Environ Sci Pollut Res (2009) 16: xxx-xxx
Twenty years of elemental analysis of marine biota within the German Environmental Specimen Bank
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Electronic Supplementary Material

A. Monitoring Data from other European Programs

Table S1: Element concentrations in Mytilus edulis in Baltic Sea and North Sea obtained in several European monitoring programs.

Cd / Hg / Pb / Reference
Baltic Sea
ESB 1992-2007 / 0.07-0.16 µg/g ww
1.41-3.15 µg/g dw / 2.62-5.12 ng/g ww
52.3-105 ng/g dw / 0.09-0.19 µg/g ww
1.93-3.46 µg/g dw / This report
BLMP 1999-2001/2002 / Western Pomerania coast / 0.72-5.1 µg/g dw / 70-190 ng/g dw / 0.55-2.1 µg/g dw / Meeresumwelt
1999-2002a
4. HELCOM Assessment / 0.25-0.8 µg/g ww / HELCOM 2001, 2002
Danish National program 2000-2006: / Coast of Zealand/Fyn/Møn / 201-290 ng/g dw / 1.30-3.23 µg/g dw / MADS database 2008
North Sea
ESB 1986-2007 / Schleswig-Holstein Wadden Sea / 0.08-0.16 µg/g ww
0.85-1.66 µg/g dw / 19.9-28.1 ng/g ww
157-332 ng/g dw / 0.10-0.19 µg/g ww
1.04-2.33 µg/g dw / This report
ESB 1985/86-2007 / Lower Saxony Wadden Sea / 0.11-0.29 µg/g ww
1.14-2.43 µg/g dw / 18.9-64.0 ng/g ww
202-457 ng/g dw / 0.19-0.51 µg/g ww
2.13-3.76 µg/g dw / This report
BLMP 1999-2002 / Schleswig-Holstein Wadden Sea / 0.08-0.17 µg/g ww / 20-31 ng/g ww / 0.13-0.55 µg/g ww / Meeresumwelt
1999-2002b
Lower Saxony Wadden Sea / 0.06-0.32 µg/g ww / 15-80 ng/g ww / 0.08-0.31 µg/g ww
Danish National program 1998-2006 / Southwest coast / 0.46-2.08 µg/g dw / 163-721 ng/g dw / 0.17-0.31 µg/g dw (only 2002-2004) / MADS database 2008
Dutch CEMP 1985-2005 / Ems-Dollart Estuary / 0.77 µg/g dw / 220 ng/g dw / 2.6 µg/g dw / RWS/RIKZ 2006
Dutch National Program 2005 / Ems-Dollart Estuary / 1.4 µg/g dw / 250 ng/g dw / 5.8 µg/g dw / Bovelander & Langenberg 2007
UK National Program 1999-2001 / British Waters / 0.10-1.18 µg/g ww / 14.7-126 ng/g ww / 0.14-2.22 µg/g ww / CEFAS 2004
French National program 2000-2004 / Atlantic coast and Channel / 0.17-3.03 µg/g dw / 30-530 ng/g dw / 0.4-9.6 µg/g dw / RNO 2006

References for Table S1:

Bovelander RW, Langenberg VT (2007) National Evaluation Report on the Joint Assessment and Monitoring Programme of the Netherlands 2005. Report RIKZ/2007.004, Feb. 2007, 45 pp

CEFAS (2004) UK National Marine Monitoring Programme - Second Report 1999-2001. http://www.jncc.gov.uk/pdf/nmmp2ndreport.pdf [Retrieved November 16, 2009]

HELCOM (2001) Environment of the Baltic Sea Area 1994 - 1998. Baltic Sea Environment Proceedings No. 82A. 26pp
http://www.helcom.fi/stc/files/Publications/Proceedings/bsep82a.pdf [Retrieved November 16, 2009]

HELCOM (2002) Environment of the Baltic Sea area 1994 - 1998. Baltic Sea Environment Proceedings No. 82B. 218pp
http://www.helcom.fi/stc/files/Publications/Proceedings/bsep82b.pdf [Retrieved November 16, 2009]

MADS database (2008): The national database for marine data. National Environmental Research Institute NERI. http://www.dmu.dk/International/Water/MarineMonitoring/MADS/ [Retrieved November 16, 2009]

Meeresumwelt 1999-2002a: Bund-Länder-Messprogramm für die Meeresumwelt von Nord- und Ostsee (BLMP) - Ostsee
http://www.bsh.de/de/Meeresdaten/Beobachtungen/BLMP-Messprogramm/PDF/Ber_99_02/ostsee9902d.pdf [Retrieved November 16, 2009]

Meeresumwelt 1999-2002b: Bund-Länder-Messprogramm für die Meeresumwelt von Nord- und Ostsee (BLMP) - Nordsee
http://www.bsh.de/de/Meeresdaten/Beobachtungen/BLMP-Messprogramm/PDF/Ber_99_02/nordsee9902c.pdf [Retrieved November 16, 2009]

RNO (2006): Surveillance du Milieu Marin. Traveaux du Réseau National d’Observation de la qualité du milieu marin. Bulletin RNO 2006, ISSN 1620-1124, 56 S. http://wwz.ifremer.fr/envlit/content/download/27640/224803/version/1/file/rno06.pdf [Retrieved November 16, 2009]

RWS/RIKZ (2006) Biological monitoring programme with the blue mussel Mytilus edulis in The Netherlands. Evaluation of the programme 1985 - 2005. Final Report 9S2146.01, 75 pp


B. Monitoring Data for Cadmium and Lead

Figure S1: Concentrations of cadmium (µg/g ww) in blue mussels (Mytilus edulis) at the marine monitoring sites of the German Environmental Specimen Bank. Data represent means of replicate measurements of pooled samples.

Figure S2: Concentrations of mercury (ng/g ww) in muscle tissue of eelpout (Zoarces viviparus) at the marine monitoring sites of the German Environmental Specimen Bank. Data represent means of replicate measurements of pooled samples.

Figure S3: Concentrations of lead (ng/g ww) in liver tissue of eelpout (Zoarces viviparus) at the marine monitoring sites of the German Environmental Specimen Bank. Data represent means of replicate measurements of pooled samples.

Figure S4: Concentrations of lead (µg/g ww) in blue mussel (Mytilus edulis) at the marine monitoring sites of the German Environmental Specimen Bank. Data represent means of replicate measurements of pooled samples.

C. Monitoring Data for Methyl Mercury

In the context of the European Water Framework Directive (EU 2000), the EU Commission has derived Environmental Quality Standards (EQS) for aquatic biota (biota-EQS) for a number of priority compounds. The recent version of the respective WFD daughter guideline proposes an EQS of 0.05 µg/L based on total mercury in water, or - optionally - a biota-EQS of 20 ng total Hg/g ww for aquatic prey (ref. EU 2008b in the main text). Originally, the biota-EQS of 20 ng/g prey (ww) had been derived for methyl mercury in order to protect predators against secondary poisoning (EU 2005). In this context the mercury biota monitoring data of the ESB were evaluated.

To elucidate the relationship between total mercury and methyl mercury, earlier studies in the context of the German ESB have differentiated between these fractions. The results indicate that the methyl mercury fractions in marine biota differ and increase with trophic level, i.e. 2 - 16 % for bladder wrack; 17 - 50 % for blue mussel, up to 93 % for eelpout and up to 98 % for herring gull egg (methyl mercury fraction of total mercury in percent; the analytical method is described below; ESB report 2007).

Figure S5 shows mercury/methyl mercury data for blue mussels from the Lower Saxony ESB-site (North Sea).

Figure S5: Concentrations of inorganic mercury and methyl mercury (ng/g ww) in blue mussels (Mytilus edulis) of the Lower Saxony monitoring site of the German Environmental Specimen Bank. Data represent means of replicate measurements of pooled annual samples. Inorganic mercury was calculated as difference between total mercury and methyl mercury.

Extraction and sample preparation for analysis of methyl mercury: 1 g of original ESB homogenate sub-samples was weighed into a light-proof vial. 20 mL of diluted hydrochloric acid (15 % w/w, e.g. J.T. Baker, Deventer) were added and the sample was extracted overnight in a mechanical shaker (150 min-1). After centrifugation (20 min at 5000 g) the liquid phase was immediately transferred to 20 mL vials. The supernatant was stored in complete absence of light (max. 2 h). Afterwards the organic Hg was separated from inorganic Hg by means of a strongly basic anionic exchange resin (DOWEX 1x8, Dow Chemical Company, Midland, USA). The entire sample was passed through the ion exchange column. Then, further 10 mL hydrochloric acid (15 %) were added to eluate the remaining residues of methyl mercury from the column. After the ion-exchange process, 2 mL of hydrogen peroxide were added to the eluates. Remaining matrix components were oxidized subjecting the eluates to UV digestion for 2 hours (MAUV-2000, Maassen, Reutlingen). Hg was quantified by ICP-MS (see section 2.2. of the main text). For the analysis of methyl mercury the standard addition method was used for quantification.

Additional Reference

ESB-Report (2007): Ausgewählte Ergebnisse aus dem Jahr 2006. Report of Fraunhofer IME on behalf of the Federal Environment Agency. Schmallenberg 2007, pp 104

EU (2005) Environmental Quality Standards (EQS). Substance Data Sheet Mercury and its Compounds, Priority Substance No. 21, CAS-No. 7439-97-6. Common Implementation Strategy for the Water Framework Directive, final version. European Commission, Brussels, 15 January 2005. http://circa.europa.eu/Public/irc/env/wfd/library?l=/framework_directive/i-priority_substances/supporting_background/substance_sheets/eqsdatasheet_150105pdf_6/_EN_1.0_&a=d [Retrieved November 16, 2009]

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