordinates Contracting Parties for each subregion in order to agree a regional monitoring sampling programme based on the strategy outlined. The group recommends that a passive sampling-based monitoring pro-gramme is initiated for the same sampling sites.

WGMS is of the opinion that this sampling design allows assessment of good envi-ronmental status for the Southern North Sea and merits to be developed into an OSPAR guideline.

Summary of the approach recommended for producing spatial sediment monitoring designs on a Regional scale:

1 ) Identify areas with ≥20% fines and/or those classed as mud using the Folk classification triangle

2 ) Create strata containing only areas ≥20% fines. 3 ) Use any existing data to estimate mean concentrations and variability 4 ) Undertake a power analysis to define the number of samples required in

each strata 5 ) Decide on how to aggregate individual strata assessments to the Regional

scale (for example, by using the weighted mean of the individual strata means, using strata area as the weighting factor)

6 ) Refine the design in the light of the additional data obtained above (e.g. the location of strata, and the number of samples required per strata)

7 ) Note, however, that while this design approach should also be applicable to the deep sea (>500 m) where sediments might be expected to have lower and less variable contaminant concentrations, it is not practically possible to routinely obtain samples from such depth.


4 Reports on seabed integrity and radionuclides-based sediment modelling.

4.1 MSFD Descriptor 6: Seafloor Integrity

A presentation was given by Dr R Parker (et al.,) which summarized sediment bioge-ochemical status and function information in the Channel and North Sea funded by the UK government. This work was focused towards indicator development in rela-tion to descriptor 6 (Seafloor Integrity) of the MSFD. New observations had been used to assess the utility of various parameters to describe status of different seabed regions (as determined using sediment type, stratification and depth), the variance in status and how they matched to ICES criteria for indicator development. The study had illustrated the possibility of defining assessment regions within the shelf sea are-as which had defined status and variability, controlling processes and would likely respond to pressures in different ways. The biogeochemical metrics that performed best were oxygen penetration (OPD, from microelectrodes), sediment redox-Fe3+/Fe2+ boundary (as described using the apparent Redox Continuity Depth-aRPD) derived from Sediment Profile Imagery (SPI) and total organic carbon levels of the sediment. All these parameters are highly relevant to contaminant behaviour, especially those that are redox sensitive such as metals. It was highlighted that the regional assessment unit approach and the proposed metrics (OPD and aRPD in par-ticular) would also link across to regional assessments of Descriptor 8 and there was potential to link up sampling approaches and key indicator parameters.

References:

Coggan et al., 2013 Mapping the structure, function and sensitivity of the seabed sed-iment habitats to support assessment of the sea-floor status and the broadscale moni-toring and management of the benthic environment. Defra final project report ME5301

Parker et al., 2012 Alternative metrics for assessing ‘sea-floor integrity’ under the Ma-rine Strategy Framework Directive. Defra project ME5301 milestone report

Parker et al., 2012 Recommended biogeochemical targets and indicators for MSFD monitoring and management of the UK seabed. Defra project ME5301 milestone re-port

4.2 Brief overview of work studying radionuclide transport in the Irish Sea (1960-2000)

John Aldrich from Cefas gave a talk on behalf of Peter Kershaw, Kins Leonard, John Aldridge and others on the study of radionuclide transport in the Irish Sea.

In his talk, results were presented from the modelling of the marine transport of Cae-sium (137Cs), Plutonium (239/240 Pu) and Americium (241Am) discharged from the Sellafield nuclear processing plant in the Irish Sea. The processes included in the model were 1) transport in the water column, 2) exchange of contaminants between dissolved and particulate phases, 3) wave-current sediment resuspension, 4) sedi-ment transport, 5) pore water exchange, and 6) mixing of material within the seabed,. Transport in the water column is by a combination of tide, wind and density driven flows. Sediment transport is based on the erosion, advection, and deposition of three sediment classes representing sand, flocculated mud/silt and fine background com-ponents. Transfer of radionuclides between the dissolved and sediment phases is im-plemented using rate equations. A layered seabed is incorporated with transfers


between layers representing biological and physical mixing processes. The results demonstrate that the model is able to reproduce observed concentrations of radionu-clides in the water column, the build-up of 239/240 Pu in the seabed over a thirty year time span and the recent changes in seabed distribution. The model is used to identi-fy and quantify the mechanizms responsible for the recent redistribution of 239/240 Pu in the region. The results suggest that while sediment transport plays an im-portant role in redistributing contaminated sediment in the eastern Irish Sea, de-sorption, followed by transport in the dissolved phase and re-absorption onto partic-ulate material is the primary mechanizm for redistribution of 239/240Pu over longer distances.


5 Microplastics and associated chemical contaminants in sediments

WGMS considered the issue of the presence of microplastics in sediments and con-cluded that it is an important topic. Microplastics are considered to be both a contam-inant and a potential source for hazardous substances.

Given the small proportion of microplastics in sediment compared to e.g. organic material and the low reported concentrations of hazardous substances on them, it probably doesn’t constitute an important factor from a hazardous substances point of view.

Still, the study of microplastics in sediment poses an analytical challenge. Currently, there seem to be no agreed upon or uniform ways to determine the amount of micro-plastics in sediment or how to separate them from the sediment for further analysis. Those are the kind of topics on WGMS could formulate advice for the wider scientific community.

At the meeting there was clearly not enough expertise and information to consider this topic more extensively and the group decided to put this on the agenda for next year’s meeting.

WGMS members are asked to bring relevant information and/or expertise to the meeting in order to do a more in-depth analysis of the problem of microplastics. Fur-thermore, this topic should indeed be discussed at the joint meeting with WGBEC and MCWG.


6 Continue collection of data and develop background concentrations for alkylated PAHs.

6.1 Develop of background concentrations for alkylated PAHs in sediments

At its meeting, WGMS reassessed the background concentrations for alkylated PAHs on the basis of an updated set of data. Sediment core data were obtained from France (2-Bay of Biscay), Scotland (3- Loch Etive) and Norway (19- Oslofjord, Southwestern Barents Sea and Northeastern Norwegian Sea). The values obtained were then com-pared to those previously proposed by the group in 2008 (Table 6.1). The new set of values (presented in the right column) is quite similar to the former one (ratios less than 2.5) with the exception of the one for C4-napthalenes (NAP C4, ratio of around 8). On the basis of this reassessment, WGMS decided that the newly calculated back-ground concentrations in the second column of the table should, from now on, be used in OSPAR assessments.

Table 6.1

Parameter

BC OSPAR (µg/kg dry weight, normalized to 2.5% TOC)

WGMS 2013 (µg/kg dry weight, normalized to 2.5% TOC)

NAPC1 2.7 3.4

NAPC2 6.7 9.2

NAPC3 3.3 5.3

NAPC4 0.3 2.0

PAC1 3.9 5.1

PAC2 3.7 4.2

PAC3 2.2 2.9

PAC4 1.6

DBTC1 1.0 1.4

DBTC2 0.7 1.1

DBTC3 0.4 0.9

CHRC1 3.7 2.7

CHRC2 3.2 2.3

CHRC3 1.1

Data were also available from a dated sediment core from the Eastern Levantine Ba-sin (Mediterranean). This core was collected within a collaborative program between Ifremer (France) and the National Council for Scientific Research (CNRS) in Lebanon. Background concentrations for PAHs were determined by the mean concentration of all the layers that date back to before 1852 (Azoury et al. 2013). The obtained values (Table 6.2) were then compared to the background concentrations recently proposed by MEDPOL (UNEP/MAP 2011) for the Mediterranean area and to the OSPAR BC (after normalization to 2.5% TOC). The values obtained for the parent PAHs are al-ways about 4 times lower than the BC proposed by MEDPOL with the exception of pyrene that was an order of magnitude lower. Considering the normalized back-ground concentration, the BC values obtained from the Levantine Basin core seem to be quite similar to the OSPAR BCs (or WGMS 2013 BC) for the alkylated PAHs and


anthracene. However, for all other PAHs, an order of magnitude difference was ob-served between the two datasets. The largest difference ratio (factor of about 50) was observed for Indeno[1,2,3-cd]pyrene and Benzo[g,h,i]perylene .

Background concentrations for Pb and Hg were also determined from this Mediter-ranean core and compared to the MEDPOL and OSPAR BC. Data reported by Elbaz-Poulichet et al. (2011) for a 3500-year record of Hg and Pb contamination in a Medi-terranean lagoon were assessed in the same way. The data are gathered in Table 6.3.

The BCs determined from the Mediterranean lagoon were similar to the OSPAR and MEDPOL ones. In contrast, the BC from the Levantine Basin core was lower than the OSPAR/MEDPOL values by a factor 4 or 7 for Pb and Hg respectively.

Taking all these observations into account, WGMS recommended that further work should be undertaken to extend the dataset and to update (if necessary) the back-ground concentration determined for parent PAHs and metals using the available new dataset or incorporating new data that might be available before the next meet-ing.

References:

S. Azoury, J. Tronczyński, JF. Chiffoleau, D. Cossa, K. Nakhlé, S Schmidt, G. Khalaf. 2013. His-torical records of Hg, Pb and PAH depositions in a dated sediment core from the Eastern Mediterranean. Environ. Sci. Technol., submitted.

UNEP/MAP (2011). Development of assessment criteria for hazardous substances in the Medi-terranean. UNEP(DEPI)/MED WG. 365/Inf.8, Athen, 41p.

F. Elbaz-Poulichet, L. Dezileau, R. Freydier, D. Cossa, and P. Sabatier. 2011. A 3500-Year Rec-ord of Hg and Pb Contamination in a Mediterranean Sedimentary Archive (The Pierre Blanche Lagoon, France). Environ. Sci. Technol. 2011, 45, 8642–8647 (extracted from support-ing information)


Table 6.2

Parameter

BC Dated sediment core Eastern Levantine Basin - Mediterranean (Azoury et al. 2013) BC OSPAR

BC WGMS 2013

BC MEDPOL cores 2011 (UNEP/MAP 2011).

μg/kg dw. μg/kg dw., normalized 2.5% TOC

μg/kg dw., normalized 2.5% TOC

μg/kg dw., normalized 2.5% TOC

μg/kg dw

Phenanthrene (P) 1.16 3.31 17 4.6

Anthracene (A) 0.26 0.73 3 0.8

PAC1 1.12 3.19 3 5.1

PAC2 0.80 2.27 4 4.2

PAC3 0.46 1.30 2 2.9

Fluoranthene 1.14 3.23 20 5.6

Pyrene 1.36 3.86 13 10.3

Benzo[a]anthracene 0.62 1.76 9 3.5

Chrysene/triphenylene (CHR) 0.77 2.19 11 1.3

C1-CHR 0.49 1.39 2.7

C2-CHR 0.22 0.61 2.3

C3-CHR 0.02 0.06 1.1

Benzo[a]pyrene 0.33 0.93 15 2.6

Indeno[1,2,3-cd]pyrene 0.63 1.78 50

1.7

Benzo[ghi]perylene 0.51 1.46 45 1.3

DBT 0.05 0.15 1

C1-DBT 0.10 0.28 1

C2-DBT 0.19 0.54 1

C3-DBT 0.08 0.23 0

Table 6.3

Parameter

BC Dated sediment core Eastern Levantine Basin - Mediterranean (Azoury et al. 2013)

BC Dated sediment core Mediterranean Lagoon (Elbaz-Poulichet et al. (2011) BC OSPAR

BC cores MEDPOL 2011 (UNEP/MAP 2011)

mg/kg dw. mg/kg dw., normalized 5% Al

mg/kg dw., mg/kg dw., normalized 5% Al

mg/kg dw., normalized 5% Al

mg/kg dw

Pb 11 6.2 20 19 25 20

Hg 0.07 0.01 0.02 0.02 0.05 0.03

Action: all members are to search for additional data.

Pending the availability of new data, WGMS will investigate adapting Parent PAH data at its meeting in 2014.


6.2 Develop of background concentrations for dioxins and related substances

Up till now, no information has reached the group concerning levels of dioxins and related substances in dated sediment cores.

Action: all members are to search for relevant data.


7 Passive sampling

7.1 Discuss the outcome of WKPSPD and as a follow-up, on the use of passive sampling for measurements in sediments in relation to assessing the state of the marine environment.

Craig Robinson (co-chair of WKPSPD) presented to WGMS the presentation of Kees Booij (co-chair WKPSPD) that he had given to the MCWG. This summarized the dis-cussions and findings of WKPSPD, with the main point of relevance to WGMS being the recommendation to replace traditional sediment monitoring of hydrophobic or-ganic contaminants with sediment passive sampling (PS) of these. The advantage of the PS approach in removing the need for normalization and the link to toxicity was recognized by WGMS. There were some concerns expressed about some of the prac-tical issues involved relating to the volumes to be collected and stored, the possible need to work on fresh sediments, and the amount of laboratory space required to un-dertake the passive sampling procedure.

With respect to coupling of PS and passive dosing, WGMS considered that by includ-ing mixture effects this complements the use of compound specific assessment crite-ria, but was not an adequate substitute for the development of suitable assessment criteria, since it does not account for chronic effects and may not protect against the most sensitive species.

Passive sampling devices in sediment have been extensively used over the last dec-ade and WGMS believes that they can potentially be a very useful tool to assess the good environmental status of the marine environment, in particular for hydrophobic contaminants because the concentration measured can be directly related to availabi-lity (and thus to toxicity). Passive sampling for polar compounds in sediment is of limited use because it does not produce quantitative results, although it can be used for screening purposes. For metals, more work is required to assess the spectrum of species measured by DGT in sediments and to determine the rates at which such spe-cies will diffuse through the hydrogel under different physical and chemical condi-tions, including varying thickness of the gel layer. In addition, the relationship between DGT values and toxicity to aquatic biota requires further study. The ap-proaches and methodologies of the passive samplers in sediments differ, therefore WGMS believes that a review of the use of passive sampling for measurements in sediments and approaches to the estimation of pore water concentrations will be nec-essary and useful.

Additionally, there is currently no GES assessment criteria related to freely dissolved contaminants, and since there is an increasing number of publication reporting toxici-ty related to freely dissolved contaminant concentrations as a result of passive do-sing techniques, these data might be suitable to derive the GES targets. The toxicity study for hydrophobic compounds using passive sampling is at an advanced stage whereas passive dosing for hydrophilic compounds is not a better alternative to the conventional toxicity testing. In addition to the existing GES assessment criteria for metals in sediment, assessment criteria reported in fluxes should be investigated, as this is how results from metal passive sampling are usually reported.


7.2 Initiate a review on the use of passive sampling for measurements in sediments

In 2012, WGMS said that it would work on producing a review of sediment passive sampling, including identification of suitable samplers and brief guidelines for their use. In 2013 WGMS has reviewed a draft TIMES document on the passive sampling of sediments for hydrophobic contaminants using silicone rubber sheets, silicone rubber bottles and LDPE strips (see table 7.1), and identified people willing to assist the author with completing this. Additionally, the group considered that there re-mains a requirement for a wider review of different passive samplers and their ap-plicability to assess sediment quality in relation to MSFD D8 and OSPAR. To this end, the group will review why the use of passive sampling is advantageous compared to e-existing monitoring techniques. The Group is aware of proposals at the recent SETAC Technical Workshop on Passive Sampling Methods to Improve Contaminat-ed Sediments (see link below) for publication of a series of papers to provide back-ground on the use of PS. The document to be produced by WGMS will address environmental monitoring, rather than management of contaminated sediments, but should be written in the light of that work, in order to avoid duplication of effort.

WGMS identified a list of passive samplers suitable for working on sediments with and a list of potential authors who the co-chairs will contact in order to establish their willingness to provide outline text ahead of the 2014 meeting of WGMS (see table).

Table 7.1

Section Type of contaminant Possible author

Why use PS of sediments in a monitoring context?

All and any To be determined?

DGT Metals Thi Bolam

DET

Silicone rubber sheets Semi-polar and hydrophobic organics

Els Monteyne / Craig Robinson

Silicone rubber coated bottles

Semi-polar and hydrophobic organics

Foppe Smedes / Philipp Mayer

LDPE strips Hydrophobic organics Ian Allan / Celine Tixier

POM Hydrophobic organics Ian Allan / Kristofer Naes?

Link to Pellston SETAC Technical Workshop Executive Summary:

http://c.ymcdn.com/sites/www.setac.org/resource/resmgr/publications_and_resources/executivesummarypassivesampl.pdf




7.3 Review the PS guideline

WGMS expresses its gratitude to Foppe Smedes for making available this draft doc-ument for use as the basis of a future TIMES publication on passive sampling of sed-iments, which is both timely and required. WGMS (CT, EM and CR) would like to offer assistance to Foppe in completing the document. WGMS consider that the doc-ument could be structured slightly differently in order to provide clear guidance on how to undertake sediment PS using (a) silicone rubber sheets, (b) silicone coated bottles, (c) LDPE strips. Additionally, the document could benefit from a more com-prehensive introductory section.

We note that this text appears to have been used to form part of a more comprehen-sive report to the Dutch Government on measuring concentrations of bioavailable hydrophobic contaminants in soils (Brant et al., 2012), although there are some signif-icant differences, particularly in relation to the section on depletion and equilibrium.

7.4 Report on ongoing and new projects involving passive sampling

7.4.1 Update on use of passive samplers in UK

Craig Robinson presented on behalf of his colleagues (CD Robinson, E Emelogu, L Webster, P Dymond, C Moffat, P Pollard, C McKenzie, T-B Seiler, S Heger, H, Hollert, IW Oliver, J Dobson, L Stevens, F Napier and F Smedes) a study on passive sampling and in vitro toxicity testing in Scottish aquatic environments

Marine Scotland Science has used silicone rubber passive samplers to determine en-vironmentally relevant concentrations of PAHs and PCBs, of water (e.g. Smedes et al., 2007 a,b,c) or of sediments (Yates et al., 2011). Recently the range of compounds in-vestigated was expanded to include PBDEs and less polar compounds such as al-kyphenols, pesticides, and herbicides (e.g. Balaam et al., 2011) – the latter have been analysed by partner laboratories and with either semi-quantitative estimates of sam-pling rates, or without calibration for sampling rates. Most recently, extracts of pas-sive samplers have been used in a variety of in vitro toxicity testing systems in order to improve understanding of the potential of the contaminant burdens to cause ad-verse environmental effects in two contrasting environments (Emelogu et al., 2013a,b).

Silicone rubber passive sampling devices (SR-PSDs) were deployed (7-12 weeks) at up to 5 sites in two localities of differing characteristics. The studied areas were the River Ythan and its estuary, and the estuary and Firth of Forth. The Ythan is a small, agriculturally dominated catchment in NE Scotland, parts of which suffer from de-clining ecological status under the WFD classification scheme; the Firth of Forth is a major coastal inlet on the Scottish east coast that has potential sources of contami-nants in the form of run-off and discharges from urban areas, industrial sites, includ-ing a major oil refinery and petrochemical complex, coal-fired power stations, and shipping.

Passive sampling for the determination of aqueous freely dissolved PCBs and PAHs followed ICES guidelines (Smedes and Booij, 2012), using PCBs and deuterated PAHs as PRCs, and GC-ECD (PCBs) and GC-MS (PAHs) analytical instrumentation. Addi-tionally, concentrations of up to 47 pesticides and 22 acid and urea herbicides were determined in the silicone rubber samplers (ng/g) using GC-MS/MS and LC-MS/MS instrumentation respectively (Emelogu et al., 2013a,b). At two locations on the R.


Ythan, continuous autosamplers were co-deployed with the SR-PSDs and composite water samples (6-8 wks) were subjected to conventional pesticide (GC-MS/MS) and herbicide (LC-MS/MS) analyses. At all ten sampling sites, additional SR samplers were deployed in order to provide extracts for use in toxicity tests.

In order to improve understanding of the potential of the develop expertise and in-troduce new techniques in a stepwise manner, initial toxicity testing was conducted using extracts of the silicone rubber samplers transferred to methanol or DMSO and exposed to cell lines or test organisms in a 24 well microtitre plate exposure system. Cytotoxicity (neutral red uptake assay) and cytochrome P450 enzyme induction (EROD activity) were determined in a rainbow trout liver cell line (RTL-1W; Emelogu et al., 2013a), effects on zebrafish were assessed using the Fish Embryo Toxicity (FET) test (Emelogu et al., 2012), and effects on marine phytoplankton (Pavlova lutheri) as-sessed using the algal growth inhibition test (Emelogu et al., submitted). In a separate experiment, the silicone rubber O-ring passive dosing procedure described by Smith et al. (2010) was used to expose the RTL-1W cell line to two PAH compounds (chrys-ene, fluoranthene) loaded from a saturated solution with a dioxin (2,3,7,8-TCDD) as a positive control; cytotoxicity and EROD activity were then determined.

Freely dissolved PAH (Σn=40 = 27-70 ng/l) concentrations showed little variability be-tween sites in the Ythan, and were similar to those determined in the estuary and Firth of Forth (49-70 ng/L). PCB concentrations were higher in the Forth (ΣICES-7 = 70-130 pg/L) than in the Ythan (3-30 pg/l), reflecting the greater population density and number of historic contaminant sources in the Forth catchment. At each site in the Ythan, 36-39 pesticides (of 47 in the method) and 4-8 acid/urea herbicides (of 22) were detected in the SR-PSD, while analysis of simultaneously obtained composite water samples failed to identify any pesticides present, although 5-6 herbicides were de-tected. From the estuary and Firth of Forth, 4-6 pesticides and 1-4 herbicides were detected in SR-PSDs.

SR-PSD extracts from the Ythan were not cytotoxic to rainbow trout liver cells, but they all induced CYP1A activity; this activity was much greater than that predicted from the use of Toxic Equivalency Factors and the determined concentrations of PAHs and PCBs. Three of the Ythan sites (the two on the stream failing WFD ecolo-gy, and the estuary) also showed toxicity to the Fish Embryo Test. Extracts from the Forth were subject to the algal growth inhibition test, and while all showed some ac-tivity, the level of growth inhibition was low.

Passive dosing of RTL-W1 cells showed that chrysene was cytotoxic and induced EROD activity, whereas fluoranthene was cytotoxic and did not induce EROD activi-ty.

To summarize, SR-PSDs were shown to sequester semi-polar compounds with log Kow down to 1.5, as well as PAH and PCBs, and shown suitable to capture infor-mation on the environmental presence of many more compounds that could be ob-tained from continuous autosamplers or spot sampling. Extracts of SR samplers were shown to dose-responsively induce the activity of cytochrome P4501A detoxification enzyme in fish liver cells and to inhibit algal growth, without being cytotoxic. Cou-pling of passive sampling with in vitro toxicity tests can be used to improve under-standing of the nature of pollutant pressures, and the coupling of passive sampling with passive dosing may provide a way to assess the significance of complex mix-tures of non-polar and semi-polar contaminants sampled from the environment without reference to predefined toxicity thresholds which are not suitable for as-


sessing freely dissolved concentrations, or where they are not available (e.g. for sed-iments).

References

Balaam, J., et al., 2011. Project C3461 – From Marine Strategy Framework to Good Environ-mental Status: The use of passive sampling for monitoring offshore waters. Cefas report to Defra. 74pp.

Emelogu et al., 2012. Linking complex mixtures of organic contaminants to biological respons-es via passive sampling and embryonic zebrafish assays. Oral presentation at the 5th In-ternational Passive Sampling Workshop and Symposium (IPSW 2012), 11-14th of September 2012, Columbia, Missouri, USA.

Emelogu, et al., 2013a. Integration of passive sampling and in vitro bioassay techniques for chemical and biological effects analysis of organic contaminants in water. Chemosphere, 90, 210–219.

Emelogu, et al., 2013b. Identification of selected organic contaminants in streams associated with agricultural activities and comparison between autosampling and silicone rubber passive sampling. Science of the Total Environment, 445–446, 261–272.

Smedes, F., Davies, I. M., and Tronczynski, J. 2007a. ICES passive sampling trial survey for water and sediment (PSTS) 2006 – 2007. Part 1: objectives, design and realization. ICES Annual Science Conference, Helsinki, 17 – 21 September, 2007.

Smedes, F., van der Zande, A., Tixier, C., and Davies, I. M. 2007b. ICES passive sampling trial survey for water and sediment (PSTS) 2006 – 2007. Part 2: laboratory intercomparison, analytical issues and lessons learned. ICES Annual Science Conference, Helsinki, 17 – 21 September, 2007.

Smedes, F., van der Zande, A., and Davies, I. M. 2007c. ICES passive sampling trial survey for water and sediment (PSTS) 2006 – 2007. Part 3: preliminary interpretation of field data. ICES Annual Science Conference, Helsinki, 17 – 21 September, 2007.

Smedes, F., Booij, K. 2012. Guidelines for passive sampling of hydrophobic contaminants in water using silicone rubber samplers. ICES Techniques in Marine Environmental Sciences No. 52. International Council for the Exploration of the Seas, Copenhagen, Denmark. 21 pp.

Yates et al., 2011 Application of silicone rubber passive samplers to investigate the bioaccumu-lation of PAHs by Nereis virens from marine sediments. Environmental Pollution, 159, 3351–3356


7.4.2 Update on use of passive samplers in Belgium

Els Monteyne presented work done in Belgium on integrated passive sampling with PDMS-strips during the project INRAM.

Monitoring of organic pollutants in the marine environment is costly and time-consuming. Many data-points need to be generated for spatial or temporal chemical assessment. The use of passive samplers (PS) to provide representative measure-ments of concentrations in water and sediments has received increasing interest by scientist and regulators during the past decade. Research conducted in the context of INRAM project (2007-2010) provided some clear indications (for PCBs and PAHs) that PS techniques may provide the link between freely dissolved concentrations and contaminant pressure.

For 4 subsequent years polydimethylsiloxane (PDMS) passive samplers were de-ployed in the 3 major harbours in Belgium and at sea. The sheets were analysed for PAHs and PCBs. With the use of the performance reference compounds (PRCs), sampling rates were calculated and water concentrations were determined. The sam-pling rates were calculated using the non-linear least-square method, taking into ac-count lower uptake rates for higher molecular weight compounds. Rs varied from 0.9 to 34.8 L d-1 for the different target compounds, while estimated freely dissolved concentrations for sum 15 PAHs varied between 3.9 and 170 ng L-1 and for sum 14 PCBs between 0.030 and 3.1 ng L-1. The samplers showed a difference in pollution pressure between the harbours, as well as within the harbours. Contaminant pressure could also be defined by ng of compound per g of sampler. Although this would be a relative scale, when linked to toxicity, this could also become a meaningful figure. Taking sorption to organic matter into account, computed concentrations from pas-sive sampling data to whole water concentrations give lower concentrations then the measured whole water concentrations. In Belgium passive sampling in a reference station with other measuring devices is done the whole year around now.

Freely dissolved concentrations of PAHs and PCBs were used as the key input pa-rameter in equilibrium models to obtain estimations of the whole water concentra-tions of these compounds as well as their concentration in sediment, suspended particulate matter (SPM) and biotic tissue. The modelling results were compared to analytical data obtained through conventional chemical analysis of spot samples orig-inating from the passive sampling area. Good correlation was found for whole water and biota. However, in the case of sediment, there was a good correlation, but also a deviation that was not accounted for in the model.

7.4.3 The Application of Passive Sampler (DGT) Technology for Improved Under-standing of Metal Behaviour at Marine Disposal Sites in the UK

Thi Bolam presented the outcome of the investigation above on behalf of her col-leagues (Thi Bolam1, Ruth Parker1, Claire Mason1, Silke Kröger1, Briony Silburn1, Dave Sivyer1, Silvana Birchenough1, Andrew Mayes2 and Gary Fones3)

1 Centre for Environment, Fisheries and Aquaculture Science, Lowestoft Laboratory, Pakefield Road, Lowestoft, Suffolk, UK, NR33 0HT; [email protected]

2 Chemistry Department, University of East Anglia, Norwich, UK, NR4 7TJ

mailto:[email protected]


There are 136 sites currently designated for dredged material disposal around the coast of England, mostly in close proximity to the coast and major ports or estuaries. The nature of the disposed material may vary from soft silts to boulders or even crushed rock according to origin, although the majority consists of finer material. Representative sites are selected for annual monitoring based on a tier-based ap-proach that classifies a number of possible issues or environmental concerns, relating to contaminants that may be associated with dredged material disposal. Key ques-tions are; what is the fate of contaminants (including metals) imported to the site with the disposed material and what effect does this have on ecological components? Con-taminant parameters are determined as part of the monitoring, such as tributyltin, polyaromatic hydrocarbons, organohalogens and trace metals measured as total met-al concentrations in bulk sediments. However, at present little is known regarding metal speciation or detailed vertical distribution and partitioning of metal contami-nants within the sediments.

Application of diffusive gradient in thin films (DGT) technology as a complementary tool to the routine monitoring was trialled at an example disposal site (Souter Point, located off the Northeast coast of England) to provide an improved understanding of metal behavior and fate. Initial results of the study are shown in this abstract. Three stations representing contrasting history and presence of maintenance dredge dis-posal, including a control station outside the disposal site, have been studied and depth profiles of fluxes of different metals (Fe, Mn, Pb, Cu, Cd, Cr, Ni, Zn) to the binding gel (Chelex 100) have been derived. Other associated measurements (PSA, porosity, TOC, oxygen, sulphides by AgI probes) were also obtained. Higher flux rates and shallower mobilization of metals (Mn and Fe) to the binding gel were ob-served at the disposal stations compared to the control station. Here we describe metal mobilization at different depths, linking the remobilization of Fe2+ and Mn2+ to the sediment (re)supply of other metals of interest with a focus on Cd, Ni and Pb and as they are on the Water Framework Directive (WFD) list of priority substances and OSPAR list of priority pollutants. Results showed that Cd, Pb and Ni exhibited signs of resupply at the sediment-water interface (SWI). There was a potential increased mobilization and source to the water column of Pb and Ni at the disposal site sta-tions, but there was no Cd source, despite higher total sediment loadings. Statistical modelling (using 95% confidence envelope GAM fitted) of the DGT flux profiles has allowed differences in sites to be robustly assessed.

Further statistical modelling (i.e. Metal:Metal couple) and understanding of mecha-nizms (i.e. investigate the processes that drive differences between sites and how dis-posal is affecting those differences) is currently underway to aid our understanding of metal cycles under disposal conditions and therefore to assist in the management of marine sediment and associated human activities.

7.4.4 Automation of the passive sampling techniques (France)

Céline Tixier gave a brief overview of the work done at Ifremer on the automation of the passive sampling technique, on behalf of her colleagues (Gonzalez J-L., Laës-Huon A., Podeur C., Rousseaux P., Forest B., Bignon L.)

3 School of Earth and Environmental Sciences, University of Portsmouth, Burnaby Building, Burnaby Road, Portsmouth, UK, PO1 3QL.


In collaboration with CEDRE (Centre of documentation, research, and experimenta-tion on accidental water pollution), Ifremer works on the development of various automated ʹsamplersʹ based on the DGT passive sampling technique (for trace metals) or SBSE technique (Stir Bare Sorptive Extraction, for organic compounds). Used in conjunction with autonomous systems, the first version (the benthic station FRAME) allowd more frequent measurements, or measurements triggered by alarms in rela-tion to ʹviolentʹ or ʹrapidʹ events (floods, storms, sediment resuspension, etc.), in the aim of assessing impact on environmental contamination. Recently, in collaboration with the company Veolia Environment, another version consists in an automated and portable version of the SBSE technique ("suitcase SBSE").


8 Provide expert knowledge and guidance to ICES Data Centre (possibly via subgroup) as requested

ICES requested WGMS to prepare, together with the ICES Data Centre, WGBEC, and MCWG, the entrance of litter and microplastic and associated contaminants data in the Environmental Data Base, and to prepare for likely future requirements for as-sessment across the ICES region and reporting under MSFD Descriptor 10.

In its brief discussion, WGMS concluded that it did not have the required expertise at this meeting. WGMS will include the topic in its agenda and should, as a result, be able to provide assistance in the coming years.


9 Miscellaneous

9.1 That MCWG, WGMS and WGBEC hold a concurrent meeting in 2014 with a full day joint plenary to address common areas of interest: a) To define the role of passive sampling in integrated monitoring and assessment (sampling strategy, assessment criteria, deployment alongside bio-indicator species) and use of toxicity tests on passive sampler extracts in monitoring programmes. b) Microplastics

WGMS considered the suggestions for a common meeting by WGBEC and MCWG.

9.2 Deliberations about the future of WGMS

WGMS discussed its further existence and future topics to some extent. The group was of the opinion that a continued existence is merited and that will enhance the scientific output of ICES. The group also recognized the benefits of working closely together with WGBEC and MCWG and concluded that the independent viewpoint it brings to the common topics benefits the overall quality of that output.

As a result of the discussion the group identified the following topics as candidates for future consideration:

1 ) Passive sampling in relation to sediment monitoring and sediments dy-namics.

2 ) Microplastics as a source of hazardous substances and contaminant. 3 ) The influence of changing hydrodynamics due to the various new con-

structions (e.g. wind mill parks) on bottom sediments with an emphasis on modelling these dynamics.

4 ) The impact of deep-sea mining. 5 ) The impact of new offshore activities e.g. due to corrosion.


10 Recommendations and Action list

The actions and recommendations are listed in Annex 4 and 5.


11 Chair(s) for 2014

Lucia Viñas and Craig Robinson will act as chairs for the time being. At the next meeting of WGMS in 2014, new arrangements for chairmanship will have to be made. At that time the group has to consider moving to the 3-year ToR.


12 Date and venue of the next meeting

WGMS will meet in March at the ICES headquarters in Copenhagen for its 33rd meet-ing.


13 Closure of the meeting

The meeting was closed on Friday, 22 March 2013 at 12h30. Both Chairs thanked the group for their collaboration to a successful meeting and thanked, on behalf of the entire group, Claire Mason, Thi Bolam and their colleagues for hosting the meeting in such an outstanding way.


Annex 1: List of participants

Name Address Phone/Fax E-mail

Thi Bolam Cefas Lowestoft Laboratory Pakefield Road Lowestoft Suffolk NR33 0HT UK

Tel: +44 1502 Fax: +44 1502 513865

[email protected]

Rob Fryer Marine Scotland Marine Laboratory PO Box 101 375 Victoria Road Aberdeen AB11 9DB UK

TEL: +44 1224 876544 FAX: +44 1224 295511

[email protected]

Claire Mason Cefas Lowestoft Laboratory Pakefield Road Lowestoft Suffolk NR33 0HT UK

Tel: +44 1502 524591 Fax: +44 1502 513865

[email protected]

Els Monteyne MUMM 3de en 23ste Linieregimentsplein B-8400 Oostende Belgium

TEL +32 59 24 20 59 FAX: +32 59 70 49 35

[email protected]

Craig Robinson Marine Scotland Marine Laboratory PO Box 101 375 Victoria Road Aberdeen AB11 9DB UK

TEL: +44 1224 876544 FAX: +44 1224 295511

[email protected]

Patrick Roose (Chair)

MUMM 3de en 23ste Linieregimentsplein B-8400 Oostende Belgium

TEL +32 59 24 20 59 FAX: +32 59 70 49 35

[email protected]

Stefan Schmolke Bundesamt fur Seeschiffahrt und Hydrographie Wüstland 2 22589 Hamburg Germany

TEL: +49 40 31903330 FAX +49 40 31905033

[email protected]

Céline Tixier Ifremer – RBE/BE/LBCO rue de lʹIle dʹYeu B.P. 21105 F-44311 Nantes Cédex 03 France

TEL:+33 2 40 374134 FAX:+33 2 40 374075

[email protected]





Lucía Viñas (Co-Chair)

Inst. Español de Oceanografía Centro Oceanográfico de Vigo Cabo Estay – Canido Apdo 1552 E-36280 Vigo Spain

Tel: + 34 986 49 21 11 Fax: + 34 986 49 86 26

lucia.vinas @vi.ieo.es


Annex 2: Agenda

The Working Group on Marine Sediments in Relation to Pollution (WGMS), chaired by Patrick Roose, Belgium, and Lucía Viñas, Spain - Lowestoft, UK, 18-22 March 2012:

1 ) Opening of the meeting 2 ) Adoption of the agenda 3 ) Sediments monitoring

a ) Finalize the development of guidelines for Spatial design of a re-gional monitoring programme for contaminants in sediments;

b ) Review and comment on the report of the 2011 meeting of OSPAR/MIME in matters concerning sediments.

4 ) Background concentrations c ) Continue collection of data and develop background concentrations

for alkylated PAHs and dioxins. 5 ) Passive Sampling

d ) Initiate a review on the use of passive sampling for measurements in sediments in relation to assessing the state of the marine environment;

e ) To report on ongoing and new projects involving passive sampling. 6 ) Miscellaneous

f ) Provide expert knowledge and guidance to ICES Data Centre (possibly via subgroup) as requested.


Annex 3: WGMS terms of reference for 2013

The Working Group on Marine Sediments in Relation to Pollution [WGMS] (Chair: L. Viñas, Spain and C. Robinson, UK) will meet in Copenhagen, Denmark 3-7 March 2013 to:

1. Sediments monitoring

g ) Finalize the development of guidelines for Spatial design of a regional monitoring programme for contaminants in sediments

h ) Review and comment on the report of the 2013 meeting of OSPAR/MIME in matters concerning sediments

2. Background concentrations

i ) Continue collection of data and develop background concentrations for alkylated PAHs and dioxins.

3. Passive Sampling

j ) Initiate a review on the use of passive sampling for measurements in sediments in relation to assessing the state of the marine environment

k ) To report on ongoing and new projects involving passive sampling 4. Miscellaneous

l ) Provide expert knowledge and guidance to ICES Data Centre (possi-bly via subgroup) as requested

WGMS will report by 15 April 2014 (via SSGHIE) for the attention of SCICOM and ACOM.

m )


Supporting Information

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

Scientific justification and relation to action plan:

1. This is a direct request from OSPAR.

2. Anticipating that the report of the proposed 2012 assessment will be available before the meeting, WGMS can review and comment the progress made;

3. Background values play an important role in the OSPAR assessments of con-taminants in sediments. WGMS has proposed background concentrations on available information. However, the amount of available data are sparse. Addi-tional information is expected and may warrant revision of the proposed back-ground concentrations (OSPAR request 3, 2007) WGMS will review new information for the further development and advise accordingly.

4. Passive samplers are increasingly used in environmental monitoring, but the approaches and methodologies differ. A document focused on their use in sed-iments, discussing the different type of passive samplers and their use, is envis-aged. The group would particularly like to develop the use of passive sampling as a tool to assess the good environmental status of the marine environment.

5. Receiving and review of national reports of projects involving the use of passive samplers by WGMS will build further experience on the field and use of passive sampling.

6. Response to internal ICES requests

Resource requirements:

None required

Participants: The Group is normally attended by some 15 members and guests.

Secretariat facilities:

None.

Financial: No financial implications.

Linkages to advisory committees:

ACOM

Linkages to other committees or groups:

WGBEC, MCWG

Linkages to other organizations:

OSPAR, HELCOM


Annex 4: Recommendations

Recommendation For follow up by

WGMS recommends that the approach outlined in section 3 is suitable for producing spatial sediment monitoring designs on a Regional scale.

ACOM, OSPAR

WGMS recommends that the approach outlined in section 3 is deve-loped into an OSPAR guideline.

ACOM, OSPAR

WGMS recommends that OSPAR coordinates the inception of a regional monitoring sampling programme based on the strategy outlined. WGMS also recommends that a passive sampling-based monitoring progamme is simultaneously initiated for the same sampling sites.

ACOM, OSPAR

WGMS recommends that the proposed BCs for alkylated PAHs are used for OSPAR assessment purposes pending the availability of additional information.

ACOM, OSPAR

WGMS recommends that WGBEC are invited to advice on the sui-tability of sediment GES targets for contaminants having specific regard to sediment composition e.g. grain size, type of organic matter.

ACOM, OSPAR

WGMS recommends that WGMS, WGBEC and MCWG meet at the ICES headquarters in 2014 and organize a joint session

WGMS, WGBEC, MCWG


Annex 5: Action list

Agenda item

6 Bring information on methodologies (sampling, analysis, separation) on and occurrence of microplastics in sediment to the meeting.

All members

4c Bring new information on background concentrations, especially for PAH (parent and alkylated) and dioxins, to the meeting.

All

5 Follow-up on the outcome of the SETAC technical workshop on passive sampling.

All

5 Contact Foppe and assist in the development of the ICES TIMES paper on PS in sediment.

Craig, Els, Céline

5 Consider the practical application of PS for national monitoring programmes.

All

5 Report on ongoing and new projects involving passive sampling. All

6 Consider future relevant topics for the group. All


Annex 6. Review of WGMS 2013 report regarding OSPAR request

Review 1

Some key points:

1 ) This discussion has been going on for some years. It is therefore likely that the solution is not easily attained, and may not be entirely satisfactory. It may therefore be that the best way forward is to state the best that can be done at this time, with a view to returning to the subject at some (unde-fined) future time when science presents new opportunities.

2 ) The fundamental position has been taken that somehow concentrations of contaminants in sediment should be compared to assessment criteria. The assessment criteria selected are ERLs and/or EACs. What follows in the WGMS report follows from this decision. We should consider later whether there is any alternative to this at this time, or that could be devel-oped in the future.

3 ) WGMS make distinction between comparisons with assessment criteria for OSPAR CEMP purposes and assessments for MSFD/GES purposes, and al-so with other studies that might address temporal changes or pollutant transport. The latter is sensible, The former is regrettable, but probably the only way to reach a conclusion.

4 ) It is correct that ERLs and EACs do not explicitly take account of particle size or the concentrations of co-factors such as organic carbon concentra-tions.

5 ) The use of non-normalised concentrations in comparisons to determine GES compliance is therefore necessary at this time.

6 ) The WG recommend that field samples should be restricted to sediments of >20% fines content. This appears to be inconsistent with the first para in section 3.2, in which comparisons of mean concentrations is cited. The use of sediments containing fine grained material is necessary to reduce the analytical effort and to ensure that numerical data above detection limits are routinely obtained. However, this clearly introduces a bias to the as-sessment if the areas of sediment with <20% fines are either not included in the assessment or are included in a way that makes unsupported assump-tions about the concentrations of contaminants in these sediments.

7 ) 3.4.1 recommendations: 1 ) OK 2 ) OK 3 ) OK 4 ) OK 5 ) Appears to omit areas with <20% fines


6 ) OK 7 ) Potentially untrue. The problem should be addressed through power

analysis of existing data etc.

8 ) The use of sediments of >20% fines will tend to be precautionary, i.e. the final estimated mean will be higher than the true Regional mean, if no ac-count is taken of coarser sediment areas. The degree of precaution is not clear – it would be helpful to have this estimated.

9 ) Alternatively, taking sand areas into account, but treating the concentra-tions as zero would tend to under-estimate the Regional mean, i.e. not be precautionary. Clear guidance is required on how the sandy areas should be included in the assessment.

10 ) As indicated by the test areas, the variance of the raw whole-sediment concentration data within strata is likely to be large. The nature of the sta-tistical test used to compare with assessment criteria needs to be under-stood, together with the degree of precaution that this introduces.

11 ) The nature of the assessment criteria is governing the way in which the as-sessment are being made. We know from passive sampling studies that the key factor in transfer of lipophyllic organic contaminants from sedi-ment to organisms is the concentration (activity) of the compound in the sediment pore water. Such concentrations would provide theoretically ex-cellent basis for quality standards, which could be applied in the water column as well.

However, most of the toxicity data in databases does not include pore water concen-trations, and concentrations in water are usually not concentrations of freely dis-solved compounds.

Some of the toxicity data are related to concentrations in the test organisms. I favour-able circumstances, these may be translated into equivalent freely dissolved concen-tration in pore water.

Similarly, ratios of contaminant concentration in solids to the organic carbon content of the solids can be used to predict concentration in pore waters.

It would be very useful to undertake a review of toxicity databases to extract data linking toxicity to concentrations of (lipophyllic) contaminants in the test organisms and to derive toxicity criteria based upon concentrations of contaminants in lipid pools. Partitioning theory could then be used to develop assessment criteria for pore water and for concentrations in sediment normalised to organic carbon.

Review 2

My overall reaction is that this work by WGMS provides some progress on the issue of sampling sediments for the purpose of responding to Descriptor 8 of the MSFD. It identifies a data and expert opinion approach to identifying strata that would be suit-able for sampling and based on available data calculates the number of samples that would be required from each strata in order to have reasonable power to determine compliance or lack of compliance with the objectives of Descriptor 8. There is a great


deal of work that remains to be done but this document provides some solid ground to build upon.

The connection between the OSPAR request and the input from WGMS is not clear. The OSPAR request being:

1 ) The selection of areas where monitoring makes most sense, i.e.; a ) depths that are sensible to monitor (does it make sense to monitor be-

low 1000 m? 500 m? 200 m? 100 m?); b ) sediment types that are sensible to use and the implication for possi-

ble spatial coverage; c ) ship time considerations; d ) time from changes in inputs to response in the sediment can be de-

tected; 2 ) The required spatial resolution of sampling within these areas.

This connection may be clearer in the previous response from WGMS but if so it should be repeated here. This seems to be directed largely at 1b.

With respect to the southern North Sea case study -

“WGMS members identified six areas as suitable strata for further analysis being: Oyster Ground, German Bight, Weisse Bank, North Frisian coast, Wadden Sea and Flemish Banks (Figure 2). The choice of these strata was based on local expert knowledge. However, although WGMS members felt these areas were sensible given their knowledge, this may need to be further refined in the future.”

It needs to be emphasized that strata selection is fundamental to whatever follows so the accepted process for selecting these strata needs to be highlighted and potentially expanded. In fact “expert knowledge” may be the best and most effective process for doing this but the weaknesses of such an approach needs to be enumerated. For ex-ample, expert knowledge is based on past activities, i.e. where we have sampled and why. However it should also be noted that it has been clearly demonstrated in other instances that a formalized approach to the use of expert knowledge can be very ef-fective in cases where data is limited. If “expert opinion” is to be used for identifying strata then a formalized approach should be identified and used.

In the RGMON report of 2012 it was noted that a decision seemed to have been made against the advice of ICES that whole sediment concentrations would be used. Is it likely then that a recommendation to use mud content as a means of identifying stra-ta will then be acceptable? Multiplying the sieved sediment contaminant concentra-tions by 0.3 to approximate whole sediment concentrations is unnecessary and perhaps misleading. It counters the previous valid arguments that have been made for the use of sieved samples.

The issue of scale should be addressed more thoroughly. This has been a major issue throughout the discussions of the MSFD. Obviously the WGMS had some discussion of this issue since some areas of fine grain sediment were not identified as useful stra-ta for this analysis. Can WGMS add anything to aid in resolving this issue? Is there some guidance that could be given that would be useful, e.g. strata should be at least X% of the total area of the region being considered? Is the relative size of the strata


dependent upon the purpose of the analysis, e.g. regional comparison vs temporal trend?

In summary, this is very useful input to the GES process/discussion but WGMS could definitely contribute more to the process of selecting strata. WGMS and others could certainly provide some useful comment on the scale issue.

ices wgms report 2013ices.dk/sites/pub/publication reports/expert group... · several developments...

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