Status of biocide monitoring in Germany. Report from North-Rhine Westphalia (NRW) surface water
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1 Status of biocide monitoring in Germany Report from North-Rhine Westphalia (NRW) surface water Workshop "Environmental monitoring of biocides in Europe - from prioritisation to measurements 5./ , Berlin Session II biocide monitoring in surface waters Dr. Harald Rahm, Dr. Friederike Vietoris, LANUV NRW Dr. Dieter Busch
2 Biocide monitoring in NRW Surface water Sediment/ Suspended matter Aquatic Biota Ground water Ground Malathion Diuron.. Cybutryne Organotin compounds Isoproturon Dimethoat Naphthalene Food Passive Sampling Sludge Waste water Liquid manure Air Dr. Dieter Busch
3 Availabel data - A short overview Matrix Period of time Substances Surface water Continual since the 80 s 19 substances, e.g. Diuron, Isoproturon, Malathion, Naphthalin, Organotin compounds, Suspended matter Continual since the 90 s Mainly organotin compounds, Naphthalene Sediments Continual since the 90 s Mainly organotin compounds, Naphthalene Ground water Continual since the 80 s 22 substances, e.g. Carbendazim, Diuron, Isoproturon, Malathion, Naphthalin Waste water Continual since the 80 s e.g. Diuron, Isoproturon, Terbutryn, Organotin compounds, Naphthalene Sludge unique Organotin compounds Ground unique Hexachlorcyclohexane,Naphthalene, Organotin Compounds, Diuron,
4 Monitoring of wastewater, groundwater and surfacewater in NRW Waste water monitoring sampling based on German and EU legislation, additional monitoring of biocides where possible Monitoring according to EU-WFD for surface water chemical and physical values from water, suspended matter and sediment and a realtime surveillance along the Rhine Monitoring according to EU-WFD for ground water chemical and physical values Biocides are part of each monitoring program but there ist no special biocide monitoring to meet the BPD!
5 Surface water WFD Monitoring NRW Monitoring of substances depends on their relevance (value > ½ EQS) Monitoring Guideline NRW:
6 Chemical analysis Substance groups are analysed in common AMPA & Glyphosat DIN F22 21 Aniline derivates DIN F16 13 Chlorophenoles DIN EN Chlorinates pesticides DIN F2 16 Nitroaromatic compounds DIN F17 8 PBDE ISO CD (s) 37 Phosphorous compunds EN ISO F6 25 neutral/basic plant treatment agents DIN EN ISO acid plant treatment agents (POC) DIN organotin compounds DIN EN ISO 17353(aq) ISO/DIS 23161(s) 15 polycyclic aromatic hydrocarbons (PAH) DIN EN ISO 17993
7 WFD monitoring: surface waters Biocides: Number of monitored water bodies ( ) Chlortoluron Terbutylazin Diuron Isoproturon Terbutryn Prometryn Chlorpyrifos-ethyl Dimethoat Fenitrothion Malathion Naphthalene TBT Monobutyltin Cybutryne Dibutytin
8 WFD monitoring: surface waters Results for biocides ( ) 60 mostly Emscherregion [%] 30 stations with values > LOD values > LOD Monobutyltin Dibutyltin Isoproturon Diuron Naphthalene TBT Terbutylazin Terbutryn Tebuconazol Chlortoluron Prometryn Dimethoat Chlorpyrifos-ethyl Malathion Fenitrothion Cybutryn
9 Surface waters assessment in accordance to WFD results > EQS / guide values ( , preliminary) 25 mostly Emscherregion 20 [% monitored water bodies] Monobutyltin Dibutytin TBT Isoproturon Diuron Naphthalene Cybutryne Terbutryn Chlorpyrifos-ethyl Terbutylazin Chlortoluron Dimethoat Fenitrothion Malathion Prometryn Tebuconazol
10 WFD monitoring: surface waters - Diuron
11 WFD monitoring: surface waters - Naphthalene
12 surveillance along the river Rhine warning and alert system for drinking water-plants along Rhine and Ruhr chemical laboratory in Düsseldorf two continous sampling stations with laboratories in Bad Honnef and Bimmen four automatic measuring and sampling stations along river Rhine seven stations in big tribuatries three more stations for retain sampling Laboratory and sampling ship Max Prüss in Duisburg possible cross-profile-sampling from Rhine-ferries
13 Example for time-scale sampling (µg/l) Isoproturon in der Lippe bei Wesel 1,20 1,00 0,80 0,60 0,40 24h-Fraktionen 8h-Fraktionen 0,20 0, Okt 25. Okt 30. Okt 04. Nov 09. Nov 14. Nov 19. Nov 24. Nov 29. Nov 04. Dez 09. Dez 14. Dez 19. Dez 24. Dez
14 Surface water: Trends?? Rhine: Kleve-Bimmen Isoproturon Rhine: Kleve-Bimmen - Diuron 0,5 0,16 0,14 0,4 0,12 0,3 0,1 [µg/l] 0,2 [µg/l] 0,08 0,06 0, average Max ,04 0, Average 2002 Max Ems: Diuron Rhine: Kleve-Bimmen - Terbutryn [µg/l] 0,4 0,35 0,3 0,25 0,2 0,15 [µg/l] 0,09 0,08 0,07 0,06 0,05 0,04 0,03 0,1 0, Average Max 0,02 0, Average Max
15 WFD monitoring: Ground Water Examples of monitored biocides ( ) [%] Naphthalene Isoproturon Diuron Terbuthylazine Chlortoluron Prometryn Terbutryn Tebuconazole Dimethoate Fenpropimorph Propiconazole Fluometuron Chlorphenylaminocarbonyldifluorbenzamid Dichlofluanid Chlorpyrifos Cybutryne Fenitrothion grundwater = memory no. station with values > LOD values > LOD
16 Waste Water: legal requirement and risk orientated investigations Results of risk orientated investigations of waste water ( ) mainly one (!) sewage works 60 [%] Emscher Region! Diuron Terbutryn Isoproturon Tebuconazol Monobutyltin Naphthalene Dibutyltin TBT Terbutylazin Prometryn Chlorpyrifos-ethyl Chlortoluron Cybutryn Dimethoat Fenitrothion Malathion no. of measuring points > LOD values > LOD
17 Information tool: waste water, surface water, ground Surface water/ waste water: River Management Plan NRW nrw.de/bewirtschaftungsplanu ng/index.jsp Internet Ground:
18 Information tool: current surface water quality
19 Results and Outlook: monitoring of biocides in water Results: monitoring of biocides in surface water, waste water and ground water is necessary und useful relevant biocides in NRW: Isoproturon, Diuron, Terbutryn, organotin compounds; local: naphthalene (industrial sources) EQS-excess: less than 3% of surface waters (length), mostly regional and in smaller brooks positve trends for many biocides positive, not for all, e.g. Isoproturon Outlook: Trend monitoring and overview will continued according to WFD Improvements: - event-related monitoring to find maximum concentrations in smaller rivers and brooks - monitoring of new biocides according to emission aspects, ecotoxicological effects - evaluating substance-lists for relevance - better combination with drinking water monitoring adapting WFD-monitoring
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