Management of Emerging Pollutants in the Marine Environment from the Perspective of a National Monitoring Authority

Transcription

1 Management of Emerging Pollutants in the Marine Environment from the Perspective of a ational Monitoring Authority.Theobald Federal Maritime and Hydrographic Agency (BSH) Hamburg

2 verview Decision processes for selecting emerging pollutants Realisation of new investigations Examples

3 Challenges for the analysis of organic pollutants in the marine environment Very low concentrations (pg/l, ng/kg) Sampling Special techniques Large sampling areas Large dynamic ranges Great variety of compounds Implementation of new pollutants Quality Assurance

4 Consequences for the Implementation of new pollutants Development of new methods or at least improvement of excisting procedures Procedure development and analysis take more time, are more expensive Principles Larger sampling amount Additional clean-up More selective detection

5 Routes to new Pollutants Scientific approach Rational, economic Approach F F F F F F F F F F F P S F F F F H Atrazin Br Br Br Br Br Br Br Br Br Br Administrative Approach (priority lists)

6 Scientific approach Structural considerations: analogues, homologues (brominated FR, fluorinated compounds such as PFS) Toxicological results on-target screening Toxicity directed analysis

7 Selection based on industrial Products Substances with intrinsic biological effects Pesticides Pharmaceuticals Personal Care Products Insecticides, Herbicides, Analgesic, Hormons, Antibiotica, Zytostatica, Fragrances, Tensides Large Volume Chemicals (without intrinsic biological effects ) Tensides, Plasticizers, Flame retardents

8 Priority Pollutant-Lists assic Pollutants lipophilic Persistent rganic Pollutants Dirty Dozen : Aldrine, Chlordane, DDT, Dieldrine, Endrine, Heptachlor, Mirex, Toxaphene PCB, HCB, PCDD, PCDF HCH PAH ovel Contaminants Hazardous Substances SPAR-List HELCM-List EU-WFD Many different substance classes, often polar

9 Ways SPAR and HELCM deal with hazardous substances HSC (DYAMEC) Persistancy Bioaccumulation Toxicity Large volume product Ways of exposure Environm. concentr. (rivers, air) Lists of Hazardous Substances Lists for priority action Lead country collects information Background papers information lacking? Mostly environmental concentrations of emerging pollutants are lacking for marine matrices ne off surveys Recommendation for further monitoring UBA BSH

10 Ranking Criteria for implementing emerging Pollutants (for monitoring agencies) Mandatory (core) parameter or voluntary parameter in monitoring program? Request by clients (politics, administration, public) In how many lists is it mentioned? Scientific challenge, environmental demand Amount of work for implementation of new analysis Funding available

11 Realisation of new investigations Problem o free valences for new method developments o additional resources from our agency Possible solutions Increase efficiency of all processes (sampling, analysis, data evaluation) Adaptation of quality/effort of existing monitoring Cooperations and research projects (funding)

12 Economic aspects Increase of efficiency Adaptation of quality levels Cooperations and research projects ptimising Quality and Effort - Monitoring Life Cycle II Quality/ Effort I III IV Phase I: Screening Phase II: Monitoring + investigation of processes, correlations, distributions etc. Phase III: Reduced monitoring, support by modelling, interpolation, indicator compounds Phase IV: End of monitoring as problems are solved Time

13 Economic aspects Increase of efficiency Adaptation of quality levels Cooperations Research projects Projects and Cooperations to investigate "novel" Compounds UBA UBA P.Lepom Extended List Standard WFD List PBDE Phthalate esters i.d. BSH rganotin-comp. "ovel" Contaminants Routine-Progr.: HCH, HCB, PCB, PAH, EKW ca. 60 Compounds, P - Pesticides onyl- Phenols, etc..heemken ARGE Elbe B. Stachel ofibrinic acid Mecoprop Swiss FRS Buser UBA P.Lepom Polyfluor. Compounds C.Caliebe University HH Prof. H.Hühnerfuss ca. 35 polar pesticides rganophosphate FR on-- Target- Screening Univers. Essen K.Bester Chloro- Ethers Screening Sediments University HH Prof. W.Francke S.Franke

14 Substance Method LQ [ng/l] Remarks WFD-Priority Pollutants Brom. Diphenylether GC-CI-MS (UBA-Project) Sed. / Biota C10-30-Chloroalkanes GC-MS-MS (UBA-Project) Sed. / Biota Anthracene LLE GC-MS Hexachlorbenzene LLE GC-MS-MS Hexachlorbutadiene LLE GC-MS 0.01 Hexachlorcyclohexane LLE GC-MS 0.01 aphthalene LLE GC-MS 0.05 PAH (6 to 16 comp.) LLE GC-MS Pentachlorobenzene LLE GC-MS Trichlorobenzenes LLE GC-MS Di(2ethylhexyl)phthalate LLE GC-MS special 5.0 rganotin Compounds LLE/Derivat. GC-AED 0.5 onylphenols LLE/Derivat. GC-MS 2 ctylphenols LLE/Derivat. GC-MS 0.5 Atrazine SPE HPLC-MS-MS 0.3 Diuron SPE HPLC-MS-MS 0.1 Isoproturon SPE HPLC-MS-MS 0.1 Simazine SPE HPLC-MS-MS 0.4 Alachlor SPE HPLC-MS-MS 0.1 Pentachlorophenol SPE HPLC-MS neg. 0.2 Chlorfenvinphos SPE GC-CI-MS 0.02 Chlorpyrifos SPE GC-CI-MS 0.01 Endosulfan SPE GC-CI-MS 0.03 Trifluralin SPE GC-CI-MS 0.005

15 Performance of Methods Down to 50 pg/l: reasonable amount of effort Sensitivity and selectivity of GC-MS (EI-SIM) ok Below 10 pg/l: problems are getting bigger Matrix background Blanks Selectivity of GC-MS (EI -SIM) often insufficient: additional pre-cleaning CI-MS MS-MS HR-MS Blank reduction: generally real hard work

16 Polyfluorinated Compounds in water of the German Bight (May 2004) ETE 3 DTET Ga 419 Mai 2004 Elbe ist significant source SGR 2 SB 2 SYLT 2 SYLT 1 LTIEF 55 PFA and PFS are main compounds 54 ng/l PFHxA PFHxS PFHpA PFA PFS PFoA PFDeA PFSA BRIFF AMRU 2 EIDER MEDEM Stade File: db2004.dsf 54 Concentrations similar to PAH and Herbicides Pattern of the compounds change PFCs can be detected in the open sea

17 Polyfluorinated Compounds in marine Sediments (2004/ 2005) UE UE 67 µg/kg 1,5 1,0 WB SSL WB 1 BL KS BL 2 Echernf. 40 bight Ruden 0.9 der ,5 ES ,0 LQ PFBuS PFHxA PFHxS PFHpA PFA PFoA PFDeA PFS PFSA

18 Triazine Herbicides Ga 405 (Jul-Aug 2003) S Atrazin Irgarol Simazin Terbutylazin ng/l 10,0 8,0 6, T4 T36 26 T9 T30 Stade S Terbutryn ,0 2,0 0,0 Atrazin Irgarol Prometryn Propazin Simazin Terbuthylazin Terbutryn S Propazin File:Ga405.dsf 10 Prometryn

19 Diuron and 2,4-D in the Baltic Sea (Mean values ) ng/l (Mean values) File:pp-Pestizide_ostsee.dsf Diuron 2,4-D

20 Trifluralin in the German Bight [pg/l] F F F pg/l winter summer 0.00 File: db2004.dsf

21 Chlorinated rganophosphate Esters Latitude Longitude TDCP TCEP TCPP km x P P P TDCP TCEP TCPP J.A. Andresen, D. Muir, D. Ueno, C. Darling,. Theobald, K. Bester; SEATAC Europe,2006: Emerging pollutants in the orth Sea and Lake ntario

22 ew contaminants for Future Surveys Polybrominated flame retardents Chlorinated and brominated phenols Endocrine discrupting compounds TBT in sediments onylphenols (re-evaluation) Phthalate esters (re-evaluation) Pharmaceuticals Komplexing agents (EDTA, TA) ew pesticides (Glyphosat) thers

23 Summary SPAR, HELCM and EU have set up valuable tools for identification and ranking of emerging pollutants Investigations on emerging pollutants is a very demanding analytical and logistic challenge - especially in the Marine Environment It is a permanent challenge, as the list of analysing compounds has to be updated constantly Rapid information exchange is necessary Cooperation with other institutions is of vital importance

24 Thank you for your attention