OSPAR chemical monitoring and assessment of the North-East Atlantic Patrick Roose, Head of Laboratory MUMM

OSPAR? OSPAR is the convention for the protection of the marine environment of the north-east Atlantic http://www.ospar.org

OSPAR area and contracting parties

The 1992 OSPAR Convention requires the Contracting Parties to: OSPAR philosophy The 1992 OSPAR Convention requires the Contracting Parties to: ”take all possible steps to prevent and eliminate pollution and take the necessary measures to protect the maritime area against adverse effects of human activities so as to safeguard health and conserve marine ecosystems and, where practicable, restore marine areas which have been adversely affected”.

OSPAR philosophy The 1992 OSPAR Convention requires the Contracting Parties, amongst other things, to “cooperate in carrying out monitoring programmes”, to develop quality assurance methods, and assessment tools.

OSPAR JAMP The main objective of the Joint Assessment and Monitoring Programme (JAMP) is to provide arrangements for preparing periodic assessments of the environmental quality status of the OSPAR Convention area and for progress assessments on the implementation of the five thematic OSPAR Strategies.

OSPAR JAMP - Programmes the Coordinated Environmental Monitoring Programme (CEMP): can be described as that part of monitoring under the JAMP where the national contributions overlap and are co-ordinated. It covers temporal trend and spatial monitoring for concentrations of selected chemicals and nutrients and for biological effects. the Comprehensive Atmospheric Monitoring Programme (CAMP): covers monitoring at coastal stations of the concentrations of selected contaminants (including nitrogen) in precipitation and air and their depositions. the Comprehensive Study on Riverine Inputs and Direct Discharges (RID): assesses, on an annual basis, all riverborne and direct inputs of selected contaminants (including nutrients) to the OSPAR Convention area and to determine the longterm trends of such inputs.22

OSPAR CEMP – Key parameters Mercury, cadmium and lead in biota and sediments PCBs in biota and sediments PAHs in biota and sediment (parent and alkylate) PBDEs in biota and sediment Nutrients in seawater Direct and indirect Eutrophication effects PAH- and Metal specific Biological effects Organotins in sediments and biota TBT specific effects

Data and information flow CEMP data from CP BE DE DK … SE UK QA QA QA QA QA QA ICES OSPAR

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data ‘Old’ organochlorines Endosulphan X X2 No Hexachlorobenzene Yes B,S Hexachlorocyclohexane isomers (HCH) W,B,S PCBs PCDDs PCDFs PCNs X1 Toxaphene (OSPAR: heptachloronorbornene ) 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data ‘New’ pesticides Alachlor X No Atrazine X2 Chlorfenvinphos Chlorpyrifos Dicofol Diuron Ethyl O-(p-nitrophenyl) phenyl phosphonothionate (EPN) X1 Flucythrinate 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data ‘New’ pesticides Isodrin X1 X No Isoproturon X2 Methoxychlor Pentachlorophenol (PCP) X3 Simazine Tetrasul Trifluralin 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data VOCs 1,2,3-Trichlorobenzene X X2 No 1,2,4-Trichlorobenzene 1,2-Dichloroethane 1,3,5-Trichlorobenzene Benzene Dichloromethane Trichloromethane X1 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data PAHs Anthracene X X2 Yes B,S Fluoranthene X3 Naphthalene Polyaromatic hydrocarbons 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data ‘New’ organohalogens Brominated flame retardants (WFD: polybrominated biphenyls only) X X2 Yes B,S 1,3,5-tribromo-2-(2,3-dibromo-2-methylpropoxy)-benzene X1 No Hexachlorobutadiene Hexachlorocyclopentadiene (HCCP) Pentabromoethylbenzene Pentachloroanisole Pentachlorobenzene 2-Propenoic acid, (pentabromo)methyl ester 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data ‘New’ organohalogens Short-chain chlorinated paraffins (SCCPs) X X2 No Tetrabromobisphenol A (TBBP-A) Hexachlorobutadiene Endocrine disruptors Nonylphenol/ethoxylates (NP/NPEOs) and related substances Octylphenol Phthalates: dibutylphthalate, diethylhexylphthalate (DEHP) 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data Metals and related compounds Cadmium X X2 Yes B,S Lead and organic lead compounds X1 Mercury and organic mercury compounds Nickel and its compounds Organic tin compounds S Nutrients Nutrients in seawater X3 W 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

OSPAR Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data Other organic chemicals 1,5,9-Cyclododecatriene X1 No 2,4,6-Tri-tert-butylphenol X 3,3'-(ureylenedimethylene)bis(3,5,5-trimethylcyclohexyl)-Diisocyanate 4-(dimethylbutylamino)-Diphenylamin (6PPD) 4-tert-Butyltoluene Clotrimazole Cyclododecane Diosgenin 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances, 3 identified by the international Scheldt commission.

Priority Substances (Groups of) substances OSPAR CEMP WFD Monitored Matrices Data Other organic chemicals Hexamethyldisiloxane (HMDS) X No Musk xylene Neodecanoic acid, ethenyl ester Perfluorooctanol sulphonic acid and its salts (PFOS) Triphenyl phosphine 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances, 3 identified by the international Scheldt commission.

Priority Substances (Groups of) substances OSPAR CEMP WFD HELCOM UNEP-POP ‘Old’ organochlorines DDTs X Endosulphan X2 Hexachlorobenzene Hexachlorocyclohexane isomers (HCH) PCBs PCDDs PCDFs PCNs Toxaphene

Priority Substances (Groups of) substances OSPAR CEMP WFD HELCOM Metals and related compounds Cadmium X Lead and organic lead compounds Mercury and organic mercury compounds Nickel and its compounds Organic tin compounds 1 Lower priority in OSPAR because of exclusive use as intermediates in closed systems or no current production and/or use in the OSPAR area; 2 first-priority hazardous substances.

OSPAR CEMP Three elements are essential for the realisation of monitoring under the CEMP: Technical guidelines Quality assurance tools Assessment tools

OSPAR CEMP - Guidelines JAMP guidelines for monitoring contaminants in biota ASMO 1997 Status - Category I Technical Annex 1 – determination of organic contaminants Technical Annex 2 – determination of metals Technical Annex 3 – determination of PAHs ASMO(1) 1999 JAMP guidelines for monitoring contaminants in sediments ASMO 1997 Technical Annex 1 – statistical aspects Technical Annex 2 – determination of CBs ASMO 1998 Technical Annex 4 – determination of TBT ASMO(1) 1999 Technical Annex 5 – normalisation of contaminant concentrations ASMO 2002 Technical Annex 6 – Determination of metals – analytical methods And more….http://www.ospar.org/eng/doc/Status_OSPAR_monitorig_guidelines.doc

OSPAR CEMP – QA/QC Accreditation is not required but encouraged Participation in proficiency testing schemes (PTS) is demanded. OSPAR has made arrangements with the QUASIMEME PTS concerning reporting of results from OSPAR labs QA/QC data should be reported together with the data During assessments the data of CPs is weighted against the provided QA information

OSPAR CEMP – QA/QC QA items: QUASIMEME Z-score CRM mean value Yes QA data absent Yes OSPAR WG MON Analytical weight: 0.2 No Two items of QA data QA data satisfactory No No Analytical weight: 0.2 Yes QA items: QUASIMEME Z-score CRM mean value Yes Analytical weight: 1 QA data satisfactory One item satisfactory No No Analytical weight: 0.2 Yes Yes Analytical weight: 1 Analytical weight: 0.7

OSPAR CEMP – Assessment tools A key objective of the OSPAR strategy is the “cessation of discharges, emissions and losses of hazardous substances by 2020”.

OSPAR CEMP – Assessment tools Background Concentration or BC The Background Concentration is the concentration of a contaminant at a “pristine” or “remote” site based on contemporary or historical data. The Background Concentration of a man-made compound is taken as zero. Background Assessment Concentration or BAC The Background Assessment Concentration is a value for testing whether the concentrations [sediments; water; biota] at a site are at or close to background.

OSPAR CEMP – BC and BAC The aim of an assessment is to demonstrate that concentrations are at or near background.

OSPAR CEMP – BC and BAC Background Assessment Concentration or BAC The BAC is a concentration greater than the BC that quantifies what is meant by near background or close to zero. The test assumes that the mean concentration [c] is above background (i.e., [c] > BAC) unless there is statistical evidence to show that it is near background (i.e., [c] ≤ BAC). Formally, the null and alternative hypotheses are: H0: [c] > BAC (i.e., concentrations above background) H1: [c] ≤ BAC (i.e., concentrations near background) and H0 is rejected in favour of H1 if the upper confidence limit on [c] is below the BAC.

OSPAR CEMP – BC and BAC

OSPAR CEMP – BC and BAC BACs should be both low enough to reflect near background concentrations and high enough that we are likely to conclude that concentrations are near background when [c] = BC. Specifically, the BAC are set to give a 90% probability of concluding that concentrations are near background when [c] = BC.

OSPAR CEMP - BC and BAC for PAHs Sediment (g kg-1 dry weight normalised to 2,5% organic carbon) BC BAC Naphthalene 5 8 Phenanthrene 17 32 Anthracene 3 Fluoranthene 20 39 Pyrene 13 24 Benz[a]anthracene 9 16 Chrysene 11 Benoz[a]pyrene 15 30 Benzo[ghi]perylene 45 80

OSPAR CEMP - BC and BAC for PCBs Polychlorinated biphenyl (CB) Sediment (g kg-1 dry weight normalised to 2,5% organic carbon) Mussel (g kg-1 dry weight) Fish liver (g kg-1 wet weight) BC BAC1 BAC2 BAC CB153 0,2 1,1 Sum7CB 1,5 4,6 1,2

OSPAR CEMP - Environmental Assessment Criteria “Environmental assessment criteria” (EACs) are tools for assessing the significance of concentrations of hazardous substances in the marine environment. They are used to assess whether there are grounds for concern about the presence of those substances and to establish priorities for action.

OSPAR CEMP - Environmental Assessment Criteria Two types of EAC have been identified: “EACs (lower)”, which are concentrations below which it is reasonable to expect that there will be an acceptable level of protection of marine species (including sensitive species) from chronic effects from the hazardous substances concerned. EACs (lower) should be used to identify potential areas of concern and to identify substances whose concentrations in the marine environment cause potential concern for marine species. EACs (lower) should not be used as firm standards or as triggers for remedial action; (b) “EACs (higher)”, which are concentrations above which it is reasonable to expect acute toxic effects on marine species. Further consideration is being given to how to define EACs (higher) and how to develop them.

OSPAR CEMP - EACs for metals EACwater EACsediment EACfish EACmussel Secondary Poisoning µg l-1 mg kg-1 dry wt μg kg-1 wet wt µg kg-1 wet wt As 0.1 (f) 0.71 (p) nr Cd 0.21 (f) 0.06 (p) 7.35 (p) 55.9 (p) ** Cr 4.2 (f) 21 (p) Cu 0.476 (f) 0.22 (p) Hg 0.055 (p) 3.5 (p) 1.7 (p) Ni 1 (f) 2.8 (p) Pb 0.13 (f) 2.22 (p) 300 (p) 1690 (p) Zn 3.0 (f) 1.48 (p) f = firm p = provisional nr = not relevant in relation to the current monitoring programme, or considered for secondary poisoning fc = further consideration dry wt = dry weight wet wt = wet weight * = sediment normalised to 1% organic carbon ** = not reported, values lower than derived from direct effects

OSPAR CEMP - EACs for organics EACwater EACsediment EACfish EACmussel Secondary Poisoning µg l-1 mg kg-1 dry wt μg kg-1 wet wt µg kg-1 wet wt DDE 0.000001 (f) 0.0016 (p)* 0.5 (f) 0.18 (f) Dieldrin 0.000023 (f) 0.0079 (p)* 1.7 (f) 0.076 (f) Lindane 0.002 (f) 0.0011 (p) 1.1 (f) 0.29 (f) nr TBT 0.0001 (f) 0.00001 (p) 2.4 (f) PBDE 0.00018 (f) 0.062 (f)* 100 (f) 5 (f) f = firm p = provisional nr = not relevant in relation to the current monitoring programme, or considered for secondary poisoning fc = further consideration dry wt = dry weight wet wt = wet weight * = sediment normalised to 1% organic carbon ** = not reported, values lower than derived from direct effects

OSPAR CEMP - EACs for organics EACwater EACsediment EACfish EACmussel Secondary Poisoning µg l-1 mg kg-1 wet wt μg kg-1 wet wt µg kg-1 wet wt ∑ group PAHs 2 rings: naphthalene 2.4 (p) 0.038 (p)* 1024 (p) 91 (p) fc 3 rings: phenanthrene & anthracene 0.17 (p) 0.031 (p)* 852 (p) 1290 (p) 4 rings: fluoranthene, pyrene, benz[a]anthracene & chrysene 0.69 (p) 0.141 (p)* 6900 (p) 5 rings: benzo[k]fluoranthene & benzo[a]pyrene 0.03 (p) 0.021 (p)* 1069 (p) 6 rings: benzo[ghi]perylene & indeno[123-cd]pyrene 0.016 (p) 0.0037 (p)* 73 (p) p = provisional fc = further consideration dry wt = dry weight wet wt = wet weight * = sediment normalised to 1% organic carbon ** = not reported, values lower than derived from direct effects

OSPAR CEMP - EACs vs EQS Group of substances / substances EQS water [ug/l] MAC-QS [ug/l] for inland waters EAC water – current range [ug/l] Calculated Lower EAC [ug/l] cadmium 0.2 0.01-0.1 0.056 lead and organic lead compounds 2.16 0.5-5 0.9 mercury and organic mercury compounds 0.05 0.07 0.005-0.05l 0.01 organic tin compounds 0.0001 0.0015 0.00001-0.0001 0.00005 lindane 0.002 0.04 0.0005-0.005 0.0017 Fluoranthene 0.09 0.069 Naphthalene 1.2 80 5-50 7.5

OSPAR CEMP - Results

assessment for lead in biota OSPAR CEMP - Results cod liver 1990 2000 400 2006-2007 CEMP assessment for lead in biota

OSPAR CEMP - Results lead benzo[a]pyrene I II III IV I II III IV 100 300 1000 3000 10000 BAC = 1520 mean concentration (ug/kg) in molluscs in final year benzo[a]pyrene IV III II I 30 BAC = 7.1 BC = 1 mean concentration (ug/kg) in molluscs in final year

benzo[a]pyrene (µg/kg dw) OSPAR CEMP - Results benzo[a]pyrene (µg/kg dw) Lead (µg/kg dw)

Phenathrene/anthracene ratio OSPAR CEMP - Results Phenathrene/anthracene ratio A ratio of less than 10 is generally accepted to indicate a pyrolytic origin

Conclusions The OSPAR commission has, in the last decades, played a leading role in the field of marine environmental monitoring Through the JAMP and it’s predecessor the JMP, a considerable experience was build both at the level of the commission and it’s contracting parties OSPAR monitoring has resulted in long time series that are now, through innovating approaches, fully showing their value Recent advances in assessment tools and innovative approaches towards assessment have resulted in tools “that work”.

Conclusions Coordinated monitoring i.e. harmonisation of protocols, QA and data reporting are essential. There has to be a willingness/obligation to do the monitoring and report the data. Good assessments require a lot of data. Harmonisation between programmes/obligations is in everybody’s interest. Even brilliant plans do not survive the contact with reality.