eea – ”chemicals and water” workshop, copenhagen 06-07 december 2010 norman green (niva)...

EEA – ”Chemicals and Water” workshop, Copenhagen 06-07 December 2010EEA – ”Chemicals and Water” workshop, Copenhagen 06-07 December 2010Norman Green (NIVA)Norman Green (NIVA)

Chemicals and Water workshopChemicals and Water workshopEEA, Copenhagen 06-07 2010EEA, Copenhagen 06-07 2010

Levels in Marine WatersLevels in Marine Waters

Norman Green, Birger Bjerkeng (NIVA/ETCw)Norman Green, Birger Bjerkeng (NIVA/ETCw)

PolicyPolicyMethodsMethodsResultsResults


EIONET data – EIONET data – marine marine sediment and sediment and biotabiotaConsiderations:Considerations:• ContaminantsContaminants – persistent, – persistent,

bioaccumulates and toxic, also bioaccumulates and toxic, also endocrine disrupting, endocrine disrupting, carcinogenic and injury to carcinogenic and injury to reproductive systemreproductive system

• Data availabilityData availability – spatial and – spatial and temporal [little or no data from temporal [little or no data from water column] from conventions water column] from conventions and member statesand member states

• SedimentSediment – surficial, – surficial, deposition/erosion areasdeposition/erosion areas

• OrganismsOrganisms of relevance – of relevance – widespread, abundant, seafood, widespread, abundant, seafood, indicators exposure indicators exposure


Some policy principles:Some policy principles:• Precautionary principlePrecautionary principle based implementation (WFD based implementation (WFD

introduction §11 and 44; MSFD introduction §27 and 44; introduction §11 and 44; MSFD introduction §27 and 44; EQSD introduction §2)EQSD introduction §2)

• Selection of contaminants:Selection of contaminants:– To a large degree based on characteristics of persistence, To a large degree based on characteristics of persistence,

accumulation in biota or toxicity (so called ”accumulation in biota or toxicity (so called ”PBTPBT” characteristics, ” characteristics, EU category I);EU category I);

– To a lesser degree on carcinogenic or mutagenic characteristics or To a lesser degree on carcinogenic or mutagenic characteristics or risk to reproduction system (so called ”risk to reproduction system (so called ”CMRCMR” characteristics, EU ” characteristics, EU category II);category II);

– But also suseptable long range transportation (But also suseptable long range transportation (LRTLRT), and; ), and;

– Discharges of a Discharges of a large and constant naturelarge and constant nature but that breakdown but that breakdown quicklyquickly

• The list over relevant substances is The list over relevant substances is re-evaluated re-evaluated regularlyregularly and can be expanded (e.g. EQSD Annex III) and can be expanded (e.g. EQSD Annex III)


• Concerns rivers, lakes, heavily modified water bodies (HMWB), coastal waters including territorial waters.

• 33 Priority Substances or groups of substances (PS) includes chemical status:

- 13 Priority Hazardous Substances (PHS) to be phased out by 2020

- 20 other Priority Substances progressive reduction

• 8 other substances or groups of substances with EQS

• 12 other substances which are to be considered included as Priority Substances by 2011 and assessed under ecological status (EQSD Annex III)

• Short term goal: obtain Good Status by 2015

• Long term goal: cessation or phasing-out of discharges, emissions and losses, with the ultimate aim of achieving concentrations in the marine environment near background values for naturally occurring substances and close to zero for man-made synthetic substances

EQSD substancesEQSD substances


Nr. Name of substance AA-EQS-value (µg/ l) in other surface water

(1) Alachlor 0,3 (2) Anthracene (A) 0,1 (3) Atrazine 0,6 (4) Benzene 8 (5) Brominated diphenylether (PBDE) (A), (1) 0,0002 (6) Cadmium and its compounds (A), (2) < 0,08 (Class 1)

(7) Short chained chloroinated parafins (SCCP) (C10-13) (A)

0,4

(8) Chlorofenvinphos 0,1 (9) Chlorpyrifos 0,03 (10) 1,2-Dichloroethane (EDC) 10 (11) Dichloromethane 20 (12) Di(2-ethylhexyl)-phthalate (DEHP) 1,3 (13) Diuron 0,2 (14) Endosulfan (A) 0,0005 (15) Fluoranthene 0,1 (16) Hexsachloro-benzene (A) 0,01 (17) Hexachloro-butadiene (HCBD) (A) 0,1 (18) Hexachloro-cyclohexane (A) 0,02 (19) Isoproturon 0,3 (20) Lead and its compounds 7,2 (21) Mercury and its compounds (A) 0,05 (22) Naphthalene 1,2 (23) Nickel and its compounds 20 (24) Nonylphenol (4-Nonylphenol) (A) 0,3 (25) Octylphenol 4-(1,1’,3,3’-

tetramethylbutyl)phenol 0,1

(26) Pentakchloro-benzene (A) 0,007 (27) Pentachlorophenol (PCP) 0,4 (28) Polyaromatiske hydrocarbons (PAH) (A) Ikke oppgitt Benzo(a)pyrene 0,05 Benzo(b)fluoranthene, Benzo(k)fluoranthene ∑ 0,03 Benzo(g,h,i)perylene, Indeno(1,2,3-

cd)pyrene ∑ 0,002

(29) Simazine 1,0

(30) Tributyltin-compounds (tributyltin cation) (A)

0,0002

(31) Trichloro-benzenes 0,4 (32) Trichloro-methane (chloroform) 2,5 (33) Trifluralin 0,03

15 Biocides4 PAHs3 Solvents4 Heavy metals2 Precursors2 Surfactants2 Flame retardants1 Plasticiser

33 Priority substances33 Priority substances

TBT

””Other” substances (8)Other” substances (8)

Annex III substances (12)Annex III substances (12)


EQSD and EQSEQSD and EQS• Earlier, EQS concerned only substances in Earlier, EQS concerned only substances in water phasewater phase• EQSD sets some EQS for biota and opens for alternative EQSD sets some EQS for biota and opens for alternative

use of use of sediment and biotasediment and biota (2008/105/EC Art. 3) (2008/105/EC Art. 3)::– EQS defined for EQS defined for HgHg, , HCBDHCBD, , HCBHCB in in ””prey tissue”prey tissue”– NB: EQS vs Klif Cl. I (ppb v.v.): Hg = 20NB: EQS vs Klif Cl. I (ppb v.v.): Hg = 20 ”prey tissue””prey tissue” vs 40 vs 40blue mussellblue mussell and 100 and 100cod musclecod muscle

– NB: EQS vs Klif Cl. I (ppb v.v.): HCB = 10NB: EQS vs Klif Cl. I (ppb v.v.): HCB = 10 ”prey tissue””prey tissue” vs 0.1 vs 0.1blue mussellblue mussell and 20 and 20cod musclecod muscle

– EQS for other matrices/substances but must provide the EQS for other matrices/substances but must provide the same same level of protectionlevel of protection as EQS for water as EQS for water

– Annual monitoringAnnual monitoring unless technical knowledge and expert unless technical knowledge and expert judgement justify another intervaljudgement justify another interval

– Provide Provide reasonsreasons and basis for alternative approach and basis for alternative approach

• Must at least ensure that there is Must at least ensure that there is no significant no significant increaseincrease in levels or classification in levels or classification (2000/60/EC Art. 4WFD 8 e.g. (2000/60/EC Art. 4WFD 8 e.g. art. 4 and 7) and MFSD (art. 14), and implied in the EQSD (art. 3). This is one of the art. 4 and 7) and MFSD (art. 14), and implied in the EQSD (art. 3). This is one of the strongest arguments for maintaining long time series.)strongest arguments for maintaining long time series.)


EEA’s CSI040 indicator EEA’s CSI040 indicator Hazardous Substances in Marine Hazardous Substances in Marine OrganismsOrganismsMethodology (I)Methodology (I)

Only biota data are currently used in the indicatorOnly biota data are currently used in the indicator– Values converted to preferred basis (wet, dry., Values converted to preferred basis (wet, dry.,

lipid)lipid)(may lead to loss of data)(may lead to loss of data)

Bivalvesoft body liver muscle

Metallic Compounds Dry Wet WetPesticides and Biocides Dry Lipid WetPolycyclic Aromatic Hydrocarbons

Dry

Polycyclic Halogenated Aromatic Compounds

Dry Lipid Wet

FishDeterminand Category

– Each time series (Determinand*Tissue*Station)Each time series (Determinand*Tissue*Station)is aggregated to median concentration per yearis aggregated to median concentration per year

– Further analysis is done on log-transformed values,Further analysis is done on log-transformed values,results back-transformed to concentrationsresults back-transformed to concentrations


CSI040 Indicator –methodology CSI040 Indicator –methodology (II)(II)• For each time series For each time series

(Station*Tissue*Determinand):(Station*Tissue*Determinand):– Trend assessment by regression Trend assessment by regression

of log-transformed medians on yearof log-transformed medians on year

• If all medians are well-defined:If all medians are well-defined:

≥≥7 years: Smooth curve by local weighted regression7 years: Smooth curve by local weighted regression(LOESS, 7 year window, minimum 3 points)(LOESS, 7 year window, minimum 3 points)

Dominant trend last 10 years (5 % sign. level)Dominant trend last 10 years (5 % sign. level)

3-6 years: linear regression3-6 years: linear regression

• ≥≥4 years: Mann-Kendall trend4 years: Mann-Kendall trend

(modified to handle low-high range medians)(modified to handle low-high range medians)

• Combining trend results (5 % significance level)Combining trend results (5 % significance level)

• Classification as:Classification as: UpUp / / DownDown / Not significant / Not applicable/ Not significant / Not applicable


HCB in Cod liver (µg/kg lipid weight), outer Oslofjord (Færder)

1992 1994 1996 1998 2000 2002 2004 2006 2008

Monitoring year

1

2

5

10

20

50

100

200

LOESS estimate 95 % lower confidence limit 95 % upper confidence limit Observations (individual fish) yearly median values yearly arithmetic averages

(Much higher concentrations before 1990)

(WFD EQS10 µg/kg wwapprox. conv.to lipid weight)

Max. conc. inrecent years

HCB in Cod liver (µg/kg lipid weight), outer Oslofjord (Færder)

1992 1994 1996 1998 2000 2002 2004 2006 2008

Monitoring year

0

20

40

60

80

100

120

140 LOESS estimate 95 % lower confidence limit 95 % upper confidence limit Observations (individual fish) yearly median values yearly arithmetic averages

(Much higher concentrations before 1990)

(WFD EQS10 µg/kg wwapprox. conv.to lipid weight)

Max. conc. inrecent years


CSI040 Indicator –methodology CSI040 Indicator –methodology (III)(III)

– Chemical status assessed for each time Chemical status assessed for each time series by current levels:series by current levels:• ≥≥2 years:2 years: Regression fit for last year Regression fit for last year

• 2 years:2 years: Average of median valuesAverage of median values

• 1 year:1 year: No classificationNo classification

Upper 95 % confidence limit for the estimateUpper 95 % confidence limit for the estimate

compared with low/high classification levels;compared with low/high classification levels;

three classes:three classes:

Green <Low

Yellow within Low – High range

Red >High

PCBs: combined assessment(consistent trend, next worst classification)


CSI040 Indicator –methodology CSI040 Indicator –methodology (IV)(IV)

• For each main region:For each main region:– Tally of time series for each determinandTally of time series for each determinand

and as sums across determinands according to and as sums across determinands according to • Time trend assessment:Time trend assessment:

– UpUp– DownDown– Not significant (NS)Not significant (NS)– Not applicable (NA) too short time series)Not applicable (NA) too short time series)

• Current level classification:Current level classification:– GreenGreen– Yellow Yellow – RedRed

– Significant dominant trend direction in each level Significant dominant trend direction in each level classclassand total over all level classesand total over all level classes

• Option: overall tally across regions and Option: overall tally across regions and determinandsdeterminands


EIONET EIONET data: data: Biota dataBiota data

CAS NamePriority substance

Priority hazardous substance

In TCM data (#records)

Used in CSI040

Indicator

309-00-2 Aldrin 3807

120-12-7 Anthracene x X 4584

50-32-8 Benzo(a)pyrene x X 4613

205-99-2 Benzo(b)fluoranthene x X 1717

191-24-2 Benzo(g,h,i)perylene x X 4575

207-08-9 Benzo(k)fluoranthene x X 2648

7440-43-9 Cadmium x X 52763 A50-29-3 DDT, p,p’ 21842

DDE, p, p' 29222 A60-57-1 Dieldrin 5983

72-20-8 Endrin 1105

206-44-0 Fluoranthene x 4739

118-74-1 Hexachlorobenzene (HCB) x X 27706 A87-68-3 Hexachlorobutadiene (HCBD) x X 284

193-39-5 Indeno(1,2,3-cd) pyrene x X 4544

465-73-6 Isodrin 195

7439-92-1 Lead x 44102 A7439-97-6 Mercury x X 57543 A7440-02-0 Nickel x 11236

608-93-5 Pentachlorobenzene x X 8832

63697-18-7 1,2,4-Trichlorobenzene ? 252

959-98-8 alpha-Endosulfan 334

7440-38-2 Arsenic 6702

7440-47-3 Chromium 17293

7440-50-8 Copper 46660

58-89-9 gamma-HCH (Lindane) 24654 A7440-66-6 Zinc 47193

PCB alsoused in assessment,listed as substance subject to review


Possible Possible additional additional matches matches between between WFD list WFD list and EIONET and EIONET datadata

WFD determinand name #recordsSoE candidate determinand name

(5) Brominated diphenylether2,2',4,4',5-pentabromodiphenyl ether (BDE99) 23652,2',4,4',6-pentabromodiphenyl ether (BD(E)100) 1445

(12) Di(2-Ethylhexyl)phthalate2-Ethylhexyl phthalate 94

(14) Endosulfanalpha-Endosulfan 334beta-endosulfan 304endosulfan sulfate 52

(22) Naphtalene1,2,3-trimethylnaphthalene 2811,2,4-trimethylnaphthalene 2811,5-dimethylnaphthalene 2621,6-dimethylnaphthalene 2791-Methylnaphthalene 12292,3,5-trimethylnaphthalene 3502,3,6-trimethylnaphthalene 2812,6-dimethylnaphthalene 3482-Methylnaphthalene 1229Acenaphthylene 3213C1-naphthalenes 47C2-naphthalenes 658C3-naphthalenes 1498C4-naphthalenes 1538Naphthalene, chloro derivs. 201


CSI040 – Organisms and CSI040 – Organisms and contaminantscontaminantsdata countdata count

Organism PCB Cd DDEPP HCB HCHG Hg Pb TotalHerring 15 15Atlantic cod 15 10 14 14 15 15 12 95Blue mussel 234 259 173 113 170 256 255 1460Mediterranean mussel 78 101 67 30 30 101 114 521Flounder 15 9 12 9 24 69Plaice 14 2 4 4 4 12 1 41Total 356 372 267 173 228 423 382 2201


CSI040 – Regions and countriesCSI040 – Regions and countriesdata countdata count

MainRegion SubRegion FR BE DK EE ES FI GB HR IE IS IT NL NO PL SE TotalAtlantic Arctic waters 5 98 159 262

Bay of Biscay and Iberian West Coast 120 79 199Celtic Seas 88 153 241North Sea 299 5 54 111 23 256 3 751

Atlantic Total 419 5 59 79 199 153 98 23 415 3 1453Baltic Baltic Sea Middle 1 11 8 20

Baltic Sea North 1 6 1 8Baltic Sea West 167 167Kattegat 46 10 56

Baltic Total 213 2 6 11 19 251Meditterranean Algero-Provencal Basin 30 30

Gulf of Lion 90 90Ligurian Sea 12 34 46North Adriatic Sea 64 93 157North Ionian Sea 17 17North Tyrrhenian Sea 12 35 47South Adriatic Sea 16 60 76South Ionian Sea 2 2South Tyrrhenian Sea 32 32

Meditterranean Total 114 80 303 497Grand Total 533 5 272 2 79 6 199 80 153 98 303 23 415 11 22 2201


CSI040 final summary of resultsCSI040 final summary of results


CSI040 Hazardous substances in marine CSI040 Hazardous substances in marine organisms - organisms - aggregated maps prepared by EEA, 2005-2008aggregated maps prepared by EEA, 2005-2008


CSI040 – Low and High limitsCSI040 – Low and High limitsexample: cadmiumexample: cadmiumNameand tissue

Latin name Low/High

µg/kg. basis Reference Comment

CADMIUM

Mussels Mytilus sp.1 Low 960 D OSPAR 2008 BAC limit

Mussels Mytilus sp. High 5000 D EU 2006 Foodstuffs limit for "bivalve molluscs", Regulation (EC) No. 1881/2006, conversion assuming 20% wet weight (cf. OSPAR CEMP assessment manual 2008, Table 2.1)

Atlantic cod, liver

Gadus morhua

Low 26 W OSPAR 2008 BAC limit

Atlantic cod, liver

Gadus morhua

High 1000 W EU 2006 Foodstuffs limit for "bivalve molluscs", Regulation (EC) No. 1881/2006

Herring, muscle

Clupea harengus

Low 26 W OSPAR 2008 BAC limit

Herring, muscle

Clupea harengus

High 1000 W EU 2006 Foodstuffs limit for "bivalve molluscs", Regulation (EC) No. 1881/2006


SoE classification vs. WFD EQSSoE classification vs. WFD EQS Need for harmonisation of SoE assessment and EQS Need for harmonisation of SoE assessment and EQS

levelslevels(classification limits and selection of test values)(classification limits and selection of test values)

Italicised values are approx. conversions:Wet:dry 5:1Lipid:wet 40:100


Sediment dataSediment data

– Broader geographical coverageBroader geographical coverage• Iceland, Ireland, United Kingdom, Norway, Iceland, Ireland, United Kingdom, Norway,

Denmark, Sweden, Estonia, Lithuania, Denmark, Sweden, Estonia, Lithuania, (Latvia), Poland, Germany, Netherlands, (Latvia), Poland, Germany, Netherlands, Belgium, France, Portugal, Italy, Malta, Belgium, France, Portugal, Italy, Malta, Croatia, Greece, Romania, Turkey, Croatia, Greece, Romania, Turkey,

– Longer time spanLonger time span•Many series back to at least 1990Many series back to at least 1990

Probably sufficient for assessment in some Probably sufficient for assessment in some subregionssubregions


Loads to northeastern Loads to northeastern AtlanticAtlantic

0

25

50

75

100

125

150

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

%

CdPbHgLindanePCB7


Loads to northeastern Loads to northeastern AtlanticAtlanticexample: cadmiumexample: cadmium

Cadmium tonnes/yearBelgium Denmark France Germany Iceland Ireland Netherlands Norway Portugal Spain Sweden UK sum %

1990 4.3 0.565 36.8 8.54 3.387 10.3 16.21 9 0.67 51.3 141.1 1001991 3.9 35.3 7.24 3.387 7 8.31 15 0.343 49.35 129.8 921992 6.7 36.5 10.55 2.307 5.7 7.902 24 0.543 34.69 128.9 91.41993 3.42 35.2 9.2 1.757 4.7 7.182 1.7 0.06 0.1059 29.2997 92.6 65.71994 3.44 35.2 8.14 2.437 12.76 9.2263 3.925 0.1 0.4239 25.8704 101.5 721995 3.81 0.00005 34.7 7.54 2.172 26.6 8.992 0.2 0.1 0.244 21.31 105.7 74.91996 2.9 0.0001 33.9 5.645 3.58 8.4 5.85 0.128 19.01 79.4 56.31997 2.65 6.35 2.55 4.05 5.2 1.35 14.5 0.47 15.35 52.5 37.21998 2.45 6.25 3.45 9.7 7.75 0.6 6.8 0.56 19.75 57.3 40.61999 58.8 41.72000 51.0 36.22001 49.3 352002 58.1 41.22003 60.7 432004 72.7 51.52005 66.1 46.92006 82.5 58.52007 2.8696 34.966 5.20314 2.84 7.0160354 2.9345 0.65 23.84 0.6618 8.58242 89.55911 63.52008 3.6083 34.97 3.42603 0.0231 3.518 7.01603535 2.6909 0.28 7.906 0.6846 9.5631 73.68289 52.2

Large change since last submissionData gap

Data available but not shown


Hazardous substances – gaps in Hazardous substances – gaps in knowledgeknowledge

Main gaps in Main gaps in knowledge, need knowledge, need for:for:

• Better estimates of Better estimates of pathways, fate, levels, pathways, fate, levels, trends and effectstrends and effects

• Better understanding of Better understanding of multiple exposure to HSmultiple exposure to HS

• Better comprehension of Better comprehension of the role of climate the role of climate changechange

• Need for consistent and Need for consistent and reliable monitoringreliable monitoring

• Need for local knowledge Need for local knowledge to interpret changesto interpret changes

• Need for remedial action Need for remedial action plans and controlsplans and controls

CSI 040 HS in marine organisms, example: leadCSI 040 HS in marine organisms, example: lead

[email protected]@niva.no

eea – ”chemicals and water” workshop, copenhagen 06-07 december 2010 norman green (niva)...

Documents

compounds a0

relevant substances

anthracene a0

endosulfan a0

nonylphenol a0

groups of substances

hexachlorocyclohexane

hexsachlorobenzene a0