Management of Emerging Pollutants in the Marine Environment from the Perspective of a ational Monitoring Authority.Theobald Federal Maritime and Hydrographic Agency (BSH) Hamburg
verview Decision processes for selecting emerging pollutants Realisation of new investigations Examples
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
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
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)
Scientific approach Structural considerations: analogues, homologues (brominated FR, fluorinated compounds such as PFS) Toxicological results on-target screening Toxicity directed analysis
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
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
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
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
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)
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
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
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 0.003 Hexachlorbenzene LLE GC-MS-MS 0.001 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 0.003 Pentachlorobenzene LLE GC-MS 0.005 Trichlorobenzenes LLE GC-MS 0.005 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
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
Polyfluorinated Compounds in water of the German Bight (May 2004) 3 4 5 6 7 8 9 56 56 ETE 3 DTET Ga 419 Mai 2004 Elbe ist significant source 55 8 7 SGR 2 SB 2 SYLT 2 SYLT 1 LTIEF 55 PFA and PFS are main compounds 54 ng/l 6 5 4 3 2 1 0 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 3 4 5 6 7 8 9
Polyfluorinated Compounds in marine Sediments (2004/ 2005) 56 4 5 6 7 8 9 10 11 12 13 14 15 56 2004 0.7 2005 UE 70 55 54 1.1 UE 67 µg/kg 1,5 1,0 WB 5 4.1 2.9 24.5SSL WB 1 BL 4 2.9 11 KS 11 4.3 BL 2 Echernf. 40 bight 710 28 Ruden 0.9 der 55 54 0,5 ES 1 0.8 0,0 LQ 0.03 0.05 0.005 PFBuS PFHxA PFHxS PFHpA PFA PFoA PFDeA PFS PFSA 4 5 6 7 8 9 10 11 12 13 14 15
Triazine Herbicides 6 4 2 0 2 4 6 8 10 62 Ga 405 (Jul-Aug 2003) 62 61 61 60 52 51 60 S Atrazin 59 58 46 48 50 45 44 43 40 59 58 Irgarol Simazin Terbutylazin 57 56 55 54 ng/l 10,0 8,0 6,0 33 29 20 17 8 T4 T36 26 T9 T30 Stade 57 56 55 54 S Terbutryn 52 51 4,0 2,0 0,0 Atrazin Irgarol Prometryn Propazin Simazin Terbuthylazin Terbutryn 14 13 29 6 12 11 104 32 52 51 S Propazin 6 4 2 0 2 4 6 8 File:Ga405.dsf 10 Prometryn
Diuron and 2,4-D in the Baltic Sea (Mean values 2000-2002) 57 9 10 11 12 13 14 15 16 17 57 56 56 55 55 10 ng/l 8 54 6 54 4 2001-2002 (Mean values) File:pp-Pestizide_ostsee.dsf Diuron 2,4-D 9 10 11 12 13 14 15 16 17 2 0
Trifluralin in the German Bight [pg/l] 2004-2005 56 3 4 5 6 7 8 9 56 14 180 F F 210 110 55 F 280 11 220 19 100 140 22 55 380 15 200 150 540 58018 540 160 160 15 120 170 15 54 16 54 26 pg/l 600 400 200 winter summer 0.00 File: db2004.dsf 3 4 5 6 7 8 9
Chlorinated rganophosphate Esters Latitude Longitude 3 4 5 6 7 8 9 56 55 54 TDCP TCEP TCPP 14.0 12.0 10.0 8.0 6.0 4.0 2.0 0.0 12 13 11 14 100 km 10 9 8 7 5 3 6 4 2 x5 1 56 55 54 P P P TDCP TCEP TCPP 3 4 5 6 7 8 9 J.A. Andresen, D. Muir, D. Ueno, C. Darling,. Theobald, K. Bester; SEATAC Europe,2006: Emerging pollutants in the orth Sea and Lake ntario
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
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
Thank you for your attention