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20140507 monitoring biocides in the rivers rhine and meuse
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20140507 monitoring biocides in the rivers rhine and meuse


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3rd International Fresenius Conference on Environmental Risk Assessment of Biocides 7 May 2014, Mainz (GER)

3rd International Fresenius Conference on Environmental Risk Assessment of Biocides 7 May 2014, Mainz (GER)

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  • 1. Monitoring biocides in the rivers Rhine and Meuse important sources for drinking water production André Bannink, RIWA 7 May 2014 environmental risk assessment of biocides 3rd International Fresenius Conference, Mainz (D) 1
  • 2. Outline • RIWA: who are we? – Why do we monitor water quality? • Which biocides concern(ed) us? Three examples 1. 3-(3,4-dichlorophenyl)-1,1-dimethylurea 2. N,N-diethyl-m-toluamide 3. Tetrakis(hydroxymethyl)phosphonium sulfate • Conclusions 2
  • 3. RIWA: who are we? • Association: water companies that use river water as source for the production of drinking water • Sources: rivers Rhine, Meuse and Scheldt • Members: supply drinking water to several millions of consumers • 530 Mm3/a in NL and 275 Mm3/a in B 3
  • 4. Our mission statement • The water quality in the rivers Rhine and Meuse should be such that it can be purified to drinking water using natural treatment Not the same as but in line with Article 7 Water Framework Directive • Avoid deterioration of water quality in order to reduce the level of purification treatment required in the production of drinking water 4
  • 5. Location of Meuse and Rhine river basins 5
  • 6. Our monitoring programme • Purpose is twofold: 1. To know the status of the river water quality 2. To detect trends in the river water quality • RIWA Members monitor their source at the intake – To meet regulatory obligations, – To control the production process, and – To fulfil RIWA monitoring programme • RIWA coordinates and reports annually 6
  • 7. RIWA Members monitor their source at intake Two examples of monitoring points continuous automatic sampling grab sampling Keizersveer (Meuse) Nieuwegein (Lek Canal, Rhine Basin) 7
  • 8. Our monitoring programme • We focus on drinking water relevant substances – Substances that fail to meet Regulatory Water Quality Standards – Substances that breech Target Values from the European River Memorandum • We sometimes detect substances that (could) have been used as a biocide 8
  • 9. Our monitoring programme • Three major concerns 1. Plant Protection Products, Biocides and their metabolites • Glyphosate / AMPA major water quality problem • Glyphosate is considered a PPP, but emissions originate mostly from use outside agriculture • AMPA is a metabolite of PPP’s as well as of coolant additives (phosphonates) 2. New Emerging Substances / Substances of Emerging Concern 3. Impact of Climate Change 9
  • 10. European River Memorandum 10
  • 11. Biocides in our monitoring programme • Who determines that a substance we have detected was used as a biocide? – We do not have this specific expertise • NL: Board for the permission of plant protection products and biocides (Ctgb) sends a list of PPPs and Biocides which are authorised annually – In return we send Ctgb our monitoring results over the past 5 years 11
  • 12. Biocides in the Netherlands • Water Quality Standard in NL for PPPs and Biocides in Surface Water used for drinking water production is 0.1 μg/L – WQS exceedances at intake points play a role in the authorisation process – Hence our co-operation with Ctgb • Sometimes multiple uses of substances – We are unable to distinguish the use as PPP from the use as a biocide 12
  • 13. Biocides detected in rivers Going back in time to learn for the future Diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) • Major problem due to use as weed killer on paved areas – Technicality: this use does not protect any crop but still it is seen as a PPP • Caused the longest intake stop ever recorded back in 1993 13
  • 14. 1993 • Intake of water from the River Meuse was stopped for 7 weeks – Diuron levels exceeded intake criterion (= 10 times the Water Quality Standard) – Maximum bridging capacity of reservoirs is approximately 90 days 14
  • 15. Biocides detected in rivers Diuron • The use of the active substance in PPPs was banned in NL in 1999 / in B in 2002 • Temporary ban in EU in 2007, re-admission in October 2008 • December 2008: placement on the list of Priority Substances under WFD 15
  • 16. Diuron in Dutch surface water: average concentrations 16
  • 17. Diuron levels in Rhine and Meuse 0.0 0.2 Concentration in μg/L 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 01/Jan/91 14/Jul/92 25/Jan/94 08/Aug/95 18/Feb/97 01/Sep/98 14/Mar/00 25/Sep/01 08/Apr/03 19/Oct/04 02/May/06 13/Nov/07 26/May/09 07/Dec/10 19/Jun/12 31/Dec/13 Keizersveer (Meuse) Nieuwegein (Rhine Delta) WQS This peak originates from an incident in B 17
  • 18. Biocides detected in rivers Diuron • Since 1999 no PPP-authorisation in NL • Currently two Biocides based on Diuron are authorised in NL 1. ACTICIDE MKX (for use in paint and plaster) 2. MIRECIDE-TF/480.F (for use in paint) 18
  • 19. Biocides detected in rivers DEET (N,N-diethyl-m-toluamide) • Use as active substance authorised in 35 biocides in NL / 17 in B – Various anti-mosquito sticks, rollers, gels and sprays • There have always been detections – Until recently under WQS – Now we also see breeches of WQS 19
  • 20. DEET in Dutch surface water average concentrations 20
  • 21. DEET levels in the River Meuse 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 23 October 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 Luik (M600) Heel (M690) Keizersveer (M865) WQS Concentration in μg/L 21
  • 22. Biocides detected in the Rhine THPS (Tetrakis(hydroxymethyl)phosphonium sulfate) 22
  • 23. Biocides detected in the Rhine THPS (Tetrakis(hydroxymethyl)phosphonium sulfate) What had happened? • Treatment of the coolant of the Leibstadt (CH) Nuclear Power Plant – 28 June 2011: 15 tonnes of 13% Sodium hypochlorite • Sodium thiosulfate was used to neutralise unused chlorine before emitting the coolant in the Rhine – 30 June 2011: 2.1 tonnes of THPS was added to the coolant system • Hydrogen peroxide was added, transforming THPS into THPO (Tris-hydroxymethylphosphine oxide) before emitting the coolant in the Rhine 23
  • 24. Biocides detected in the Rhine THPS (Tetrakis(hydroxymethyl)phosphonium sulfate) Drinking water companies in CH, DE and NL were agitated because • No information was shared beforehand even though the company involved did inform the authorities • There were no analytical methods available to measure THPS and THPO at the time • Intakes for drinking water production in CH and DE were stopped out of precaution Modelling was performed to estimate concentrations at intake points, samples were take for future analysis 24
  • 25. THPO in the Rhine Model results vs measurements 25
  • 26. Biocides detected in the Rhine THPS and THPO Measured concentrations were significantly lower than the predictions from the model • But still well over the 0.1 μg/L Drinking water companies demanded steps to be taken to prevent future incidents • Better information sharing and stricter permits • International Commission for the Protection of the Rhine makes inventory of all coolant emissions 26
  • 27. Biocides of concern for drinking water production 27 RIVM Study 601712007/2010 KWR Study BTO 2013.205(s): LC/MS and GC/MS methods adapted, only irgarol was found (< WQS)
  • 28. Conclusions • Biocides are currently not a continuous concern to the production of drinking water from Rhine and Meuse – caution is necessary since incidents have occurred • Concerns about the future, because – Not all individual substances can be analysed yet – New techniques are developed and implemented (2014: method for quaternary ammonium compounds operational) 28
  • 29. Recommendations • Emissions of coolant into the rivers is an issue to follow up on – Besides biocides also other compounds are emitted eg. anti-foaming agents, anti-corrosion agents • Emissions have a larger impact under low flow conditions (especially for the Meuse) – This should be considered in the permit – This becomes more important under changing climate 29
  • 30. Thank you for your attention! André Bannink Are there any questions? @BanninkAndre My publications can be found on 30