Monitoring of persistent organic compoundsin European surface waters: current situation and perspectives

Branislav Vrana

EU Water Framework Directive (WFD) - Directive 2000/60/EC

management structure for future European water policy, with the following main objectives:

expanding the scope of water protection to all waters, surface waters and groundwater; achieving "good status" for all waters by a certain deadline; water management based on river basins; "combined approach" of emission limit values and quality standards; getting the prices right: charges for water and waste water reflecting the true costs; getting the citizen involved more closely; streamlining legislation.

EU Water Framework Directive

“Status of water“ is the overall expression of status of a surface water body, which is given by ist ecological status and chemical status, depending which of them is worse.

„Good status“ is the status of a water body, when both chemical and ecological status is „good“

“Chemical status” refers to priority substances or priority hazardous substances for which environmental quality standards (EQS) are proposed

Strategy for dealing with pollution of water from chemicals

Article 16 of the Water Framework Directive 2000/60/EC (WFD)List of 33 priority substances, revision every 4 years:

organic substances • pesticides• polycyclic aromatic hydrocarbons (PAHs)• benzene• halogenated solvents• brominated flame retardants• plasticisers• surfactants• antifouling agents

heavy metals (Cd, Hg, Ni, Pb)8 other pollutants that pose a particular risk to animal and plant life in the aquatic environment and to human health

• chlorinated pesticidesriver basin specific pollutants – substances that can have a harmful effect on biological quality, and which may be identified by Member States as being discharged to surface waters in significant quantities – assessment of ecological status

priority pollutants - progressive reductionpriority hazardous substances – (persistent, bioaccumulative and toxic) -cessation or phasing-out of discharges, emissions and losses

Identification of substances of priority concern

a simplified risk-based assessment procedureevidence regarding the intrinsic hazard of the substance concerned, and in particular its aquatic ecotoxicity and human toxicity via aquatic exposure routesevidence from monitoring of widespread environmental contamination,other proven factors, which may indicate the possibility of widespread environmental contamination, such as production or use volume and use patterns.

POPs in the WFD priority pollutant list

Cyclodiene pesticidesAldrinDieldrinEndrinIsodrin

HexachlorobenzeneDDT and its isomersEndosulfanHexachlorocyclohexane (all isomers)PentachlorobenzenePentabromodiphenylether (6 congeners)

Priority substance list will be updated in 2011, proposed list includes POPs:

PCBs, PCDD/PCDF, Heptachlor/Heptachlor epoxide, PFOS, PBDE (including octa)

Limits on concentrations in surface waters

Directive 2008/105/EC on environmental quality standards (EQS) on Community levelCompliance checking provisions have been established for

inland surface waters (rivers and lakes) other surface waters (transitional, coastal and territorial waters)

Limits on concentrations in surface waters -EQS

Two types of EQSAnnual average concentrations (AA-EQS) for protection against long-term and chronic effectsMaximum allowable concentrations (MAC EQS) to avoid serious irreversible consequences for eco-systems due to acute exposure in the short-term

EQS values have been so far limited for the majority of substances to surface water only (for organic compounds based on total concentration)EQS based on concentration in biota only for Hg, HCB and hexachlorobutadiene Member states may derive country specific EQS for sediment and biota and use them instead of the EQS for water

Monitoring of long term trends

Monitoring in sediments and biota:Compounds with bioaccumulation potentialAssessment of long-term impacts of anthropogenic activity and temporal trends Member States should ensure that existing levels of contamination in biota and sediments will not increase

POPs are relevant compounds

EQS values for compliance checking in water (μg/L)

CompoundAA-EQSInland surfacewaters

AA-EQSOther

surfacewaters

MAC-EQS Inland surfacewaters

MAC-EQSOthersurfacewaters

Cyclodiene pesticides Σ = 0.01 Σ = 0.005 not applicable not applicable

Hexachlorobenzene 0.01 0.01 0.05 0.05DDT total 0.025 0.025 not applicable not applicable

Endosulfan 0.005 0.0005 0.01 0.004Hexachlorocyclohexane 0.02 0.002 0.04 0.02Pentachlorobenzene 0.007 0.0007 not applicable not applicable

PBDE (sum of 6 congeners)

0.0005 0.0002 not applicable not applicable

Annual average concentration < AA EQSMaximum concentration < MAC EQS

Limit of quantification < 30% of EQS value

Expanded measurement uncertainty< 50% at EQS level

Minimal performance criteria of analytical methods: Commission Directive 2009/90/EC

Good chemical status:

Difficulties

only 75% of the 41 hazardous substances for which Europe-wide EQSs have been proposed can be eliably monitored in water with acceptable uncertainty when applying existing standardised methodsDifficulties especially for some POPs: PBDE, organochlorine pesticides

lack of validated, sufficiently sensitive methods that are applicable in routine laboratory conditionsvalidated methods for measurement of total concentration of highly hydrophobic compounds, especially in water with high suspended particulate matter contents

SolutionsViable and standardisable methods for new priority substancesLowering analytical costsUse of effect-based screening Introduction of new sampling matrices and alternative sampling concepts

e.g. passive samplers for measuring time-weighted average concentrations of dissolved contaminants

• data for contaminant environmental fate modelling• reliable trend monitoring• biomimetic samples to provide concentrations correlated to

those in biota