Monsanto Survey of Glyphosate and Ampa in Groundwaters and Surface Waters in Europe Final Report

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SURVEY OF GLYPHOSATE AND AMPA IN GROUNDWATERS AND SURFACE WATERS IN EUROPE FINAL REPORT

WRc Ref: UC8073.02 NOVEMBER 2009

SURVEY OF GLYPHOSATE AND AMPA IN GROUNDWATERS AND SURFACE WATERS IN EUROPE

Report No.: UC8073.02

Date: November 2009

Authors: Helene Horth and Karen Blackmore

Contract Manager: Karen Blackmore

Contract No.: 15276-0

RESTRICTION: This report has the following limited distribution:

External: 3 copies

Internal: 3 copies

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WRc Swindon, Frankland Road, Blagrove, Swindon, Wiltshire, SN5 8YF. Telephone: + 44 (0) 1793 865000 Fax: + 44 (0) 1793 865001 Website: www.wrcplc.co.uk

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CONTENTS

SUMMARY 1

1. INTRODUCTION 5 1.1 Acknowledgements 7

2. AUSTRIA 8 2.1 Introduction 8 2.2 Surface Water 8 2.3 Groundwater 9 2.4 Summary 10

3. BELGIUM 11 3.1 Introduction 11 3.2 Surface Water 11 3.3 Groundwater 15 3.4 Summary 18

4. BULGARIA 19 4.1 Summary 19

5. CYPRUS 20 5.1 Summary 20

6. CZECH REPUBLIC 21 6.1 Summary 21

7. DENMARK 22 7.1 Introduction 22 7.2 Surface Water 22 7.3 Groundwater 22 7.4 Summary 26

8. ESTONIA 27 8.1 Summary 27

9. FINLAND 28 9.1 Introduction 28 9.2 Surface Water 28 9.3 Groundwater 29 9.4 Summary 30

10. FRANCE 31

10.1 Introduction 31 10.2 Surface Water 31 10.3 Groundwater 34 10.4 Summary 36

11. GERMANY 37 11.1 Introduction 37 11.2 Surface Water 37 11.3 Groundwater 47 11.4 Summary 49

12. GREECE 50 12.1 Summary 50

13. HUNGARY 51 13.1 Summary 51

14. IRELAND 52 14.1 Introduction 52 14.2 Surface Water 52 14.3 Groundwater 54 14.4 Summary 54

15. ITALY 55 15.1 Introduction 55 15.2 Surface Water 55 15.3 Groundwater 56 15.4 Summary 56

16. LATVIA 57 16.1 Introduction 57 16.2 Surface Water 57 16.3 Groundwater 57 16.4 Summary 57

17. LITHUANIA 58 17.1 Summary 58

18. LUXEMBOURG 59 18.1 Summary 59

19. MALTA 60 19.1 Introduction 60 19.2 Groundwater 60 19.3 Summary 60

20. NORWAY 61 20.1 Introduction 61 20.2 Surface Water 61 20.3 Groundwater 63 20.4 Summary 64

21. POLAND 65 21.1 Summary 65

22. PORTUGAL 66 22.1 Summary 66

23. ROMANIA 67 23.1 Summary 67

24. SLOVAK REPUBLIC 68 24.1 Introduction 68 24.2 Surface Water 68 24.3 Groundwater 69 24.4 Summary 69

25. SLOVENIA 70 25.1 Summary 70

26. SPAIN 71 26.1 Introduction 71 26.2 Surface Water 71 26.3 Groundwater 72 26.4 Summary 72

27. SWEDEN 73 27.1 Introduction 73 27.2 Surface Water 73 27.3 Groundwater 76 27.4 Summary 79

28. SWITZERLAND 80 28.1 Introduction 80 28.2 Surface water 80 28.3 Groundwater 81 28.4 Summary 83

29. THE NETHERLANDS 84 29.1 Introduction 84 29.2 Surface Water 84

29.3 Groundwater 91 29.4 Summary 92

30. UNITED KINGDOM 94 30.1 Introduction 94 30.2 Surface Water 94 30.3 Groundwater 96 30.4 Summary 98

31. CONCLUSION 99

REFERENCES 101

APPENDICES

APPENDIX A PROFESSIONALS / ORGANISATIONS CONTACTED 111

LIST OF TABLES

Table 1 Summary of glyphosate and AMPA data in surface water in Europe 3

Table 2 Summary of glyphosate and AMPA data in surface water in Europe 4

Table 2.1 Glyphosate and AMPA in groundwater in Austria, 2004 (source: UBA, 2006) 10 Table 3.1 Glyphosate and AMPA in surface waters in Flanders, 2000-2006 (source: MIRA, 2007) 11 Table 3.2 Glyphosate results for Escaut RBD, 2001-2006 (source: Denis Godeaux, Direction Eaux de Surface, Wallonie) 13 Table 3.3 Glyphosate results for the Meuse RBD, 2001-2006 (source: Denis Godeaux, Direction Eaux de Surface, Wallonie) 14 Table 3.4 Glyphosate results for the Rhine (Moselle) RBD, 2003-2004 (source: Denis Godeaux, Direction Eaux de Surface, Wallonie) 15 Table 3.5 Percentage detection of AMPA and glyphosate at groundwater monitoring sites in Flanders, spring 2006 (source: MIRA, 2007 and details from www.milieurapport.be) 16 Table 7.1 Glyphosate and AMPA in the main groundwater surveys in Denmark, 1993 – 20071) (source: GEUS, 2009) 24 Table 7.2 Glyphosate and AMPA in the main groundwater surveys in Denmark, 1993 – 2002 (source: GEUS, 2003) 24 Table 7.3 Glyphosate and AMPA in agricultural watersheds (shallow groundwater) and ‘other observation boreholes’ (mainly small private water supplies) in Denmark, 1993 – 2002, and 1993 – 2007 (source: GEUS, 2003 and 2009) 25 Table 9.1 Surface water monitoring in two rivers in Finland, 2007 to 2009 (source: Mira Grönroos, Finnish Environment Institute SKYE, personal communication, 2009) 29 Table 9.2 Groundwater monitoring in Finland, 2002 to 2008 (source: Tapini Säynätkari, Finnish Environment Institute SKYE, personal communication, 2009) 30 Table 10.1 Glyphosate in French surface waters, 1997 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) 32 Table 10.2 AMPA in French surface waters, 1998 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) 32 Table 10.3 Glyphosate and AMPA detections in the Ile de France region in 2005-06 and 2006-07 (source: DIREN, 2006; DIREN, 2008) 33 Table 10.4 Glyphosate in French groundwater, 1999 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) 35 Table 10.5 AMPA in French groundwater, 1999 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) 35

Table 11.1 Glyphosate and AMPA in surface water in the State of Baden Württemberg, 2006 - 2008 (source: Claudia Früh, LUBW, personal communication, 2009) 38 Table 11.2 Glyphosate and AMPA in the river Main, State of Hessen, 2007-2008 (source: Dr. Peter Seel, Hessisches Landesamt für Umwelt und Geologie, Wiesbaden, personal communication, 2009) 39 Table 11.3 Glyphosate and AMPA in surface waters in Nordrhein-Westfalen, 2006-2008 (Source: NRW FlussWinIMS database, 2009, http://www.elwasims.nrw.de/ims/FlussWinIMS/start.htm) 40 Table 11.4 Glyphosate and AMPA in surface waters in the State of Rheinland- Pfalz, 2004-2007 (source: LUWG, 2009) 41 Table 11.5 Glyphosate and AMPA in surface water in Sachsen-Anhalt, 01.01.2009-04.09.2009 (source: Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009) 44 Table 11.6 Glyphosate and AMPA in surface waters in Thüringen, 1997-2008 (source: data provided by Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009) 45 Table 11.7 Glyphosate and AMPA at water intakes on the Rhine, 1999-2004 (in g l-1) (source: Brauch et al., 2002 and 2003; ARW 2004) 46 Table 11.8 Glyphosate and AMPA on the river Rhine, monthly analyses in 2004 (in g l-1) (source: ARW, 2004) 47 Table 11.9 Glyphosate and AMPA in raw water intakes at Styrom-Ost and Hengsen waterworks (river Ruhr) in 2005 (source: Schlett et al., 2005) 47 Table 11.10 Glyphosate and AMPA in groundwater in Germany, 1996-2008 (source: Dr Wolter, UBA, personal communication, 2009) 48 Table 14.1 Glyphosate monitoring in surface waters in Ireland, 2007 to 2009 (source: provided to Monsanto by Dr.Ciaran O'Donnell, personal communication, 2009) 52 Table 14.2 Glyphosate results from the SE River Basin District, Ireland, 2005 - 2006 (source: TNO, 2007 and TNO, 2008) 53 Table 15.1 Results of glyphosate monitoring in surface waters of the Lombardy Region of Italy, 2005-2007 (source: data provided to Monsanto by Giuseppina Veraldi, Arpa Lombardia) 55 Table 15.2 Results of glyphosate groundwater monitoring in the Lombardy Region of Italy, 2005-2007 (source: provided to Monsanto by Giuseppina Veraldi, Arpa Lombardia) 56 Table 20.1 Glyphosate application in agricultural areas and glyphosate and AMPA detected in streams and rivers in Norway, 1997-2006 (source: Ludvigsen and Lode, 2008) 62 Table 20.2 Glyphosate and AMPA in groundwater in agricultural areas in Norway (source: Ludvigsen and Lode, 2008) 63 Table 24.1 Glyphosate in surface waters in Slovak Republic 2006 – 2008 (source: Lea Mrafkova, Slovak Hydrometeorological Institute, personal communication, 2009) 68

Table 26.1 Glyphosate data from two river basin districts in Spain with water quality issues (Javier Cachón de Mesa, Head of Environmental Information, Ministry of Environment, personal communication, 2009) 71 Table 27.1 Glyphosate in Swedish surface water, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se) 74 Table 27.2 AMPA in Swedish surface water, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se) 75 Table 27.3 Glyphosate in Swedish groundwater, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se) 77 Table 27.4 Glyphosate detection in groundwater in Regions M, C, O and S, 2000 – 2008 * (source: SLU Pesticides Database, 2008, http://pesticid.slu.se) 78 Table 27.5 AMPA in Swedish groundwater, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se) 79 Table 28.1 Glyphosate and AMPA in surface water in Switzerland (source: Hanke et al., 2008) 81 Table 28.2 Glyphosate and AMPA in groundwater in Switzerland (BAFU, 2009) 82 Table 29.1 Glyphosate and AMPA in surface water in the Netherlands in 2006 (source: Pesticides Atlas, 2008, last updated 13 Dec. 2008) 85 Table 29.2 Glyphosate and AMPA detections in raw water intakes (surface water) in the Netherlands, 2000-2007 (source: Drinking water quality reports 2000 - 2006, Versteegh et al., 2002 - 2008 and undated) 87 Table 29.3 Glyphosate and AMPA in the River Rhine at Lobith in the Netherlands, summary of results, 1999-2002 (sources: RIWA, no date and no date - a) 90 Table 29.4 Glyphosate and AMPA in the River Rhine at Lobith in the Netherlands, monthly results, 1999-2002 (sources: RIWA, no date and no date - a) 90 Table 29.5 Maximum concentrations of glyphosate and AMPA in the River Rhine in the Netherlands, 2001 and 2002 (source: RIWA, no date – a) 91 Table 29.6 Glyphosate and AMPA in groundwater in the Netherlands in 2003 - 2006 (source: Van der Linden et al., 2007) 91 Table 29.7 Glyphosate and AMPA in the Maas RBD, 2007 (from Verhagen et al., 2008) 92 Table 30.1 Glyphosate in surface water in the UK, 1993 - 2007 (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009) 95 Table 30.2 Investigations of pollution incidents in surface water 1996 - 2007 (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009) 96 Table 30.3 Glyphosate analyses in groundwater monitoring programmes 1995- 2007 in the UK (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009) 97 Table 30.4 Investigation of pollution incidents in groundwater in Wales (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009) 97

LIST OF FIGURES

Figure 3.1 Glyphosate concentrations in surface waters of the Walloon Region, 2001-2005 (source: DGRNE, 2007) 12 Figure 3.2 Pesticides and metabolites monitored in groundwater of the Walloon Region (in percentage of sites affected), 01/01/2000 to 01/03/2006 (from DGRNE, 2007) 17 Figure 9.1 Pesticide sales in Finland (source: TemaNord, 2007 via Savela & Hynninen, 2004) 28 Figure 11.1 Glyphosate concentrations in the river Nahe, April 2001 to December 2002 (source: LUWG, 2007b) 43 Figure 11.2 Glyphosate load in the river Nahe, April 2001 to December 2002 (source: LUWG, 2007b) 43 Figure 27.1 Detection frequency in surface water (>10%), 2003 data (source: Kreuger & Adielsson, 2006) 76 Figure 29.1 Glyphosate in surface water in the Netherlands in 2006, in terms of sites and the 0.1 µg l-1 drinking water standard (source: Pesticides Atlas, 2008, last updated 13 Dec. 2008) 86 Figure 29.2 Glyphosate in surface water in the Netherlands in 2006, in terms of sites exceeding the 0.1 µg l-1 drinking water standard on a monthly basis (source: Pesticides Atlas, 2008, last updated 13 Dec. 2008) 86 Figure 29.3 Glyphosate concentrations in surface waters in Flevoland, 2003- 2007 (from Waterschap Zuiderzeeland, 2008) 88

Monsanto

SUMMARY

WRc has undertaken a review on behalf of Monsanto Europe of glyphosate and AMPA monitoring data for surface water and groundwater from across Europe. This review was to some extent based on an earlier review carried out on behalf of Monsanto Europe (WRc Report CO 4789/3, Horth et al., 2004) but has been extended to include all 27 European Union Member States, as well as Norway and Switzerland. At the same time some data over about 10 years old, have been omitted where more up to date information has become available.

Information has been obtained from professional contacts across Europe (government departments and research organisations), and including some data provided by Monsanto Europe, as well as from web and literature searches, and by querying on line databases.

Much more data have become available since the 2004 review and including some from relatively new EU Member States. Tables 1 and 2 provide an overview of the main data for surface water and groundwater, respectively. The summarised data are not precise but present our best estimate, mainly because of the various forms in which the data were obtained, e.g. some results in terms of samples, others in terms of sites, and other gaps in information.

Data have been obtained for a total of 16 countries (surface water data for 13 and groundwater data for 13, with most countries including both). Data were mainly at national level, but in some cases regional, as from Belgium (two regions), Italy (one region), and Germany (surface water data for several Länder). In two countries (Czech Republic and Slovenia) monitoring has started in 2009 but data are not available as yet; six countries have confirmed that there is no monitoring of glyphosate and AMPA (Bulgaria, Hungary, Latvia, Lithuania, Luxembourg, Romania), whilst we have been unable to obtain any information from the remaining five countries (Cyprus, Estonia, Greece, Poland and Portugal).

Surface water

Glyphosate and AMPA have been frequently detected in surface waters, AMPA usually at higher concentrations and in a larger proportion of samples. Glyphosate has been analysed in about 50 000 samples from about 3 800 sites (1993-2009) and detected in about 30% of samples and 23% above 0.1 µg l-1; AMPA has been analysed in about 34 000 samples from 28 000 sites (1997-2009) and detected in about 50% of samples and 45% above 0.1 µg l-1.

Glyphosate has a high usage rate and has been rated among the most frequently detected herbicides in some countries, notably in the Netherlands. It has been suggested that urban run-off can be a significant source of glyphosate in surface waters (France and the Netherlands). There have been some indications of an upward trend in recent years, e.g. in Belgium – Flanders and the Netherlands (the opposite in NL - Flevoland), but the data may not be adequate to conclude on trends and co-incides with higher numbers of sites and samples analysed.

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Flanders, and a Maximum Tolerable Risk (MTR) standard at 77 µg l-1, and a pesticide authorisation standard of 64 µg l-1 in the Netherlands, whilst some professionals (Belgium – Wallonia and Rheinland-Pfalz (Germany) suggested that an EQS should be set. However, none of these standards have been exceeded on a regular basis. Perhaps more importantly, the Netherlands apply the drinking water standard of 0.1 µg l-1 for pesticides to surface water intakes at waterworks, and LAWA in Germany has set a target value of 0.1 µg l-1 for the same purpose.

Where data allowed interpretation, glyphosate has been linked to application periods (from spring through to autumn) and run-off events and does not seem to persist. The more persistent presence of AMPA in surface waters throughout the year may be mainly derived from aminophosphonate containing complexing agents in detergents and cooling waters, entering surface waters via wastewater treatment effluents, rather than from the degradation of glyphosate. This seems to be a fairly widely accepted view now, with more evidence having become available, and might explain why AMPA is not always found at higher concentrations, as for example in Sweden, where the population density is low.

Groundwater

Glyphosate and AMPA have been increasingly analysed and occasionally detected in groundwater. Glyphosate has been analysed in about 36 000 samples from about 9 000 sites (1993-2009) and detected in 1.3% of samples and 0.7% above 0.1 µg l-1; AMPA has been analysed in about 28 000 samples from 8 000 sites (1993-2008) and detected in 1.7% of samples and 0.9% above 0.1 µg l-1. These seem to occur in shallow water or springwater, which is often included in groundwater surveys, sometimes associated with contamination incidents (where the information is available), and even unsuitable sampling sites and analytical techniques (investigations in France and Germany).

To date, there seems to be no evidence of any persistent and confirmed groundwater contamination with glyphosate or AMPA, although some findings may warrant further investigation. Reports from some countries stated that groundwater contamination with glyphosate and AMPA was not of concern, e.g. Belgium – Wallonia, Finland and Norway, although the latter referred to potential contamination of shallow groundwater near agricultural fields and farm wells. There is some concern over glyphosate migration to aquifers where the soil cover is thin (Austria) or through certain types of soil (Denmark) and perhaps slower degradation rates in cold climates (Scandinavian countries).

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Table 1 Summary of glyphosate and AMPA data in surface water in Europe

Country / Date No. sites No. Detected (samples) Samples Max. LoQ Substance samples ≥ 0.1 µg l-1 Conc. (LoD) No. % No. % µg l-1 µg l-1 Austria AMPA 2001-02 ? 345 ≥90 ≥26 90 26 3.4 ? Belgium Glyphosate 2006 105 ≥ 1260 83 (s) 79 (s) ? ? <10 ? (Flanders) ≤ 2520 Glyphosate 2001 -06 26 531 ≥ 429 ≥ 81 429 81 1.3 ≤ 0.1 (Wallonia) AMPA 2006 105 ≥ 1260 97 (s) 92 (s) ? ? <10 ? (Flanders) ≤ 2520 Finland Glyphosate 2002-09 3 26 3 11.5 2 7.7 0.46 0.1 AMPA 2002-09 3 26 3 11.5 1 3.8 0.22 0.05 France Glyphosate 97-06 2493 39166 12680 32 10495 27 50 0.05-0.2 AMPA 98-06 2217 28963 15983 55 14583 50 48.9 0.05-0.1 Germany (Baden-Württemberg, Rheinland-Pfalz, Thüringen & River Rhine combined) Glyphosate 1997-08 104 1176 264 22 96 8 4.7 0.02-1.5 AMPA 1997-08 65 660 449 68 392 59 3.6 0.05-0.5 Ireland Glyphosate 2007-09 256 1700 98 5.8 ≥1 ≥ 0.06 1.8 (0.08) Italy (Lombardia Region) Glyphosate 2005-07 150 714 142 20 13 1.8 11.0 (0.1) Norway Glyphosate 97-06 11 80 74 92.5 ≤ 57 ≤ 71 0.93 (0.01) AMPA 97-06 11 80 74 92.5 ≤ 48 ≤ 60 0.54 (0.01) Slovak Republic Glyphosate 2006-08 40 330 105 31.8 49 14.8 3.6 (0.05) Spain * Glyphosate 2006-08 115 748 96 7.4 80 11 15.3 0.003-0.1 Sweden Gly 2000-08 ≥ 21 881 218 24.7 ≥8 ≥0.9 13.0 <0.1 AMPA 2000-08 ≥ 21 868 118 13.6 ≥7 ≥0.8 4.0 <0.1 The Netherlands Glyphosate 2006 300 1384 215 (s) 72 (s) 109 (s) 36 (s) >1.0 <0.1 AMPA 2006 305 1410 305 (s) 100 (s) ≥ 50 (s) ≥16 (s) >8.0 ? UK Glyphosate 93-07 ≥92 2809 297 10.6 297 10.6 8.8 0.1

Total Glyphosate 93-09 ≥ 3716 ≥ 50805 ≥ 14704 ~29 ≥ 11700 ~23 50 0.003-0.2 AMPA 97-09 ≥ 2728 ≥ 33612 ≥ 17119 ~50 ≥ 15172 ~45 48.9 0.05-0.5 Notes: LoQ = limit of quantification (LoD = limit of detection) ? no information (s) sites (number of samples not known) - not relevant * data from sites with known quality problems

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Table 2 Summary of glyphosate and AMPA data in groundwater in Europe

Country / Date No. No. Detected (samples) Samples ≥ 0.1 µg l-1 Max. LoQ Substance sites samples Conc. (LoD) No. % No. % µg l-1 µg l-1 Austria Glyphosate 2004 ~950 3633 7 0.19 2 0.06 >0.1 <0.1 AMPA 2004 ~950 3636 44 1.2 11 0.3 0.75 <0.1 Belgium (Flanders & Wallonia) Glyphosate 2000-06 854 ≥ 950 3 s 0.4 (s) 1 (s) 0.1 (s) ≤ 0.5 0.01 AMPA 2000-06 854 ≥ 950 50 s 5.9 (s) 12 (s) 1.4 (s) ≥ 0.5 0.01 Denmark Glyphosate 93-07 1791 7818 79 1.0 8 0.1 8.7 (<0.1) AMPA 93-07 1804 7816 57 0.7 11 0.1 13 (<0.1) Finland Glyphosate 2002-08 80 80 0 - 0 - - 0.1 AMPA 2002-08 80 80 0 - 0 - - 0.05 France Glyphosate 99-06 3800 17694 344 1.9 241 1.4 24 0.05-0.2 AMPA 99-06 2828 11506 267 2.3 184 1.6 19 0.05-0.1 Germany Glyphosate 2007 196 ≥ 196 7 (s) 3.6 (s) 0 - ≤ 0.1 <0.1 AMPA 2007 326 ≥ 326 10 (s) 3.1 (s) 5 1.5 ≥ 1 Italy (Lombardia Region) Glyphosate 2005-07 183 404 5 1.2 5 1.2 1.2 (0.1) Malta Glyphosate 2009 18 ≥ 18 0 - 0 - - (0.01) Norway Glyphosate 99-00 7 8 0 - 0 - - (0.01) AMPA 99-00 7 8 1 12.5 0 - 0.02 (0.01) Sweden Glyphosate 2000-08 ≥ 21 3063 16 0.52 ≥ 3 ≤ 6 ≥ 0.09 ≤ 0.19 1.7 (<0.1) AMPA 2000-08 ≥ 21 3009 18 0.60 ≥ 2 ≥ 0.07 0.68 (<0.1) Switzerland Glyphosate 2005-06 117 ≥ 234 4 (s) 3.4 3 (s) 2.6 (s) 0.21 (0.05) AMPA 2005-06 117 ≥ 232 ≥ 10 ≤ 17 (s) ≥ 9 ≤ 14 (s) ≥ 6 ≤ 11 (s) ≥ 5 ≤ 9 (s) 0.46 (0.05) The Netherlands Glyphosate 2003-06 <691 691 4 0.58 4 0.58 4.7 (<0.1) AMPA 2003-06 <691 691 21 3.0 21 3.0 5.1 (<0.1) UK Glyphosate 95-07 ≥ 217 1509 13 0.9 ≤ 3 ≤ 0.2 0.47 (0.014-0.4)

Total Glyphosate 93-09 ≥ 8925 ≥ 36298 ≥ 482 ~1.3 ≥ 270 ~0.7 24 0.01-0.4 AMPA 93-08 ≥ 7678 ≥ 28254 ≥ 478 ~1.7 ≥ 252 ~0.9 19 0.01-0.1 Notes: LoQ = limit of quantification (LoD = limit of detection) (s) sites (number of samples not known) - not relevant

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1. INTRODUCTION

WRc has been requested to carry out an update of an earlier survey (WRc Report CO 4789/3, Horth et al., 2004) of glyphosate occurrence in groundwaters and surface waters in Europe, including an investigation of where analyses have been carried out, an attempt to obtain any available data, and assessment and reporting of the data. The work has been requested by Monsanto Europe.

The survey was undertaken of glyphosate monitoring programmes and occurrence data across Europe (29 Member States of the European Union, as well as Norway and Switzerland). This study is based on an earlier review of the 15 Member States, Norway and Switzerland (Horth et al., 2004) which has been updated to include the new Member States, as well as any additional more recent data for the countries reviewed previously.

The herbicide glyphosate has been increasingly used in recent years, often to replace other herbicides, which have been banned or restricted due to their occurrence in water sources. Glyphosate is degraded by soil micro-organisms (half-life in soil usually less than 60 days) and strongly absorbed to soil and, therefore, considered to be unlikely to cause long-term groundwater contamination. In contrast to many other pesticides, glyphosate is highly water soluble and polar. Consequently it is more difficult to analyse glyphosate in water, particularly at the low concentrations of interest in the context of the EU limit for pesticides in drinking water. The first European Drinking Water Directive 80/778/EEC (1980) and the revised Council Directive 98/83/EC (1998) both prescribe maximum admissible concentrations (MAC) of 0.1 µg l-1 for individual pesticides, and 0.5 µg l-1 for total pesticides. However, the analytical techniques have been improving and more and more data are becoming available.

In addition to glyphosate, data for its main degradation product, AMPA (aminomethyl phosphonic acid), have also been included where available. It is worth noting that the revised Drinking Water Directive (98/83/EC) includes ‘relevant’ metabolites of pesticides in the pesticides parameter, although the precise interpretation of this phrase is far from clear at present and will, no doubt, be interpreted differently in different EU Member States. The Dutch authorities have classified AMPA as non-relevant (http://www.ctb-wageningen.nl/ in the pesticide database (select all pesticides) under Roundup Dry registration number 11229N – prolongation of authorisation of 15/03/2002). It is also worth noting that more evidence has been produced in recent years to demonstrate that AMPA inputs into waters is not only derived from the degradation of glyphosate, but also from aminophosphonates used in detergents and cooling waters, with the main inputs being through wastewater treatment effluents and cooling water discharges.

Contacts at national or regional authorities and research institutes in each of the countries were approached for data obtained through relevant research projects and/or national or regional monitoring programmes. The main contacts are listed in Appendix A. In some cases, contacts did not seem to have comprehensive monitoring programmes or were unable to provide information.

In addition, thorough internal (WRc) and external (e.g. British library) literature searches were performed for academic papers/journals and reports containing relevant data, as were web searches, and in some cases on line databases were queried.

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A critical assessment of the data is provided, where possible, from the available information, including details of:

 Type of sample (focusing on surface water and groundwater);

 Number and type of sampling sites;

 Number of samples analysed, sampling frequency;

 Number of positive findings (numerical value where possible), negative findings (with indication of limit of detection, if available);

 Any indications concerning correlation with pesticide application, accidental spillage, or other explanations for positive findings;

 Whether data have been acquired under an analytical quality control (AQC) programme;

 Whether data are part of a national or regional or other programme of analysis; and

 An indication of the method of analysis (e.g. gas chromatography – mass spectrometry (GC-MS), high performance liquid chromatography (HPLC), non-specific multi-residue or screening techniques).

It is worth noting that some laboratories make a distinction between limit of detection (LoD - usually the method limit of detection established by analysing standards) and the limit of determination or limit of quantification (LoDtm or LoQ), where the sample matrix is taken into consideration and below which reliable quantification is not possible, although the substance may be detected. The latter is usually somewhat higher and gives a better indication of the true limit, particularly in surface water samples where there is normally significant ‘background noise’ in analytical determinations. However, the difference between the two limits may be insignificant, particularly in groundwater analyses. Most studies do not distinguish between these two limits, and it is often not clear which limit is reported. However, frequently the LoD as quoted does take into account the sample matrix and represents what others may call the LoDtm/LoQ. In general, we have quoted the given limits as limits of detection (LoD), whereas limits of determination/ quantification (LoDtm / LoQ) are presented only where specific reference has been made to this limit in reported studies.

In monitoring programmes, a concentration value of 0.1 µg l-1 is often used as an orientation value for pesticide contamination of waters, although such low levels do not usually reflect concentrations of concern in terms of ecological or human toxicity. For example, Environmental Quality Standards or Objectives (EQS, EQO) in surface waters are usually considerably higher than this value.

The reason for applying this low value is the use of the waters as sources for drinking water supplies. Within the European Community a limit of 0.1 µg l-1 applies in drinking water for individual pesticides (except for a few specified substances with lower limits). In addition, a limit of 0.5 µg l-1 applies for the sum of pesticides (EU Drinking Water Directive 1998 - 98/83/EC and the previous 1980 Directive - 80/788/EC). These limits are not based on toxicological considerations, but compliance is a legal requirement.

Keeping pesticide concentrations below the above standard is considered particularly important in the case of groundwater, which is often supplied to consumers after minimal

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treatment. In contrast, more extensive treatment is usually required for surface waters, sometimes including advanced treatment techniques (e.g. activated carbon adsorption, advanced oxidation techniques), which may result in the removal of pesticides, along with other raw water contaminants. However, it is sometimes necessary to install additional treatment processes, specifically to remove pesticides, in order to achieve the prescribed drinking water limits.

It is also worth noting that pesticide concentrations are much more variable in surface waters, compared with groundwater, which tends to exhibit relatively constant levels over a considerable period of time (often many years) except where aquifers are highly fractured and allow rapid surface water inflow through fissures. In surface waters, short-term peaks are likely to occur, for example due to run-off after application of pesticides followed by rainfall, thereby producing seasonal patterns linked to pesticide application. Hence, a higher sampling frequency is required to provide a conclusive picture of pesticide concentrations in river waters. However, groundwater usually requires a much longer period for recovery, once affected.

Although every effort has been made to include all available data, it is inevitable that we may have missed some and new data may become available in future. We recommend, therefore, that the report should be updated, as new data become available.

In some cases, where the reason for a result (such as an isolated positive finding or an unusually high concentration of a pesticide) is not clear in terms of its significance to water contamination, it may be worth trying to obtain some further follow-up information. However, such detailed investigations were outside the scope of this study.

1.1 Acknowledgements

Much of the data presented in this report is unpublished, or only available in national reports, which may not be available in the open literature. Much of this information has been provided by the researchers involved.

The main contacts and organisations approached to obtain information are listed in Appendix A, though not all of these have responded to requests for information. The helpful assistance of those who provided information is gratefully acknowledged.

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2. AUSTRIA

2.1 Introduction

Austria has extensive groundwater and surface water monitoring programmes and the results are published periodically. The monitoring programmes are lead by the Federal Ministry of Environment (Bundesministerium für Land- und Forstwirtschaft, Umwelt und Wasserwirtschaft (BMLFUW), with co-operation from the Federal States. The programmes are constantly reviewed, in terms of sites and substances monitored.

The analyses are sub-contracted to specialist laboratories, which are appointed and inspected by the BMLFU; to ensure reliability of the results, the laboratories have to demonstrate analytical quality control (AQC) procedures, must be accredited for the analytical methods used, and take part in on-going national ring tests.

Glyphosate and AMPA were first included in the groundwater monitoring programme in 2004, following special investigations starting in 2001. Glyphosate and AMPA are not so far part of the surface water monitoring programme, although a special investigation was started in 2004 (UBA, 2006).

2.2 Surface Water

The most recent available water quality report from Austria (UBA, 2006), covering the period 1 January 2003 to 31 December 2004, does not include glyphosate, neither in the routine surface water monitoring programme (289 monitoring stations, monthly sampling), nor in a special survey carried out during 2003-04 in connection with the implementation of the Water Framework Directive (WFD) (2000/60/EC), where additional substances of potential concern were monitored at 32 monitoring stations.

However, due to high glyphosate usage, a special investigation of glyphosate and AMPA was carried out in 2004 at surface water monitoring stations (it is not clear whether all stations were included or what the sampling frequency was). Where the substances were detected, the survey was continued in 2005 (UBA, 2006).

It was reported that glyphosate was detected predominantly in the Federal State of Niederösterreich (highest frequency and concentrations, with a maximum concentration of 3.6 µg l-1). Values above 0.1 µg l-1 were observed infrequently in the other Federal States (Burgenland, Kärnten, Oberösterreich, Steiermark, Vorarlberg and Vienna).

AMPA was generally found more frequently and at higher concentrations than glyphosate, also predominantly in Niederösterreich, where the maximum concentration was at 3.6 µg l-1, as for glyphosate.

No further details, such as number of sites and samples analysed and number of detections or concentrations found, were provided. The report indicated that AMPA could have been derived from other sources, such as the degradation of aminopolyphosphonates used in detergents and cooling waters, and entering surface waters via waste water discharges (Fürhacker et al., 2005, quoted in UBA, 2006).

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A poster presentation (Pfeffer et al., undated) reported a survey of surface waters in 2001 - 2002, showing AMPA concentrations >0.1 µg l-1 in 90 of 345 river water samples, with a maximum concentration of 3.39 µg l-1 and average concentrations of 0.37 µg l-1. It also reported AMPA concentrations between 9 µg l-1 and 27 µg l-1 in influents of wastewater treatment plants (WWTPs); AMPA was partially removed or even enhanced during waste water treatment, and concentrations were considerably higher in the river downstream of WWTPs, compared with upstream. The paper also concluded that photo-oxidation of N- containing phosphonates produced AMPA and that the former were the main source of AMPA in surface waters.

Earlier reports did not include glyphosate or AMPA, although a significant number of pesticides were monitored in surface waters in Austria in the years 1992 to 2002 (BAW-BMLF, 1999; BMLF, 1997; 1999; 2001; 2002; UBA 2004).

2.3 Groundwater

Austria’s drinking water supplies are derived almost entirely (99%) from groundwater sources. For this reason it is considered very important to protect the quality of groundwater and there is an extensive national groundwater quality monitoring network in Austria. The network covers, in the main, the important Karst and other aquifers. It was designed to concentrate on the large valley and basin topographies, which include important groundwater resources, subject to intensive and varied forms of economic exploitation. The network has been used as the basis for national data collection since 1991 when the network comprised 776 wells; by 1996 this had increased to 1 719 wells. The programme is continuously reviewed and revised if considered necessary, in terms of sites and substances monitored.

The most recent report (UBA, 2006) covers the period 1 January 2003 to 31 January 2004, when a wide range of pesticides and metabolites were monitored at a total of 1 980 monitoring stations (1 728 pore water monitoring stations, and 252 springs from Karst / fractured aquifers); all were normally sampled four times per year. The report also summarises changes in the monitoring programme.

Following concerns over high glyphosate usage and possible vulnerability of groundwater, particularly in areas of thin soil cover, glyphosate and AMPA were added to the routine monitoring programme for the first time in 2004, though only at about half the monitoring stations (950), selected on the basis of agricultural activity, and monitored in most cases four times per year.

The results are presented in Table 2.1. Glyphosate was detected in 7 samples, 2 of these above 0.1 µg l-1 (at two different sites in the Steiermark, one in the Sauggautal and one in the Lower Murtal). AMPA was detected somewhat more frequently and at higher concentrations, with a maximum concentration of 0.75 µg l-1 (Burgenland); other detections were observed in the Federal States of Niederösterreich, Salzburg, Steiermark and Vorarlberg. The detection limits (LoD) for glyphosate and AMPA were not provided, but appeared to be <0.1 µg l-1, on the basis of the results, as presented.

These seem to be isolated cases, for example the glyphosate detections >0.1 µg l-1 were observed only once at each of two sites, although most sites were sampled quarterly. There is no information about the type of groundwater, although the results, as presented, related to ‘pore’ groundwater only, not the springs from fractured aquifers.

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Table 2.1 Glyphosate and AMPA in groundwater in Austria, 2004 (source: UBA, 2006)

Number of > LoD > 0.1 µg l-1 Substance samples Number % Number % analysed Glyphosate 3 633 7 0.19 2 0.06 AMPA 3 636 44 1.21 11 0.3 LoD = Limit of detection

There is a mention that traces of AMPA were detected in two springwater sources (in Vorarlberg), but it was considered unclear at the time whether these findings were related to glyphosate or to aminophosphonates from detergents (Fürhacker et al., 2005, quoted in UBA, 2006).

Whilst earlier monitoring programmes included a significant number of pesticides, glyphosate and AMPA were not monitored in the years 1992 to 2003 (BMLF, 1997; 1999; 2001; 2002; UBA 2004 and 2006).

2.4 Summary

Glyphosate and AMPA have so far not been part of the surface water monitoring programme, although a special investigation was started in 2004, where glyphosate was detected mainly in one Federal State (Niederösterreich) and infrequently in the others. AMPA was found frequently (26% of samples) in another investigation of surface waters; the authors also found relatively high levels of AMPA in wastewater treatment influents and it was sometimes enhanced during treatment. The authors concluded that N-containing phosphonates were the main source of AMPA in surface waters.

Glyphosate and AMPA were first included in the groundwater monitoring programme in 2004, following special investigations starting in 2001, and concerns over potential groundwater contamination in agricultural areas, where glyphosate usage was extensive, and where soil cover above aquifers is thin. Glyphosate was detected in isolated cases (7 samples or 0.2%, with 2 samples or 0.06% from 2 different sites above 0.1 µg l-1). AMPA was detected somewhat more frequently and at higher concentrations, with a maximum concentration of 0.75 µg l-1. There is no information about the type of groundwater, although the results, as presented, related to ‘pore’ groundwater only, not the springs from fractured aquifers. Traces of AMPA were also found in two springwater samples and it was considered unclear at the time whether these findings were related to glyphosate or to aminophosphonates from detergents.

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3. BELGIUM

3.1 Introduction

Data were available for the Flanders and Wallonia Regions, but not for Brussels. Glyphosate and AMPA were monitored in surface waters and groundwater in Flanders; in Wallonia glyphosate, but not AMPA, was monitored in surface water, whereas both substances were monitored in groundwater. The available results are presented below.

3.2 Surface Water

3.2.1 Flanders

The Flemish Environment Agency (MIRA, 2007) has been monitoring the presence of pesticides in surface water for over ten years; glyphosate and AMPA have been monitored since 2000. In 2006, about 100 substances, including glyphosate and its by-product AMPA, were monitored once or twice a month at 105 sampling points. Out of the 100 substances, seven pesticides and two by-products were found in 30-50% of the samples. These included MCPA, terbutylazine, diuron, chloridazon, diazinon, bentazone, endosulfan-sulfate, and carbendazim. Five other pesticides and two by-products were found in more than 50% of samples, including glyphosate (79%), simazine, isoproturon, metalachlor, atrazine, AMPA (92%) and 2-hydroxy-atrazine. As in 2005, glyphosate and AMPA were frequently found at all the sampling points, but always at concentrations below the PNEC (Proposed No-Effect Concentration) of 10 µg l-1 and the MAC (Maximum Admissible Concentration) of 100 µg l-1 values for glyphosate. No target EQS has been set in Flanders.

The results for glyphosate and AMPA for the years 2000-2006 are shown in Table 3.1. It shows a high percentage detection for both substances and consistently higher concentrations of AMPA, compared with glyphosate (3 year averages up to about 1 µg l-1 for glyphosate, and up to 3 µg l-1 for AMPA). The three year averages seem to indicate a gradual increase in the concentrations of glyphosate and AMPA during the monitoring period 2000- 2005.

Table 3.1 Glyphosate and AMPA in surface waters in Flanders, 2000-2006 (source: MIRA, 2007)

Description 2000 2001 2002 2003 2004 2005 2006 Percentage of sites detected (at least once) Glyphosate 79 74 81 84 91 89 79 AMPA 95 87 90 86 92 88 92 Average concentration, as calculated for the preceding 3 years in each case (µg l-1) Glyphosate 0.37 0.63 0.76 0.88 1.01 0.92 - AMPA 1.39 1.71 2.48 2.96 3.37 2.99 - Note: - data not provided

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3.2.2 Wallonia

The latest available report from the regional environment ministry on surface water quality for 2004 (DGRNE, 2007) lists atrazine, lindane and glyphosate as the top three pesticides exceeding 0.1 µg l-1 in surface water. Glyphosate concentrations (see Figure 3.1, EAU 4-7 extracted from DGRNE, 2007) exceeded 0.1 µg l-1 at more than 80% of monitoring sites. In addition, there seemed to be an increase in the annual highest concentrations (90 percentile) since 2003 in most rivers for which previous data were available.

Figure 3.1 Glyphosate concentrations in surface waters of the Walloon Region, 2001-2005 (source: DGRNE, 2007)

More detailed glyphosate data for 2001 to 2006 were received via Monsanto (M-A. Reding / Christophe Gustin, personal communication, 2009, as received from Denis Godeaux, Direction Eaux de Surface, Wallonie in 2007) for four river basin districts (RBD), i.e. Escaut, Meuse, Oise and Rhine. However, the Oise did not include any glyphosate monitoring data. The data received include the river sampled, the location, the number sampled and the 90th percentile result (P90) and is summarised in Tables 3.2 – 3.4. It is understood that AMPA will also be included from 2007.

In the absence of a Quality Objective (QO) value, the drinking water limit of 0.1 g l-1 was used to judge glyphosate. A note attached to the data suggested that a QO should be set, taking into account a PNEC (Proposed No Effect Concentration – value not given) in water. The data also included a Risk Characterization Ratio (RCR, calculated as the ratio PEC/PNEC). If this ratio were greater than one, the substance would be considered an ecological risk. For glyphosate there were no occasions where the RCR was greater than one.

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For the Escaut RBD there were 9 different rivers sampled from 11 locations, with a total of 119 samples (see Table 3.2). The highest 90th percentile result was 3.6 g l-1 with the majority being > 0.1 g l-1.

Table 3.2 Glyphosate results for Escaut RBD, 2001-2006 (source: Denis Godeaux, Direction Eaux de Surface, Wallonie)

Year River Location No. samples P90 (g l-1) RCR 2001 Dendre Ath 2 0.211 0.004 Escaut Antoing 2 0.274 0.005 Escaut Hérinnes 2 0.124 0.002 Espierres Estaimpuis 2 <0.1 - Haine Hensies 2 <0.1 - La Grande Espierres Spiere-Helkijn 2 0.262 0.004 Rhosnes Orroir 2 0.598 0.010 2002 Dendre Ath 2 0.530 0.009 Escaut Antoing 2 0.567 0.009 Escaut Hérinnes 2 0.229 0.004 Espierres Estaimpuis 2 1.199 0.020 Haine Hensies 2 1.335 0.022 La Grande Espierres Spiere-Helkijn 2 0.167 0.003 Rhosnes Orroir 2 0.881 0.015 2003 Dendre Deux-Acren 4 0.851 0.014 Dyle Sint-Agatha-Rode 3 1.264 0.021 Escaut Antoing 4 0.253 0.004 Escaut Hérinnes 4 0.273 0.005 Haine Hensies 4 2.099 0.035 Lys Warneton 3 0.415 0.007 Senne Quenast 6 0.360 0.006 2004 Dendre Deux-Acren 13 2.307 0.038 Dyle Sint-Agatha-Rode 13 0.642 0.011 Escaut Antoing 13 0.782 0.013 Escaut Hérinnes 13 0.792 0.013 Haine Hensies 13 1.224 0.020 Lys Warneton 5 1.003 0.017 Senne Quenast 13 0.830 0.014 2005 Escaut Antoing 13 3.623 0.060 Escaut Hérinnes 13 2.873 0.048 2006 Escaut Antoing 13 1.772 0.030 Escaut Hérinnes 13 1.063 0.018 2001 - 2006 9 rivers 11 locations 191 samples Max 3.6 Max 0.060

Key Exceedance of the drinking water standard (0.1 g l-1) in the absence of a QO value

Risk Characterization Ratio (PEC/PNEC) > 1 = ecological risk

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For the Meuse RBD there were 9 different rivers sampled from 13 locations, with a total of 319 samples (see Table 3.3). The highest 90th percentile result was 1.328 g l-1, with most above 0.1 g l-1, except in 2001.

Table 3.3 Glyphosate results for the Meuse RBD, 2001-2006 (source: Denis Godeaux, Direction Eaux de Surface, Wallonie)

Year River Location No. samples P90 (g l-1) RCR 2001 Mehaigne Moha 2 <0.1 - Meuse Dave 2 <0.1 - Meuse Andenne 2 <0.1 - Meuse Visé 2 <0.1 - Ourthe Chênée 2 <0.1 - Sambre Solre-sur-Sambre 2 <0.1 - Sambre Roselies 2 <0.1 - Sambre Namur 2 <0.1 - Semois Bohan 2 <0.1 - Ton Lamorteau 2 <0.1 - 2002 Mehaigne Moha 2 0.187 0.003 Meuse Dave 2 <0.1 - Meuse Andenne 2 0.142 0.002 Meuse Visé 2 0.174 0.003 Ourthe Chênée 2 <0.1 - Sambre Solre-sur-Sambre 2 0.279 0.005 Sambre Roselies 2 0.266 0.004 Sambre Namur 2 0.291 0.005 Semois Bohan 2 <0.1 - 2003 Amblève Comblain-au-Pont 3 <0.1 - Lesse Dinant 3 0.206 0.003 Meuse Dave 4 <0.1 - Meuse Andenne 4 <0.1 - Meuse Visé 4 0.103 0.002 Ourthe Chênée 4 <0.1 - Sambre Solre-sur-Sambre 4 0.181 0.003 Sambre Roselies 3 0.165 0.003 Sambre Namur 3 0.218 0.004 Semois Bohan 3 0.142 0.002 Ton Lamorteau 3 <0.1 - Vesdre Vaux-sous-Chèvremont 3 <0.1 - 2004 Amblève Comblain-au-Pont 5 0.081 0.001 Lesse Dinant 6 0.154 0.003 Meuse Dave 13 0.142 0.002 Meuse Andenne 14 0.123 0.002 Meuse Visé 14 0.215 0.004 Ourthe Chênée 14 0.131 0.002 Sambre Solre-sur-Sambre 13 0.590 0.010 Sambre Namur 13 0.303 0.005 Semois Bohan 5 <0.05 - Ton Lamorteau 5 0.082 0.001 Vesdre Vaux-sous-Chèvremont 6 0.494 0.008

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Year River Location No. samples P90 (g l-1) RCR 2005 Meuse Dave 13 0.158 0.003 Meuse Andenne 13 0.356 0.006 Meuse Visé 13 0.93 0.016 Ourthe Chênée 13 0.273 0.005 Sambre Namur 13 1.328 0.022 2006 Meuse Dave 14 0.134 0.002 Meuse Andenne 13 0.093 0.002 Meuse Visé 13 0.259 0.004 Ourthe Chênée 13 0.057 0.001 Sambre Namur 14 0.304 0.005 2001 - 2006 9 rivers 13 locations 319 Max 1.328 Max 0.022

Key Exceedance of the drinking water standard (0.1 g l-1) in the absence of a QO value

Risk Characterization Ratio (PEC/PNEC) > 1 = ecological risk

For the Rhine RBD (Moselle) there were two rivers, each sampled from one location, with a total of 21 samples (see Table 3.4) in 2003 and 2004 only. The highest 90th percentile result was 0.225 g l-1, with most above 0.1 g l-1.

Table 3.4 Glyphosate results for the Rhine (Moselle) RBD, 2003-2004 (source: Denis Godeaux, Direction Eaux de Surface, Wallonie)

Year River Location No. samples P90 (g l-1) RCR 2003 Our Reuland 5 <0.1 - Sûre Tintange 5 0.116 0.002 2004 Our Reuland 5 0.063 0.001 Sûre Tintange 6 0.225 0.004 2003-2004 2 rivers 2 locations 21 Max 0.225 Max 0.004

Key Exceedance of the drinking water standard (0.1 g l-1) in the absence of a QO value

Risk Characterization Ratio (PEC/PNEC) > 1 = ecological risk

3.3 Groundwater

3.3.1 Flanders

The groundwater monitoring network in the Flanders region includes glyphosate and AMPA among the pesticides which are normally monitored twice a year (MIRA, 2007). In total, 404 wells were sampled for pesticides analyses (about 500 sampling points, including the phreatic surface and different groundwater levels in some wells), encompassing the various hydrogeologically homogeneous zones in Flanders. The results for the spring 2006 monitoring

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campaign are summarised in Table 3.5. Data were given for percentage detection, but the numbers of wells have been calculated from these. Glyphosate was detected in three wells (0.5%) in total, with one well (0.2%) above 0.1 µg l-1 (none were above 0.5 µg l-1). AMPA was found at a higher proportion of wells (37 in total) and at higher concentrations, with 11 wells (2.7%) above 0.1 µg l-1 and one well (0.2%) above 0.5 µg l-1. Whether these were at shallow wells would need to be clarified; there were sampling points in wells mainly at the phreatic surface and in some of the wells at different groundwater levels.

Table 3.5 Percentage detection of AMPA and glyphosate at groundwater monitoring sites in Flanders, spring 2006 (source: MIRA, 2007 and details from www.milieurapport.be)

Concentration range (µg l-1) Number (%) of wells AMPA Glyphosate 0.01 - ≤ 0.1 25 (6.2) 2 (0.5) 0.1 - ≤ 0.5 11 (2.7) 1 (0.2) ≥ 0.5 1 (0.2) 0

Note: Data presented as percentage only, but numbers calculated from these.

3.3.2 Wallonia

About 65 pesticides and metabolites, including glyphosate and AMPA, have been monitored in groundwater between 2000 and 2006 at about 450 abstraction sites. Groundwater quality data (see Figure 3.2, EAU 4-12 extracted from DGRNE, 2007) showed that AMPA was found at 3% of the 450 most important abstraction sites (~13 sites) between January 2000 and March 2006, at concentrations in the range 0.025-0.05 µg l-1. There was no detection of glyphosate in groundwater during that period.

Glyphosate and AMPA are not among the substances of concern with respect to groundwater contamination, which is assessed in Wallonia, using the French evaluation system (Système d’évalation de la qualité des eaux souterraines - SEQ-ESO) and focusing on the eight most relevant pesticides (atrazine, desethylatrazine, simazine, diuron, isoproturon, bentazone, bromacyl, chloridazon).

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Figure 3.2 Pesticides and metabolites monitored in groundwater of the Walloon Region (in percentage of sites affected), 01/01/2000 to 01/03/2006 (from DGRNE, 2007)

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3.4 Summary

Data were available for the Flanders and Wallonia Regions, but not Brussels. Both substances were monitored in groundwater; in surface water both were monitored in Flanders, but only glyphosate in Wallonia. However it is understood that, from 2007, results from Wallonia (not included in this study) will also include AMPA data.

Glyphosate and AMPA, where measured/reported, have been detected frequently in surface waters, i.e. glyphosate and AMPA in Flanders, and glyphosate only in Wallonia, with the highest concentrations of glyphosate and AMPA in Flanders at less than 10 µg l-1 (no further details available) and glyphosate in Wallonia at 1.33 µg l-1. Average glyphosate and AMPA concentrations, as calculated over 3 years, suggested an increase over the period 2000-2005 in Flanders.

AMPA, but not glyphosate, has been detected at a small number of sites (3% or 13 sites) and low concentrations (≤0.05 µg l-1) in groundwater in Wallonia in the period 2001-2006, whereas glyphosate and to a somewhat greater extent, AMPA, have been detected at a small number of sites in Flanders (glyphosate at 3 sites or 0.7%, with one site (0.2%) >0.1 µg l-1; AMPA at 37 sites (9%) with 12 sites (3%) >0.1 µg l-1) in 2006.

Glyphosate and AMPA are not among the substances of concern with respect to groundwater contamination in Wallonia. For Flanders, it may be worth trying to obtain more details, concerning the depth of the groundwater and number of samples with detections at each of the three sites.

In Wallonia, glyphosate concentrations in surface waters were well below the level which would indicate an ecological risk but it was suggested that a quality objective should be set for glyphosate in surface water, taking into account the PNEC (Proposed No-Effect Concentration).

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4. BULGARIA

4.1 Summary

A pesticide monitoring programme for groundwater and surface water was started in 2008 in Bulgaria. However, it does not include glyphosate or AMPA as these pesticides are not on the list of priority substances according to the WFD (Misho Mollov, National Focal Point for Water (EIONET) at the Bulgarian Executive Environment Agency (BEEA), personal communication, 2009).

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5. CYPRUS

5.1 Summary

We have been unable to obtain any information from Cyprus.

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6. CZECH REPUBLIC

6.1 Summary

Glyphosate and AMPA have been included in pesticide screening of surface water this year (2009). Results will be available at the beginning of next year (2010) (Vít Kodes, Czech Hydrometeorological Institute, Department of Water Quality, personal communication, 2009). Glyphosate and AMPA are not monitored in groundwater (Vít Kodes, Czech Hydrometeorological Institute, Department of Water Quality, personal communication, 2009).

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7. DENMARK

7.1 Introduction

Almost all water supplies in Denmark are derived from groundwater sources; thus the emphasis in Denmark is on groundwater quality monitoring, including pesticide surveys. Glyphosate and AMPA are also monitored in more recently established surface water monitoring programmes, but no detailed data appear to be available.

Glyphosate has been sold in Denmark since 1975, and the amount is still increasing. At 328 tonnes in 2008, glyphosate is now the most widely used herbicide in Denmark, representing 60% of the total amount of herbicides sold. It is used predominantly for agricultural and, to a much lesser extent, non-agricultural purposes (Miljøministeriet, 2009).

Earlier results up to 1999 and small investigations are discussed in the previous WRc review (Horth et al., 2004). Further details concerning investigations into glyphosate detections in groundwater are presented in the WRc Drinking Water Report (Horth and Gendebien, 2008).

7.2 Surface Water

A national monitoring programme, which includes surface water monitoring, has been in place since 1997 (Danish Aquatic Monitoring and Assessment programme, NOVA). In 2003 this was replaced by NOVANA (National Monitoring and Assessment Programme for the Aquatic and Terrestrial Environments), which covers the period from 2004 to the present.

Pesticide monitoring in surface waters was included for the first time in NOVANA (Svendsen, et al., 2005 and TemaNord, 2007), and Glyphosate and AMPA are included in the NOVANA subprogramme for watercourses, being monitored 12 times a year, with a detection limit of 0.01 g l-1 (Svendsen, et al., 2005). Detailed results do not appear to be available; a presentation by Boutrup (undated) merely mentioned that glyphosate was detected in 46% of sites (or samples or water courses? – it was not indicated) in 2004. We tried to obtain further information, but did not receive a reply.

7.3 Groundwater

An extensive groundwater monitoring programme has been in place since 1989 (GEUS, 2009) and carried out by the Geological Survey of Denmark and Greenland (GEUS – Danmarks og Grønlands Geologiske Undersøgelse) of the Ministry of Environment. In 2003, a major revision of the groundwater monitoring programme was undertaken and the new programme has been incorporated into NOVANA.

The groundwater monitoring programme essentially consists of several parts, namely general groundwater monitoring sites (GRUMO programme), a special survey of agricultural monitoring catchments (LOOP programme) and monitoring at waterworks intakes and by regional authorities, as explained in more detail below (GEUS, 1998-2009).

The so-called GRUMO survey initially comprised a basic set of 8 pesticides and did not include glyphosate. The 8 substances were monitored at all main groundwater survey sites,

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although other pesticides were also monitored at certain sites. The survey has been extended over the years to include other pesticides (e.g. glyphosate in 1993) and the number of monitoring sites has also increased over the years.

The so-called LOOP programme was designed to monitor agricultural watersheds and consists of relatively shallow sampling boreholes (varying from 1.5 to 5 m depth to reach the groundwater table) in the catchments surrounding existing groundwater monitoring boreholes. The number of sites and pesticides monitored are smaller than in the general groundwater monitoring programme.

In addition, water works and county authorities also monitor pesticides at abstraction wells for drinking water supply. Data from a number of other observation boreholes are also included, such as groundwater monitoring stations maintained by public water suppliers. The latter include a recent survey of small wells for private supplies; this is summarised and discussed in the WRc Drinking Water Report (Horth and Gendebien, 2008).

All these results are collated at GEUS on a database, and groundwater quality reports are produced periodically. Only results from accredited laboratories are included (Dr. Walter Brüsch, GEUS, personal communication). In view of the emphasis on AQC and the evaluation of the results at GEUS, we consider the data reliable, despite the absence of details of analytical techniques and the variety of sources of data.

Under the current NOVANA programme, the overall groundwater monitoring programme has been maintained with some modifications; the number of pesticides monitored has been revised and reduced on the basis of earlier findings, the selection of sampling points has altered to some extent, omitting sites not considered relevant in terms of representing overall groundwater quality.

Glyphosate and AMPA are only monitored in the upper levels of aquifers, i.e. at most down to 15 metres below the groundwater level (GEUS, 2009).

Table 7.1 shows glyphosate and AMPA data for the main groundwater survey and the survey of wells for public water supplies from the most recent summary report (GEUS, 2009), where all pesticides data for 1989-2007 have been collated. However, glyphosate and AMPA have only been monitored since 1993 (GEUS, 2003).

In total (general groundwater monitoring network plus controls on wells for public water supplies), glyphosate and AMPA were analysed in over 7 800 samples from about 1 800 sites. Glyphosate was detected in 1% of samples analysed from 3.9% of sites surveyed, with 8 samples (0.1%) or 8 sites (0.45%) at concentrations above 0.1 g l-1. AMPA was detected in 0.7% of samples from 2.4% of sites, with 11 samples (0.14%) or 11 sites (0.6%) at concentrations above 0.1 g l-1.

The data shows (Table 7.1) that whereas glyphosate and AMPA have been detected more than once at some groundwater survey sites, all detections at water supply wells and all findings above 0.1 g l-1 have clearly been obtained once only at any given site.

The report (GEUS, 2009) concludes that glyphosate and AMPA are found increasingly in relatively shallow groundwater (less than 15 m depth) in the GRUMO survey, but also in wells used for abstraction of public water supplies.

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Table 7.1 Glyphosate and AMPA in the main groundwater surveys in Denmark, 1993 – 20071) (source: GEUS, 2009)

Data source / Samples Sampling sites Concentration survey / Anal. Detected ≥ 0.1 g l-1 Anal. Detected ≥ 0.1 g l-1 Average* Median* Max. substance No. No. % No. % No. No. % No. % g l-1 g l-1 g l-1

Groundwater survey – GRUMO Glyphosate 7022 65 0.92 6 0.08 1316 56 4.3 6 0.46 0.048 0.022 0.52 AMPA 7011 49 0.70 8 0.11 1316 36 2.7 8 0.61 0.087 0.026 1.0

Wells for public water supply Glyphosate 796 14 1.8 2 0.25 475 14 2.9 2 0.42 0.65 0.020 8.7 AMPA 805 8 1.0 3 0.37 488 8 1.6 3 0.61 1.70 0.024 13

Total - Groundwater survey and wells for public water supply Glyphosate 7818 79 1.0 8 0.10 1791 70 3.9 8 0.45 0.048-0.65 0.020-0.022 8.7 AMPA 7816 57 0.73 11 0.14 1804 44 2.4 11 0.61 0.087-1.7 0.024-0.026 13 1) Notes: report summarised pesticides data for 1989-2007, but glyphosate and AMPA have only been monitored since 1993 * based on all positive samples

For comparison, Table 7.2 shows the same data from an earlier summary report (GEUS, 2003), where data for 1993-2002 have been collated. In total, glyphosate and AMPA were analysed in almost 3 700 samples from over 1 200 sites. Glyphosate and AMPA were detected in a small proportion of samples, i.e. glyphosate in 0.6% of all samples analysed, from 1.7% of sites surveyed; and AMPA in 0.8% of samples, from 1.9% of sites. AMPA was found at concentrations equal to or above 0.1 g l-1 in five samples from 5 sites, whereas glyphosate was detected in only one sample/site at a concentration of 0.1 g l-1. Overall, this set of data does show lower rates of detections and concentrations observed, compared with the period 1993 – 2007 (Table 7.1), however it should be noted that all data shows very low (<1%) levels of detections above 0.1 g l-1.

Table 7.2 Glyphosate and AMPA in the main groundwater surveys in Denmark, 1993 – 2002 (source: GEUS, 2003)

Groundwater survey – GRUMO Glyphosate 3 331 18 0.5 1 0.03 940 17 1.8 1 0.1 0.03 0.02 0.10 AMPA 3 319 26 0.8 4 0.12 939 21 2.2 4 0.4 0.09 0.02 1.0

Wells for public water supply Glyphosate 351 4 1.1 0 - 274 4 1.5 0 - 0.018 0.017 0.03 AMPA 376 3 0.8 1 0.3 296 3 1.0 1 0.3 0.043 0.017 0.1

Total - Groundwater survey and wells for public water supply Glyphosate 3 682 22 0.6 1 0.03 1 214 21 1.7 1 0.08 0.02-0.03 0.02 0.10 AMPA 3 695 29 0.8 5 0.14 1 235 24 1.9 5 0.40 0.04-0.09 0.02 1.0 Notes: - no data or not relevant * based on all positive samples

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Table 7.3 shows glyphosate and AMPA data for shallow groundwater observation boreholes in agricultural watersheds (LOOP survey) and ‘other observation boreholes’, which includes a recent survey of small private wells, as collated in an earlier report (GEUS, 2003) for 1993- 2002. For comparison, data for ‘other wells and observation boreholes’ from the most recent report (GEUS, 2009) has also been included. These data show higher proportions of positive findings and higher concentrations of glyphosate and AMPA, compared with the main surveys.

Table 7.3 Glyphosate and AMPA in agricultural watersheds (shallow groundwater) and ‘other observation boreholes’ (mainly small private water supplies) in Denmark, 1993 – 2002, and 1993 – 2007 (source: GEUS, 2003 and 2009)

Agricultural watersheds (shallow observation boreholes) – LOOP, 1993 – 2002 (GEUS, 2003) Glyphosate 408 20 4.9 11 2.7 58 9 15.5 7 12.1 0.380 0.130 2.60 AMPA 405 25 6.2 14 3.5 58 11 19.0 6 10.3 0.130 0.075 0.7

Other observation boreholes, 1993 – 2002 (GEUS, 2003) Glyphosate 744 54 7.3 9 1.2 693 42 6.1 8 1.2 0.202 0.028 5.3 AMPA 739 76 10.3 24 3.2 690 54 7.8 21 3.0 0.237 0.042 5.7

Other wells and boreholes, including small private water supplies 1993 – 2007 (from GEUS, 2009) 1) Glyphosate 1905 84 4.4 18 0.94 1284 64 5.0 13 1.0 0.36 0.028 11.3 AMPA 1827 113 6.2 35 1.9 1276 80 6.3 27 2.1 1.11 0.040 69.4 Notes: 1) it is not clear whether this includes the LOOP survey * based on all positive samples

Brüsch and Rosenberg (2008) recently carried out a separate study of glyphosate detections (2001-2002) in small supplies. The authors concluded that all positive findings were related to shallow groundwater, probably due to rapid transfer of surface water run-off from courtyards or nearby fields through horizontal fracture zones or macro pore systems. The report is discussed in more detail in the WRc Drinking Water Report (Horth and Gendebien, 2008).

There is inadequate information about the actual groundwater depth in the reported positive findings, other than the depth being less than 15 metres in all samples analysed since 2004. It would be interesting if these could be investigated further, including the possibility of superficial or accidental contamination.

Work is ongoing in Denmark to establish leaching of glyphosate through soils, e.g. Kjær et al. (2005) and Kjær et al., (undated). The authors found some leaching of glyphosate and AMPA through soil to subsoil depth (1 metre below surface) and concluded that there was a potential risk of contamination of the aquatic environment.

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7.4 Summary

Glyphosate and AMPA are monitored in surface water and groundwater in Denmark, but no detailed results of surface water monitoring seem to be available.

The most recent groundwater monitoring report, which summarises data from 1993 – 2007, suggests that glyphosate and AMPA detections in groundwater are increasing in shallow wells in agricultural areas, but also in wells used for the abstraction of public drinking water supplies. Whereas glyphosate and AMPA have been detected more than once at some groundwater survey sites, all detections at water supply wells and all findings above 0.1 g l-1 have clearly been obtained once only at any given sampling site.

Whilst investigations into earlier detections (2001-2002) have shown that these occurred in shallow groundwater wells only, and appeared to be due to rapid transfer of surface water from nearby surfaces, the recent reported findings relate to groundwater at less than 15 metre depth, with no further details available, and may need further investigation, especially to establish whether they are isolated incidents or occur in repeat analyses at the sites concerned.

Work is ongoing in Denmark to establish leaching of glyphosate through soils.

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8. ESTONIA

8.1 Summary

We have been unable to obtain any information from Estonia.

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9. FINLAND

9.1 Introduction

Historically, pesticide monitoring in Finland was mainly in the form of screening investigations, however a more permanent monitoring campaign is being established to meet the needs of the Water Framework Directive.

Figure 9.1 shows the pesticide sales in Finland between 1976 and 2003, which shows there has been a steady increase of glyphosate sales, with a large rise between 2000 and 2003.

Figure 9.1 Pesticide sales in Finland (source: TemaNord, 2007 via Savela & Hynninen, 2004)

9.2 Surface Water

Recent results (2007-2009) of monitoring of glyphosate and AMPA in Finland were received from the Finnish Environment Institute SKYE (Mira Grönroos, personal communication, 2009). These are shown in Table 9.1. During 2007 and 2008 only one river was sampled (at up to two sites); however, in 2009 sampling was carried out from an additional river (from one site only). From the 26 samples, only three samples exceeded the limit of detection (LoD not provided), with two of these being above the limit of quantification (0.1 g l-1 for glyphosate and 0.05 g l-1 for AMPA). The two sites sampled in 2009 ('Lepsämänjoki 2.6' and 'Skatila vp 9600') will be sampled in 2009 until the end of October.

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Table 9.1 Surface water monitoring in two rivers in Finland, 2007 to 2009 (source: Mira Grönroos, Finnish Environment Institute SKYE, personal communication, 2009)

No. of No. of No. of samples No. > No. > % > Max conc. -1 -1 sites samples detected * LoQ** 0.1 µg l 0.1 µg l (g l-1 ) analysed River Gly AMP Gly AMP Gly AMP Gly AMP Gly AMP Gly AMP Gly AMP

Lepsämänjoki 1 1 8 8 1 1 0 0 0 0 - - <0.1 <0.05 (2007) (12.5%) (12.5%)

Lepsämänjoki 2 2 14 14 2 2 2 2 2 1 14.3 7.1 0.46 0.22 (2008) (8.3%) (8.3%)

Lepsämänjoki 1 1 2 2 0 0 (0%) 0 0 - - - - nd nd (2009) (0%)

Lepsämänjoki 2 2 24 24 3 3 2 2 2 1 8.3 4.2 0.46 0.22 (Total 2007- (12.5%) (12.5%) 2009)

Kyrönjoki (2009) 1 1 2 2 0 0 0 0 0 0 - - nd nd

TOTAL (2 3 3 26 26 3 3 2 2 2 1 7.7 3.9 0.46 0.22 rivers) (11.5%) (11.5%)

Notes: * below Limit of Quantification but above limit of detection (LoD not provided) ** LoQ = Limit of Quantification = 0.1 g l-1 for glyphosate and 0.05 g l-1 for AMPA nd = not detected

9.3 Groundwater

The occurrence of pesticides in untreated groundwater in the wells of water intakes was studied in a screening project "Occurrence of pesticides in groundwater – TOPO". This followed the discovery at a waterworks of increased concentrations of pesticides and their breakdown products through routine raw water monitoring (Gustafsson 2004 in TemaNord, 2007). A total of 189 aquifers were included in the study. During 2002-2005, a total of 295 samples were collected from 282 sampling sites, which were situated in 190 groundwater areas covering southern and central Finland. The study focused on areas where pesticides are used or were probably used in the past. Within this project six sampling sites with agricultural pressures were selected for analyses of glyphosate and AMPA. From those six sites no glyphosate or AMPA were detected (Tapini Säynätkari, Finnish Environment Institute SKYE, personal communication 2009 and TemaNord, 2007), as shown in Table 9.2.

During 2007 and 2008 approximately 170 groundwater samples were taken from areas with agricultural pressures. Pesticides were analysed in 75 samples, with glyphosate and AMPA analysed in most of the samples and no glyphosate or AMPA were detected. The limits of quantification were 0.1 g l-1 for glyphosate and 0.05 g l-1 for AMPA (Tapini Säynätkari, Finnish Environment Institute SKYE, personal communication 2009).

The monitoring of pesticides will continue to some extent in areas with agricultural pressures in the future. Although glyphosate is very commonly used, it has not been found in groundwaters so far and it will not be included in the monitoring programme, at least not in the next few years (personal communication Tapini Säynätkari, 2009).

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Table 9.2 Groundwater monitoring in Finland, 2002 to 2008 (source: Tapini Säynätkari, Finnish Environment Institute SKYE, personal communication, 2009)

Year Glyphosate AMPA Number of Number of Number of Number of sites/samples detections* sites/samples detections* analysed analysed 2002-2005 6 0 6 0 2007-2008 75 0 75 0 Total 2002-08 81 0 81 0 * Limit of Quantification = 0.1 g l-1 for glyphosate and 0.05 g l-1 for AMPA

9.4 Summary

There is limited surface water and groundwater monitoring for glyphosate and AMPA in Finland.

Glyphosate and AMPA have been analysed in two rivers between 2007 and the present. In total, glyphosate was detected in 3 of 26 samples, two of these at levels above the limit of quantification (0.1 g l-1), and at a maximum concentration of 0.46 g l-1. AMPA was also detected in 3 samples, only one exceeded 0.1 g l-1 at a level of 0.22 g l-1.

Analyses at about 80 groundwater sites between 2007 and 2008 have not revealed any glyphosate or AMPA, despite the fact it is very commonly used. Therefore, although monitoring of pesticides will continue to some extent in the future in areas with agricultural pressures, glyphosate and AMPA will not be included in the routine monitoring programme, at least not in next few years.

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10. FRANCE

10.1 Introduction

The Institut Français de l’Environnement (Ifen) has collated, assessed and summarised the results of pesticide monitoring programmes from various sources throughout France and French Overseas Departments (Ifen, 1998, 2000, 2001 and 2001a, 2002, 2003). These comprised predominantly data from Departmental and Regional monitoring programmes run by national agencies, such as the Agences de l’Eau and the Directions Régionales de l’Environnement (DIREN). The Departmental Health Authorities (DDASS) and public water suppliers also provided data from their programmes concerned with the quality of raw water destined for drinking water production. In addition, data for some local monitoring networks were included.

Clearly, the data were derived from a large number of sources and the report does not provide details of individual monitoring programmes or methods of analyses. However, analyses were performed to national standard methods or equivalent, by accredited laboratories and assessed at Ifen.

We received all the IFEN data available for glyphosate and AMPA in surface water and groundwater as extracted from the IFEN database (via Monsanto, Annick Geeraerts, personal communication, 2009). This included data for surface water from 1997 to 2006 and data for groundwater from 1999 to 2006. The data was received as excel files, with all repeated and incoherent data having been deleted.

10.2 Surface Water

10.2.1 National collation of data

Data extracted from the Ifen database (provided via Monsanto, Annick Geeraerts, personal communication 2009) has been analysed and is summarised below (Tables 10.1 and 10.2).

Glyphosate was analysed in nearly 40 000 samples from around 2 500 sites, between 1997 and 2006 (Table 10.1). It was detected at levels above the limit of quantification (0.2 – 0.05 g l-1) in 1 651 sites (66%), and at above 0.1 g l-1 in 1 564 sites (63%). Overall, from the 40 000 samples, it was detected in 12 680 samples (32%) at levels above the limit of quantification, with 10 495 samples (27%) above 0.1 g l-1. The maximum concentration was apparently 3 257 g l-1, although this figure may need further investigation. The next highest concentration reported was 50 g l-1.

AMPA was analysed in nearly 29 000 samples from around 2 200 sites, between 1998 and 2006 (Table 10.2). It was detected at levels above the limit of quantification (0.1 – 0.05 g l-1) in 1 651 sites (74%), and at above 0.1 g l-1 in 1 593 sites (72%). Overall it was detected in nearly 16 000 samples (55%) at levels above the limit of quantification, with 14 583 samples (50%) above 0.1 g l-1. The maximum concentration reported was 48.9 g l-1.

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Table 10.1 Glyphosate in French surface waters, 1997 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) Date No. of No. of % No. of % No. of No. of % No. of % LoQ Max. Sites* sites > LoQ sites > 0.1 samples samples > LoQ samples > 0.1 g l-1 (µg l-1) Conc. > LoQ > 0.1 g l-1 g l-1 > LoQ > 0.1 g l-1 (µg l-1) 1997 2 2 100% 2 100% 4 3 75% 2 50% 0.1 1.5 1998 15 11 73% 11 73% 51 39 76% 39 76% 0.1 3.4 1999 79 42 53% 40 51% 289 105 36% 96 33% 0.2 - 0.05 35.0 2000 211 118 56% 110 52% 832 274 33% 229 28% 0.2 - 0.05 6.36 2001 401 211 53% 194 48% 2213 589 27% 463 21% 0.2 - 0.05 41.0 2002 849 583 69% 535 63% 5133 1864 36% 1421 28% 0.1 - 0.05 40.59 2003 1065 689 65% 649 61% 6458 2092 32% 1799 28% 0.1 - 0.05 3257 *** 2004 1313 875 67% 765 58% 7526 2687 36% 2179 29% 0.1 - 0.05 50.00 2005 1481 962 65% 902 61% 8700 2952 34% 2547 29% 0.1 - 0.05 9.60 2006 1316 738 56% 664 50% 7960 2075 26% 1720 22% 0.1 - 0.05 34.0 TOTAL* 2493 1651 66% 1564 63% 39166 12680 32% 10495 27% 0.2 – 0.05 50.0 * Total of sites not cumulative as includes where sites monitored in more than one year ** Some LoQs were higher, up to 1 g l-1 *** This high value may require further investigation (so has been excluded from summary statistics). The next highest maximum in 2003 (from all sites) was 50 g l-1. Table 10.2 AMPA in French surface waters, 1998 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) Date No. of No. of % No. of % No. of No. of % No. of % LoQ Max. Sites* sites > LoQ sites > 0.1 samples samples > LoQ samples > 0.1 g l-1 (µg l-1) Conc. > LoQ > 0.1 g l-1 g l-1 > LoQ > 0.1 g l-1 (µg l-1) 1998 1 0 - - - 2 0 - - - 0.10 <0.1 1999 49 37 76% 34 69% 108 63 58% 58 54% 0.05 – 0.10 5.05 2000 58 46 79% 44 76% 215 103 48% 89 41% 0.05 – 0.25 2.99 2001 86 63 73% 60 70% 289 177 61% 150 52% 0.05 – 0.25 4.20 2002 608 450 74% 434 71% 3029 1581 52% 1389 46% 0.05 – 0.5 48.9 2003 681 598 88% 573 84% 3963 2340 59% 2201 56% 0.05 – 0.10 48.1 2004 1047 598 57% 573 55% 6228 3427 55% 3065 49% 0.05 – 0.10 17.0 2005 1203 921 77% 858 71% 7323 4311 59% 3969 54% 0.05 – 0.10 30.0 2006 1295 929 72% 897 69% 7806 3981 51% 3662 47% 0.05 – 0.10 27.5 TOTAL* 2217 1651 74% 1593 72% 28963 15983 55% 14583 50% 0.05 – 0.10 48.9 * Total of sites not cumulative as includes where sites monitored in more than one year ** Some LoQs were higher, some up to 1 g l-1.

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10.2.2 Regional data

Ile de France

A paper on the Marne watershed (Blanchoud et al., 2007), stated that a new pesticide monitoring programme had started (2004/2005) in the Ile-de-France region, with glyphosate and AMPA being among the pesticides added. Results from the 2004/2005 programme showed frequent contamination with AMPA (88%) and glyphosate (61%).

The most recent report from this region was therefore obtained and reviewed (DIREN, 2008). This presented results from 2006 and 2007. Glyphosate and AMPA were highlighted as one of the main contaminants in rivers, with both frequently found in more than 30% and 65% respectively of the analysed water samples (respectively 200/610 samples and 410/610 samples).

Surveillance monitoring was undertaken at fixed periods (the last two week of every other month) and therefore does not highlight periods that are more favourable for the transfer of contaminants to surface water. Glyphosate and AMPA were found at each sampling period throughout the year. High concentrations (>5 g l-1) of both glyphosate and AMPA were found in July 2006 compared to July 2007 due to storm conditions and supposed higher dilution factor in July 2007. Spring is often when the contamination is higher due to the application rate and higher rainfall and was demonstrated by the sampling in May 2007. Glyphosate and AMPA were identified very frequently and at high concentration during that sampling period.

The publication concludes that the main contaminants (amongst others) are glyphosate and AMPA. Actions taken in river catchment are considered to be effective even though some contaminants (like atrazine and desethylatrazine) which have been banned are still being detected, indicating that they are persistent in the environment and will require more time to be eliminated. Concentrations of glyphosate and AMPA detected were lower than detailed in the previous report (DIREN, 2006), as shown in Table 10.3.

Table 10.3 Glyphosate and AMPA detections in the Ile de France region in 2005-06 and 2006-07 (source: DIREN, 2006; DIREN, 2008)

Year Substance No. of No. of % of Max. LoQ Month of samples analyses analyses conc. g l-1 detection of ≥ 1.0 g l-1 ≥ 1.0 g l-1 g l-1 maximum conc. 2005-06 AMPA 384 116 30% 12.1 0.1 Oct-05 Glyphosate 303 46 15% 34 0.1 May-06 2006-07 AMPA 414 44 11% 5.9 0.1 Nov-06 Glyphosate 197 10 5% 4.7 0.1 Sept-06 Note: LoQ = Limit of quantification

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Orge watershed (focusing on urban run-off)

A study of glyphosate and AMPA transfer in the Orge watershed was carried out during 2007 and 2008 (Botta et al., 2009). Water samples were collected in surface water, wastewater sewer, storm sewer and wastewater treatment plants (WWTP). The annual glyphosate estimated load was 1.9 kg year−1 upstream (agricultural zone) and 179.5 kg year−1 at the catchment outlet (urban zone), suggesting that the contamination of this basin by glyphosate was essentially from urban origin (road and railway applications). Glyphosate reached surface water mainly through storm sewer during rainfall events, with maximum concentrations detected in storm sewers just after a rainfall event (75–90 g l-1). High concentrations of glyphosate in surface water during rainfall events reflected urban runoff impact. AMPA was always detected in the sewerage system, and it reached surface water mainly via WWTP effluent and also through storm sewers. Variations in concentrations of AMPA during hydrological episodes were minor compared to glyphosate variations. The authors concluded that their study highlighted that AMPA and glyphosate origins in urban areas are different and that during dry periods, detergent degradation seemed to be the major source of AMPA in wastewater treatment effluent, discharged to surface waters.

10.3 Groundwater

Data extracted from the Ifen database (provided via Monsanto, Annick Geeraerts, personal communication, 2009) has been analysed and is summarised in the Tables below (Tables 10.4 and 10.5).

Glyphosate results from groundwater were available from 1999 – 2006 (Table 10.4) and AMPA results from 1999 – 2006 (Table 10.5).

Glyphosate was analysed in nearly 18 000 samples from around 3 800 sites. It was detected at levels above the limit of quantification (0.05 – 0.01 g l-1) in 257 sites (7%), and at above 0.1 g l-1 in 185 sites (5%). Overall, from the 17 694 samples, it was detected in 344 samples (1.9%) at levels above the limit of quantification, with 241 samples (1.4%) above 0.1 g l-1. The maximum concentration was apparently 24 g l-1 in 2005, although this figure may need further investigation, the next highest concentration that year (from all sites) was 0.8 g l-1. Overall, the highest concentration detected was 24 g l-1, with the next highest at 6.8 g l-1.

AMPA was analysed in around 11 500 samples from around 2 800 sites. It was detected at levels above the limit of quantification (0.05 – 0.01 g l-1) in 156 sites (5.5%), and at above 0.1 g l-1 in 109 sites (3.9%). Overall it was detected in 267 samples (2.3%) at levels above the limit of quantification, with 184 samples (1.6%) above 0.1 g l-1. The maximum concentration was 19 g l-1 in 2005, although this figure may need further investigation, the next highest concentration that year (from all sites) was 1.5 g l-1. Overall, there were two high concentrations at 19 g l-1and 8 g l-1, the rest were all below 1.65 g l-1.

Earlier investigations (ISL, 2007; Horth and Gendebien, 2008) relating to a small number of detections of glyphosate in drinking waters, most of which were derived from groundwater, revealed that the detections were most likely due to sample contamination or analytical problems. However, these related to 2001-2003 and more recent findings in groundwater may warrant further investigation.

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Table 10.4 Glyphosate in French groundwater, 1999 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) Date No. No. of % No. of % No. of No. of % No. of % LoQ** Max. Conc. of sites > LoQ sites > 0.1 samples samples > LoQ samples > 0.1 (µg l-1) (µg l-1) sites > LoQ > 0.1 g l-1 g l-1 > LoQ > 0.1 g l-1 g l-1 1999 195 5 2.6 5 2.6 369 5 1.4 5 1.4 0.1 0.4 2000 649 6 0.9 2 0.3 948 6 0.6 2 0.2 0.1 0.4 2001 342 19 5.6 13 3.8 734 29 3.9 15 2.0 0.05 – 0.1 0.54 2002 684 29 4.2 17 2.5 1283 33 2.6 19 1.5 0.05 – 0.1 2.17 2003 980 22 2.2 19 1.9 1922 23 1.2 21 1.1 0.05 – 0.1 6.78 2004 2258 87 3.9 57 2.5 4512 91 2.0 60 1.3 0.05 – 0.1 4.95 2005 1327 44 3.3 32 2.4 3331 57 1.7 43 1.3 0.05 – 0.1 24.0 (next highest 0.8) 2006 1850 83 4.5 63 3.4 4595 100 2.2 76 1.7 0.05 – 0.1 4.87 TOTAL* 3800 257 6.8 185 4.9 17694 344 1.9 241 1.4 0.05 – 0.1 24.0 * Total of sites not cumulative as includes where sites monitored in more than one year ** Some LoDs were higher, up to 1.0 g l-1 Table 10.5 AMPA in French groundwater, 1999 – 2006 (source: extracted from the Ifen database, provided via Monsanto, Annick Geeraerts, personal communication, 2009) Date No. No. of % No. of % No. of No. of % No. of % LoQ** Max. Conc. of sites > LoQ sites > 0.1 samples samples > LoQ samples > 0.1 (µg l-1) (µg l-1) sites > LoQ > 0.1 g l-1 g l-1 > LoQ > 0.1 g l-1 g l-1 1999 0 - - - - 0 ------2000 369 0 - - - 380 0 - - - 0.1 <1.0 2001 58 1 1.7 1 1.7 107 1 0.9 1 0.9 0.05 – 0.1 0.9 2002 117 29 24.8 17 14.5 270 57 21.1 23 0.9 0.05 – 0.1 0.59 2003 457 36 7.9 30 6.6 985 41 4.2 35 8.5 0.05 – 0.1 1.65 2004 1631 59 3.6 40 2.5 3342 67 2.0 46 3.6 0.05 – 0.1 8.0 (next highest 1.5) 2005 967 32 3.3 25 2.6 2541 49 1.9 42 1.4 0.05 – 0.1 19 (next highest 1.5) 2006 1559 34 2.2 21 1.3 3881 52 1.3 37 1.7 0.05 – 0.1 0.965 TOTAL* 2828 156 5.5 109 3.9 11506 267 2.3 184 1.6 0.05 – 0.1 19 * Total of sites not cumulative as includes where sites monitored in more than one year ** Some LoQs were higher, up to 1.0 g l-1

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10.4 Summary

Data from national and local surveys of surface water and groundwater were collated on a database by Ifen, extracts of which were made available by Monsanto for this review, covering data 1999-2006. Two recent regional studies were obtained from the literature, one of these focusing on urban run-off.

A relatively small number of data points were reported for the 1998-1999 period, but sampling increased in subsequent years (2000 and 2001).

The data from the Ifen database (covering the years 1997-2006 for surface water and 1999- 2006 for groundwater) show glyphosate was detected in 1.9% of groundwater samples (6.8% of sites), with 1.4% (or 4.9% of sites) at concentrations above 0.1 g l-1. It was found in a much higher proportion of surface water samples (32%, and 66% of the sites), with 27% of samples (63% of sites) at concentrations over 0.1 g l-1. The maximum concentrations of glyphosate found were 3257 g l-1 in surface water (this may be a suspect result, the next highest was 50 g l-1) and 24.0 g l-1 in groundwater (next highest 1.65 g l-1). Similar trends were found for AMPA, with detections in 2.3% of groundwater samples, with 1.6% found above 0.1 g l-1. Again there was a much higher proportion of detections in surface water samples (55%, or 74% of the sites); with 50% of samples (74% of sites) at concentrations over 0.1 g l-1. The maximum concentrations of AMPA found were 48.9 g l-1 in surface water and 19 g l-1 (next highest 8 g l-1) in groundwater.

The high detections in surface waters were confirmed by the reports from the Ile de France region (2005-2007), where glyphosate and AMPA were highlighted as one of the main contaminants in rivers, with both frequently found in more than 30% and 65%, respectively, of the analysed water samples.

The study of glyphosate and AMPA in wastewaters and urban run-off concluded that a high input of glyphosate originated from urban run-off and that detergent degradation seemed to be the major source of AMPA in wastewater treatment effluent, discharged to surface waters.

Earlier investigations relating to a small number of detections of glyphosate in drinking waters, most of which were derived from groundwater, revealed that the detections were most likely due to sample contamination or analytical problems. However, these related to 2001-2003 and more recent findings in groundwater may warrant further investigation.

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11. GERMANY

11.1 Introduction

Groundwater data have been received, as collated by the Federal Environment Agency (Umweltbundesamt - UBA), whereas surface water data are not available in a collated form at national (Bund) level. However, we have received data and information for several States (Länder) via LAWA (Bund/ Länder-Arbeitsgemeinschaft Wasser), directly through professional contacts or obtained from other sources (e.g. web sites, on line database).

In addition, separate data were received from ARW (Arbeitsgemeinschaft Rhein- Wasserwerke) for the river Rhine (via Monsanto) and a small amount of data from the river Ruhr is included.

Earlier monitoring data and specific investigations are included in the previous WRc review (Horth et al., 2004).

11.2 Surface Water

11.2.1 Baden-Württemberg

All the available data for glyphosate and AMPA monitoring in surface water of the State of Baden-Württemberg for 2006-2008 were kindly provided by Claudia Früh (personal communication, 2009) of the LUBW (Landesanstalt für Umwelt, Messungen und Naturschutz Baden-Württemberg) and is summarised in Table 11.1. Glyphosate and AMPA were monitored only in the larger rivers. The limit of quantification was 0.05 g l-1.

Glyphosate was detected overall in about half of all samples analysed, and at all except one monitoring station (Öhningen on the river Rhine), though only once in 2007 in Karlsruhe (river Rhine). AMPA was detected in nearly all samples (94%), also with the exception of the monitoring station at Öhningen. Glyphosate was found at concentrations at or above 0.1 g l-1 in 26% of all samples, whereas AMPA was found above 0.1 g l-1 in 75% of samples; maximum concentrations were 0.33 g l-1 and 1.2 g l-1, respectively.

It was pointed out by Claudia Früh (personal communication, 2009) that AMPA was not only a metabolite of glyphosate, but could occur in waters in significant amounts from industrial sources and effluents due to the use of complexing agents. This has previously been suggested and seems to be accepted increasingly (see also Section 2 – Austria). For example, Reupert and Schlett (1997) have demonstrated the formation of AMPA from aminopolyphosphonate (used in detergents and as cooling water additive). Moreover, Landrieux and co-workers (1999) and Lange & Post (2000) suggested that relatively constant levels of AMPA throughout the year may be derived from wastewater effluent discharges into surface waters, whereas increased short-term levels may occur as a result of biodegradation of glyphosate, and therefore linked to glyphosate applications and run-off.

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Table 11.1 Glyphosate and AMPA in surface water in the State of Baden Württemberg, 2006 - 2008 (source: Claudia Früh, LUBW, personal communication, 2009)

River/ canal Monitoring Year No. of No. of samples (%) No. of samples (%) Maximum conc. station samples ≥ LoQ* (g l-1) ≥ 0.1 g l-1 g l-1 Gly AMPA Gly AMPA Gly AMPA Danube Ulm-Wiblingen 2006 12 5 (42%) 12 (100%) 1 (8%) 9 (75%) 0.16 0.24 2007 13 6 (46%) 13 (100%) 1 (8%) 8 (62%) 0.30 0.30 2008 13 4 (31%) 13 (100%) 2 (15%) 8 (62%) 0.17 0.24 Ulm-Böfingen 2006 13 2 (15%) 12 (92%) 0 5 (38%) 0.10 0.15 Rhine Öhningen 2006 4 0 0 0 0 <0.05 <0.05 2007 5 0 0 0 0 <0.05 <0.05 2008 4 0 0 0 0 <0.05 <0.05 Gambsheim 2006 13 3 (23%) 13 (100%) 0 8 (62%) 0.07 0.15 Karlsruhe 2006 13 0 13 (100%) 0 10 (77%) <0.05 0.18 2007 13 1 (8%) 13 (100%) 0 2 (15%) 0.10 0.16 2008 13 0 13 (100%) 0 7 (54%) <0.05 0.15 Mannheim, Rhein 2006 13 3 (23%) 13 (100%) 0 11 (85%) 0.05 0.27 Neckar Mannheim, 2006 13 12 (92%) 13 (100%) 8 (62%) 13 (100%) 0.20 0.97 Neckar 2007 13 10 (77%) 13 (100%) 7 (54%) 13 (100%) 0.30 0.90 2008 13 11 (85%) 13 (100%) 6 (46%) 13 (100%) 0.22 1.19 Deizisau, l.U. 2006 13 11 (85%) 13 (100%) 6 (46%) 12 (92%) 0.19 0.80 2007 13 12 (92%) 13 (100%) 3 (23%) 13 (100%) 0.20 0.70 2008 13 12 (92%) 13 (100%) 6 (46%) 13 (100%) 0.27 0.72 Schleusen- Kochendorf, F.M. 2006 13 12 (92%) 13 (100%) 8 (62%) 13 (100%) 0.28 1.10 kanal 2007 13 13 (100%) 13 (100%) 8 (62%) 13 (100%) 0.30 1.00 2008 13 13 (100%) 13 (100%) 8 (62%) 13 (100%) 0.33 1.16 TOTAL 2006 - 2009 246 130 (53%) 232 (94%) 64 (26%) 184 (75%) 0.33 1.19 (9 sites)

*LoQ (Limit of Quantification) = 0.05 g l-1

11.2.2 Bremen

Only AMPA seems to have been analysed in a small amount of samples from two monitoring sites, and not detected in any. At the site Hemelingen on the river Weser, it was analysed in six samples taken between February and September 2006, and at Köhlerbrücke on the Ochtum it was analysed once in May 2006. All were reported as <0.1 g l-1 (data provided by Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009).

11.2.3 Hessen

Glyphosate and AMPA data were provided by Dr. Peter Seel (Hessisches Landesamt für Umwelt und Geologie, Wiesbaden, personal communication, 2009). These substances have been monitored since 2007 in the river Main. The data are presented in (Table 11.2) and relate to 2007 and 2008, where glyphosate and AMPA were monitored in 12 samples each year at the Main monitoring station. The limit of quantification was 0.05 g l-1. No quality standards have been set or proposed for glyphosate or AMPA. Average and maximum concentrations were typically lower for glyphosate (less than 0.1 g l-1 and less than 0.2 g l-1, respectively) than for AMPA (less than 0.5 g l-1 and less than 1 g l-1, respectively).

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Table 11.2 Glyphosate and AMPA in the river Main, State of Hessen, 2007-2008 (source: Dr. Peter Seel, Hessisches Landesamt für Umwelt und Geologie, Wiesbaden, personal communication, 2009)

Year Substance Number of Average Maximum samples concentration concentration analysed (g l-1) (g l-1) 2008 Glyphosate 12 0.09 0.18 AMPA 12 0.46 0.92 2007 Glyphosate 12 0.08 0.14 AMPA 12 0.42 0.73

11.2.4 Mecklenburg-Vorpommern

Between April and September 2008, glyphosate was detected in two thirds of all samples analysed from 59 sites in Mecklenburg-Vorpommern. The proposed Quality Standard of 28 g l-1 was exceeded at one site, with an average concentration of 30.6 g l-1, and a maximum concentration of 171 g l-1. Six other sites had maximum concentrations in the range 1-3 g l-1, whilst the remainder were below 1 g l-1, as were the average concentrations (from a presentation slide by Bachor A. (2009), provided by Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009).

11.2.5 Niedersachsen

AMPA, but not glyphosate, has been monitored in Niedersachsen (NLWKN, 2007, report provided by Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009). German standard methods of analyses (DIN 38407-20) involving various gas chromatography – mass spectrometry techniques (this refers to all analyses) were used; the limit of quantification for AMPA was 0.1 g l-1. Quality standards for all substances analysed were given, no standard has been set for AMPA, which was analysed at 47 sites (from 37 rivers and two from the North Sea) in 2006. Most samples were taken either in May or September/October, only one sample per site, although a few results were presented as ‘average’ values. A time series was also conducted at the monitoring station Herbrum on the river Ems, where 12 samples were analysed between November 2005 and September 2006.

AMPA was never detected, i.e. all the results were reported as <0.1 g l-1 (in total 59 samples from 47 monitoring stations, mainly analysed in 2006.

11.2.6 Nordrhein-Westfalen

Glyphosate and AMPA are monitored in the State of Nordrhein-Westfalen (NRW). The database NRW FlussWinIMS (2009) was queried on line (link provided by Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication) and the results for 2006-2008 shown in Table 11.3. Glyphosate was frequently detected, but always at concentrations below 1.0 g l-1, with the majority of sites (except in 2008) mainly at concentrations below 0.1 g l-1 or below the limit of quantification. AMPA was generally found at higher concentrations, i.e. frequently above 1.0 g l-1, but never above 5.0 g l-1.

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Table 11.3 Glyphosate and AMPA in surface waters in Nordrhein-Westfalen, 2006- 2008 (Source: NRW FlussWinIMS database, 2009, http://www.elwasims.nrw.de/ims/FlussWinIMS/start.htm)

Year Substance Number of sites ≤ 0.1 g l-1 * ≥ 0.1 g l-1 ≥ 1.0 g l-1 ≥ 5.0 g l-1 2008 Glyphosate 40 47 0 - AMPA 29 33 33 0 2007 Glyphosate 48 17 0 - AMPA 34 39 10 0 2006 Glyphosate 99 32 0 - AMPA 58 80 21 0

Note: * includes numbers below the limit of quantification (LoQ) – no LoQ value(s) provided

11.2.7 Rheinland-Pfalz

WFD Operational Monitoring

The operational monitoring programme under the requirements of the EU Water Framework Directive (WFD) included glyphosate and AMPA in the special pesticide monitoring programme, as described in LUWG (2009). Pesticide monitoring focused on smaller rivers in agricultural areas, with agricultural land use (arable land, including vineyards and special crops) ranging from 7.4% to 83.5% of surface area in the catchments above the monitoring stations. The sampling points were generally located at or just above the rivers’ confluence with other rivers.

The results for 14 sites, covering the period April 2004 to February 2007, are collated in Table 11.4, including the percentage arable land for each site. The monitoring station on the river Selz at Ingelheim is used for trend analyses and data were based on 14-day composite samples, although insufficient data are available to date to comment on trends for glyphosate and AMPA (2004 and 2006 data). All other sites cover the period 2005-06 or 2006-07 and the results were based on spot samples.

In total 304 samples were analysed from the 14 sites; glyphosate was detected greater than the limit of quantification of 0.05 g l-1 in 56 samples (18%) and at or above 0.1 g l-1 in 47 samples (15%). AMPA was detected in a higher proportion of samples and mostly at higher concentrations, i.e. above 0.05 g l-1 in 152 samples (50%), and at or above 0.1 g l-1 in 143 samples (47%). The highest average concentration for glyphosate was at 1.1 g l-1 and the maximum concentration 2.3 g l-1; for AMPA these values were 2.5 g l-1 and 3.6 g l-1, respectively.

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Table 11.4 Glyphosate and AMPA in surface waters in the State of Rheinland-Pfalz, 2004-2007 (source: LUWG, 2009)

River / Site % agri- Time scale Sub- Number of Concentration Number of samples cultural stance samples (g l-1) surface analysed Average Max > LoQ ≥0.1g l-1 . Selz / Ingelheim * 83.5 05.04.04-18.10.04 Gly 15 1.1 1.7 15 15 AMPA 15 2.5 3.3 15 15 09-01.06-25.12.06 Gly 26 0.04 0.47 1 1 AMPA 26 0.43 2.5 10 9 Alsenz / Mündung 37.5 15.04.05-14.03.06 Gly 21 0.03 0.14 1 1 (Confluence) AMPA 21 0.06 1.2 7 6 Lauter / 19.4 15.04.05-14.03.06 Gly 21 0.05 0.32 2 2 Lauterecken AMPA 21 0.57 1.6 15 14 Glan / Oderheim 27.9 15.04.05-14.03.06 Gly 21 0.07 0.22 9 5 AMPA 21 0.47 1.6 13 12 Wiesbach / below 66.2 15.04.05-14.03.06 Gly 21 0.16 0.7 6 6 Gensingen AMPA 21 0.49 2 13 13 Flaumbach 33.1 01.03.06-31.01.07 Gly 20 0.05 0.52 1 1 AMPA 20 0.23 3.0 5 4 Mühlbach 40.7 0.6.03.06-06.02.07 Gly 21 nd - 0 0 AMPA 21 nd - 0 0 Sieg 7.4 24.02.06-07.02.07 Gly 20 0.09 0.44 4 4 AMPA 20 0.79 3.6 14 14 Pfrimm 65.4 20.03.06-12.02.07 Gly 18 0.16 1.1 6 4 AMPA 18 0.44 3.1 11 10 Isenach 48.5 20.03.06-12.02.07 Gly 18 0.05 0.19 4 3 AMPA 18 0.55 3.0 15 14 Nette 38.3 02.03.06-01.02.07 Gly 20 nd nd 0 0 AMPA 20 nd nd 0 0 Hornbach 33.2 01.03.06-31.01.07 Gly 21 0.04 0.19 3 1 AMPA 21 0.27 1.1 11 9 Elzbach 39.7 13.03.06-15.02.07 Gly 20 0.07 0.8 1 1 AMPA 20 0.16 1.1 9 9 Schwarzbach 23.5 01.03.06-31.01.07 Gly 21 0.19 2.3 3 3 AMPA 21 0.29 0.87 14 14 Total – 14 sites 7.4-83.5 April 04-Feb. 07 Gly 304 nd-1.1 2.3 56 47 (18%) (15%) AMPA 304 nd-2.5 3.6 152 143 (50%) (47%) Notes: * 14 day composite sample, all other sites spot samples LoQ (limit of quantification) 0.05 g l-1 nd = not detected

From the data summarised in Table 11.4, there does not seem to be an obvious correlation between agricultural land use and glyphosate and AMPA detection or concentrations; the data were applied, together with many other parameters, to assess water bodies at risk, as required under the WFD, rather than an interpretation of individual substances. The authors did point out that glyphosate inputs could also arise from non-agricultural usage and that AMPA could be derived from the degradation of complexing agents in detergents. Glyphosate and AMPA were included in the monitoring programme on the basis of earlier investigations in the catchments. The criterion of 0.1 g l-1 was applied to pesticides in the absence of an EQS (Environmental Quality Standard) on the basis of the quality objectives set by LAWA for surface water destined for drinking water production (LUWG, 2007a). However, glyphosate and AMPA were not used directly in the risk assessment and classification of water bodies.

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River Nahe

The Environment Agency of the State of Rheinland-Pfalz (LUWG, 2007b) selected the river Nahe for a special study of potential contaminants in 2001-2002. The study included substances likely to be found on the basis of land use (largely agriculture) and therefore included glyphosate among other herbicides.

Glyphosate was analysed in 2001-2002; 14-day composite samples were collected at the monitoring station Grolsheim from April 2001 to December 2002. The analyses were carried out by LUFA Speyer, where the specialist analysis was available; the limit of quantification was 0.05 g l-1. The results are shown in terms of glyphosate concentrations and river flow in Figure 11.1, and also as loads, calculated from the 14 day composite samples and the river flow, in Figure 11.2.

In 2001 glyphosate concentrations increased steadily from April to August up to a maximum of 0.49 g l-1, at similarly low river flows throughout, followed by a decrease to a minimum of 0.04 g l-1 in December. With the exception of the late February sample, the concentrations remained below 0.1 g l-1 until March 2002.

The maximum loads occurred in February 2002 (almost 1.5 kg/d) and end of December 2002 (1.8 kg/d), clearly linked to high river flow events. Annual average loads were in the range 0.3- 0.6 kg/d, or a total of 146 kg/a, for the period April 2001 to March 2002, which was higher than the load of any other substance monitored. In view of this, the authors considered it important to propose quality objectives for use in quality criteria under the Water Framework Directive.

11.2.8 Sachsen

In Saxony glyphosate and AMPA are being monitored for the first time in 2009 and data are not yet available (Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication).

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Note: Konz = concentration; Abfluss = river flow

Figure 11.1 Glyphosate concentrations in the river Nahe, April 2001 to December 2002 (source: LUWG, 2007b)

Note: Fracht = load, Abfluss = river flow

Figure 11.2 Glyphosate load in the river Nahe, April 2001 to December 2002 (source: LUWG, 2007b)

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11.2.9 Sachsen-Anhalt

Glyphosate and AMPA were analysed for the first time in 2009 in Sachsen-Anhalt and data were provided by Beate Zedler (LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009). These data are summarised in Table 11.5. A total of 76 samples were taken in the period January to September 2009. Glyphosate was detected in 69 samples (91%) at concentrations ranging from 0.05 g l-1 to 0.63 g l-1, and an average concentration of 0.20 g l-1. AMPA was found somewhat less frequently (61 or 80% of samples) and at lower concentrations overall (range 0.05-0.23 g l-1, average 0.120 g l-1.

Table 11.5 Glyphosate and AMPA in surface water in Sachsen-Anhalt, 01.01.2009- 04.09.2009 (source: Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009)

Substance Number of Number Minimum Maximum Average analyses (%) >LoQ concentration concentration concentration g l-1 g l-1 g l-1 Glyphosate 76 69 (91) 0.050 0.630 0.203 AMPA 76 61 (80%) 0.050 0.230 0.120

Note: Relates to values >LoQ (limit of quantification) only – LoQ value not supplied

11.2.10 Thüringen

Glyphosate and AMPA data for the Federal State of Thüringen for 1997-2008 was provided through LAWA (Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009) and are summarised in Table 11.6. In total, 578 samples from 77 sites (49 rivers) were analysed for glyphosate in this period, and glyphosate was detected and found at concentrations above 0.1 g l-1 in 43 samples (7.4%) with a maximum concentration of 4.7 g l-1. AMPA was analysed in only 62 samples (not analysed in 2007 and 2008) from 38 sites (22 rivers) and found at concentrations above 0.1 g l-1 at a higher proportion of samples (17 samples, 27%) but the maximum concentration was lower at 1.1 g l-1.

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Table 11.6 Glyphosate and AMPA in surface waters in Thüringen, 1997-2008 (source: data provided by Beate Zedler, LAWA - Representative, Ministry of Environment, Hessen, personal communication, 2009)

Year No. of No. of No. of No. samples No. samples LoQ Max. conc. rivers sites samples (%) > LoQ (%) > 0.1 g l-1 (g l-1) (g l-1) 1997 Gly 8 8 48 0 (0%) - 0.02 <0.02 AMPA 8 8 10 3 (30%) 3 (30%) 0.1 – 0.5 0.23 2000 Gly 8 14 96 0 (0%) - 0.05 <0.05 AMPA 4 10 20 4 (20%) 4 (20%) 0.1 – 0.5 0.86 2005 Gly 6 10 66 4 (6%) 4 (6%) 0.12 1.06 AMPA 5 8 13 5 (38.5%) 5 (38.5%) 0.1 – 0.5 0.56 2006 Gly 27 42 232 0 (0%) - 0.12 <0.12 AMPA 13 19 19 5 (26.3%) 5 (26.3%) 0.1 – 0.5 1.1 2007 Gly 12 16 74 38 (51%) 38 (51%) 0.12 4.7 AMPA 0 0 0 - - - - 2008 Gly 8 10 62 1 (1.6%) 1 (1.6%) 0.12 or 1.5 0.326 AMPA 0 0 0 - - - - Total (1997 – 2008) * Gly 49 77 578 43 (7.4%) 43 (7.4%) 0.02 – 1.5 4.7 AMPA 22 38 62 17 (27%) 17 (27%) 0.1 – 0.5 1.1

Note: * sites not added where there is overlap

11.2.11 River Rhine - AWR

The Working Group of River Rhine Waterworks in Germany (Arbeitsgemeinschaft Rhein- Wasserwerke – AWR) undertakes raw water monitoring at water intakes on the river Rhine. Monitoring includes glyphosate and AMPA at a few selected sites (4 sites; the monitoring station at Frankfurt seems to have been on the river Main before joining the Rhine, whilst the others were on the Rhine). Target values of 0.05 g l-1 have been set for glyphosate and AMPA (Brauch et al., 2002 and 2003), or 0.1 g l-1 by the International AWR (IAWR Memorandum, in: Brauch et al., 2003). Samples were analysed monthly and based on 28 day composite samples. Whilst 90 percentile values and maximum concentrations were reported for the years 2001-2003, only 90 percentiles were available for 1999-2000, and only maximum concentrations for 2004. The results are summarised in Table 11.7.

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Table 11.7 Glyphosate and AMPA at water intakes on the Rhine, 1999-2004 (in g l-1) (source: Brauch et al., 2002 and 2003; ARW 2004)

Site 1999 2000 2001 2002 2003 2004 P90 P90 P90 Max. P90 Max. P90 Max. Max. Glyphosate Mainz 0.06 <0.05 0.07 0.11 0.10 0.13 0.12 0.21 0.44 Köln - - 0.11 0.15 0.08 0.08 0.09 0.10 0.19 Düsseldorf <0.05 0.13 0.08 0.10 0.07 0.08 0.08 0.10 0.17 Frankfurt /M - - 0.12 0.15 <0.05 0.11 0.12 0.14 0.14 AMPA Mainz 0.19 0.25 0.24 0.25 0.27 0.28 0.46 0.52 0.25 Köln - - 0.53 0.87 0.40 0.42 0.60 0.64 0.51 Düsseldorf 0.38 0.52 0.32 0.35 0.43 0.45 0.65 0.71 0.49 Frankfurt /M - - 0.67 0.80 0.46 0.46 0.65 0.66 0.82 Notes: for 1999/2000: only 90 percentiles available; for 2004: only maximum concentrations - no data

Glyphosate was detected at all stations between 2001 and 2004, with 90 percentile concentrations around 0.1 g l-1, and apparently increasing over the years. AMPA concentrations were consistently higher at concentrations ranging from about 0.2-0.6 g l-1. The 2003 and 2004 data were also reported in terms of monthly results, based on 28 day composite samples (Brauch et al., 2003; ARW 2004); data for 2004 are shown in Table 11.8.

This shows that all glyphosate concentrations above 0.1 g l-1 were found between March and September, whereas AMPA concentrations were consistently much higher and seemed to be increasing downstream (compare Mainz with Frankfurt). The overall pattern agrees broadly with earlier findings reported in the previous WRc review (Horth et al., 2004), e.g. Landrieux and co-workers, (1999).

11.2.12 River Ruhr

Data from a large water supplier (AWWR) in the Ruhr area, producing about 300 million m3 /a of drinking water, shows that glyphosate and AMPA were present in the raw water intakes for drinking water production (surface water derived from the river Ruhr) (Schlett et al., 2005). Examples for two treatment works are shown in Table 11.9. Nevertheless, these were removed during treatment and no longer found in partially or final treated water. (Further details are included in the recent WRc drinking water review, Horth and Gendebien, 2008).

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Table 11.8 Glyphosate and AMPA on the river Rhine, monthly analyses in 2004 (in g l-1) (source: ARW, 2004)

Site Mainz Köln Düsseldorf Frankfurt /Main Date Gly AMPA Gly AMPA Gly AMPA Gly AMPA 15.01 <0.05 0.19 <0.05 0.31 <0.05 0.27 <0.05 0.16 10.02 0.07 0.13 0.05 0.13 0.06 0.15 <0.05 0.16 11.03 0.18 0.19 0.07 0.23 0.08 0.24 <0.05 0.23 05.04 0.08 0.17 0.06 0.25 0.07 0.24 <0.05 0.27 05.05 0.44 0.25 0.19 0.36 0.17 0.34 0.07 0.35 04.06 0.09 0.22 0.10 0.36 0.10 0.34 0.09 0.29 29.06 0.16 0.21 0.11 0.35 0.09 0.34 0.07 0.41 29.07 0.05 0.24 0.08 0.44 0.07 0.41 0.12 0.82 23.08 0.05 0.24 0.09 0.51 0.09 0.49 0.14 0.76 22.09 0.10 0.30 0.08 0.40 0.08 0.44 0.11 0.48 22.10 <0.05 0.21 0.07 0.47 <0.05 0.30 0.09 0.48 16.11 <0.05 0.21 0.06 0.34 0.05 0.30 0.09 0.49 13.12 <0.05 0.22 <0.05 0.28 <0.05 0.26 0.07 0.38

Table 11.9 Glyphosate and AMPA in raw water intakes at Styrom-Ost and Hengsen waterworks (river Ruhr) in 2005 (source: Schlett et al., 2005)

Sampling point Parameter Number of Concentration (g l-1) samples minimum maximum Styrom-Ost Glyphosate 75 < 0.05 0.19 AMPA 75 < 0.08 0.70 Hengsen Glyphosate 13 < 0.05 0.09 AMPA 13 < 0.08 1.10

11.3 Groundwater

Groundwater data for glyphosate and AMPA for the years 1996 to 2008 were kindly provided by Dr Wolter of the Federal Environment Agency (UBA), where data from the Länder (Federal States) are collated. These are shown in Table 11.10. It must be noted that the 2008 data was incomplete because not all the Länder had submitted the 2008 data (Dr Wolter, UBA, personal communication, 2009). Although we have no details of the specific analytical methods used, some general information about monitoring programmes was provided in a separate report (UBA, 2006a), including reference to the use of standard methods and extensive AQC procedures.

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Table 11.10 Glyphosate and AMPA in groundwater in Germany, 1996-2008 (source: Dr Wolter, UBA, personal communication, 2009)

Year Total number Not detected Detected of sites (number of (number of sites) analysed sites) ≤ 0.1 g l-1 0.1 – 1.0 g l-1 ≥ 1.0 g l-1

Glyphosate 1996 143 141 0 2 0 1997 430 430 0 0 0 1998 116 116 0 0 0 1999 144 142 2 0 0 2000 130 130 0 0 0 2001 89 89 0 0 0 2002 256 250 5 1 0 2003 194 192 2 0 0 2004 215 211 3 1 0 2005 235 225 5 5 0 2006 222 220 2 0 0 2007 196 189 7 0 0 2008* 229 229 0 0 0 AMPA 1996 26 26 0 0 0 1997 139 137 2 0 0 1998 69 69 0 0 0 1999 25 19 6 0 0 2000 64 62 0 2 0 2001 62 60 1 1 0 2002 262 251 4 7 0 2003 72 67 2 3 0 2004 150 132 7 11 0 2005 174 168 3 3 0 2006 387 387 0 0 0 2007 326 316 5 3 2 2008* 230 228 0 2 0 Note: data for 2008 incomplete, as not all Länder had submitted the data

The data were presented in terms of numbers of sites without indication of sampling frequencies, although groundwater is often monitored just once a year because the quality is unlikely to change rapidly. In the period 1996-2008 glyphosate was detected at a small number of sites, with concentrations in most cases at or below 0.1 g l-1, and all at less than 0.1 g l-1. AMPA was detected somewhat more frequently, and at higher concentrations overall, with many in the range 0.1-1.0 g l-1 and two above 1.0 g l-1. We do not know whether any of the ‘positive’ sites were the same in different years, nor whether shallow groundwater or springwater was included in the survey, or for example private supplies of which there are considerable numbers in Germany.

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However, a thorough analysis of all positive findings up to 2004, conducted by the Fresenius Institute in Germany (Schmidt and Reichert, 2006) concluded that all the results (24 locations) were explained either by invalid analyses, or well contamination with surface water or bank filtrate, wastewater or waste deposits. Some observation wells were found to be unsuitable for groundwater monitoring purposes and inappropriate analytical techniques without accreditation were used in some cases. The investigations showed that that there was not a single case of real groundwater contamination linked to normal and proper usage of glyphosate. The post-2004 detections have not been investigated.

11.4 Summary

Whilst there is a national collation of groundwater data, this does not apply to surface water data.

Glyphosate and AMPA monitoring data for surface water were obtained for several Federal States, as well as the ARW for the Rhine and a small amount for the river Ruhr. Glyphosate is frequently detected in surface waters and AMPA usually at higher frequencies and concentrations. Two states analysed AMPA only, which was not found at any monitoring stations (Bremen and Niedersachsen). An example of monthly sampling of the river Rhine showed very variable levels of glyphosate throughout the year, with the highest concentrations between March and September, whereas AMPA was consistently present at much higher concentrations and seemed to be increasing downstream.

In the absence of a Quality Standard (QS) for glyphosate (and AMPA), the 0.1 g l-1 target value for surface waters used as sources for drinking water production, as set by LAWA, is often used in the assessment of monitoring results, although one State (Mecklenburg- Vorpommern) referred to a proposed QS of 28 g l-1.

Some publications / professionals referred to AMPA in surface waters being derived at significant levels from sources other than glyphosate.

Groundwater data is collated at Federal level and glyphosate and AMPA data has been obtained for the years 1996-2008 (though 2008 data incomplete). Glyphosate and AMPA have been reported for a small number of sites, with AMPA at higher frequency and concentrations. However, an investigation (up to 2004) of sites with glyphosate detections showed all these to have been due to invalid analyses or contaminated observation wells.

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12. GREECE

12.1 Summary

A number of pesticide studies have been carried out in Greece, however, none of these included analyses for glyphosate and AMPA (Albanis et al., 2003; Papastergiou and Papadopoulou-Mourkidou, 2001; Miliadis and Malatou, 1997; Miliadis, 1998 and 1998a; Albanis et al, 1998).

We have been unable to obtain any more recent information from Greece.

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13. HUNGARY

13.1 Summary

According to the relevant national organisations in Hungary (Ministry of Environment and Water (KvVM), Central Directorate for Water and Environment (VKKI), Soil Science and Agrochemistry Research Institute of the Hungarian Academy of Sciences (MTA TAKI) and VITUKI Central Water Analytical Laboratory) there is no monitoring at any level for glyphosate or AMPA (János FEHÉR, "VITUKI" Environmental and Water Management Research Institute, personal communication, 2009).

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14. IRELAND

14.1 Introduction

As part of the Water Framework Directive (WFD) the Irish EPA carry out a monitoring programme of both surface water and groundwater. Glyphosate is included as a “relevant pollutant” for surface water and as part of the “Additional determinands” list for groundwater. Surface water data have been obtained, but no groundwater data. It is not clear whether groundwater monitoring for “Additional determinands” has started.

AMPA is not included in any monitoring programme in Ireland.

14.2 Surface Water

The Irish monitoring programme includes the priority substances in Annex IX and X of the WFD as well as a number of "relevant pollutants" as defined in Annex VIII of the Directive. The relevant pollutants were selected after a desk study followed by a monitoring exercise. Compounds which were found consistently were added to the list, this included glyphosate (information provided to Monsanto by Dr.Ciaran O'Donnell, personal communication, 2009). Monitoring commenced in July 2007 at 180 river sites and 76 lake sites. One third of these sites are sampled monthly during each of the years 2007, 2008 or 2009. All sites will have been monitored by the end of 2009.

While there has not been a formal report on the monitoring, raw data was released to the EU Commission on request, as part of the review by INERIS. We have received information from the EPA (provided to Monsanto from Dr.Ciaran O'Donnell, personal communication, 2009) that there are now over 1 700 results from this monitoring. Glyphosate has appeared above the detection limit (0.08 g l-1) in 98 samples. The levels range from <0.08 to 1.8 g l-1 (see Table 14.1).

Table 14.1 Glyphosate monitoring in surface waters in Ireland, 2007 to 2009 (source: provided to Monsanto by Dr.Ciaran O'Donnell, personal communication, 2009)

Date Number of No. of No. (%) of samples L.o.D. Max conc sites samples > LoD (g l-1) (g l-1) 2007 - 2009 180 (in rivers) 1 700 98 (5.8%) 0.08 1.8 76 (in lakes)

While these levels are not high when compared to a proposed Environmental Quality Standard (EQS) of approximately 60 g l-1, nevertheless the Irish consider it significant and they are going to continue to monitor for it in order to control the situation (Dr.Ciaran O'Donnell, personal communication 2009).

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14.2.1 South Eastern River Basin District

Reports were obtained (TNO, 2008 and TNO, 2007) of the South Eastern River Basin District Project (SERBD) which was carried out by Carlow County Council as part of the National Programme to test for relevance of all the candidate parameters of the WFD and to provide data to further the requirements to establish Environmental Quality Standards (EQS) levels for Irish waters. SERBD was an 18 month monitoring programme which incorporated sites downstream of major towns, sites associated with agriculture, mining and forestry activities and rural households, groundwater sites and two discharge effluent sites. The laboratory of TNO Environmental and Geosciences in The Netherlands provided the analytical services. Results of water samples, sediment samples and biota samples are included in the report. The study was carried out in three phases:

 Phase 1 – water samples from 23 sites (carried out during the second half of 2005);  Phase 2 – water samples continued to be collected. New target sites and biota samples included (carried out during the first half of 2006); and  Phase 3 – water samples from target sites only. Also biota and sediment samples (carried out during the second half of 2006).

In summary report no. 1 (TNO, 2008) the results from all 23 sites were listed. Glyphosate was the 4th most frequently found pesticide. It was only analysed in aqueous samples, not in sediments, due to the fact that it adsorbs strongly to sediments and so there was poor and irreproducible recoveries on analysis.

Glyphosate was detected at concentrations at or above the limit of detection (LoD = 0.1 g l-1) in 40 out of 287 samples (14%), with a maximum concentration of 4.0 g l-1. The 90th percentile result was 0.12 g l-1 (see Table 14.2).

In summary report no. 2 (TNO, 2007) glyphosate, as a ‘Relevant Pollutant’, was analysed in 40 water samples from target sites, being found in low concentrations at three sites. It was also analysed in 21 water samples from the forestry and sheep dipping target sites, but was not detected (see Table 14.2).

Table 14.2 Glyphosate results from the SE River Basin District, Ireland, 2005 - 2006 (source: TNO, 2007 and TNO, 2008)

Location No. sites No. No. samples detected Max. conc. LoD samples Number % µg l-1 µg l-1 Initial sites 23 287 40 13.9 4.0 0.1 Target sites ? 40 3 7.5 0.2 0.1 Sheep dip ? 21 0 - - 0.1 and forestry target sites TOTAL ≥ 25 348 43 12.3 4.0 0.1

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14.3 Groundwater

The Irish EPA website states that the WFD groundwater quality monitoring programme in Ireland will include a standard suite of determinands to be analysed at each monitoring location within the surveillance and operational monitoring networks. Additional determinands will be analysed on a case-by-case basis for operational monitoring. The pressures identified in the WFD Article 5 Risk Assessment have influenced the selection of these determinands. Glyphosate is included on this “Additional determinands” list. Monitoring results will be published on the EPA website, but none were available at the time of completing this review and it is not clear if, or when, this type of monitoring started. (Source: EPA website, http://www.epa.ie/downloads/pubs/water/other/wfd/#d.en.22416).

14.3.1 South Eastern River Basin District

Although the reports of the SERBD (TNO, 2008 and TNO, 2007) mention that it incorporates groundwater sites, the data from the groundwater sites were not readily split from the overall results.

14.4 Summary

The Irish national surface water monitoring programme includes glyphosate analyses in over 1 700 samples, taken between 2007 and 2009. Glyphosate was found above the detection limit (0.08 g l-1) in 98 samples (5.8%); the levels ranged from <0.08 to 1.8 g l-1.

The South Eastern River Basin District Project (SERBD) carried out monitoring between 2005 and 2006 to test for the relevance of all the candidate parameters of the WFD and to provide data to further the requirements to establish Environmental Quality Standards (EQS) levels. In this survey glyphosate was found above the detection limit (0.1 g l-1) in 43 out of 348 samples (12.3%), with a maximum concentration of 4.0 g l-1. Ireland has a proposed EQS of 60 g l-1 for glyphosate.

Glyphosate is included in the groundwater monitoring programme as one of the “Additional determinands” but no data were available at the time of completing this review, and it is not clear if monitoring has started.

AMPA is not included in the Irish monitoring programme for either surface water or groundwater.

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15. ITALY

15.1 Introduction

There does not appear to be any national monitoring programme or collation of data in Italy. However, glyphosate data were obtained for surface water and groundwater in the Lombardy Region.

A presentation paper by Capri on pesticide monitoring in Italy was also obtained from the literature search (Capri, 2007). It was not clear if glyphosate or AMPA were among the pesticides included in the monitoring suite, but they were not among the 64 herbicides/ pesticides detected. This paper also concluded that Italy still lacked an overall national picture with regard to pesticide monitoring data (based on 2005 data).

A regional report on the state of the environment in Emilia-Romagna (Regione Emilia- Romagna, 2000) included pesticides monitoring data for surface water and groundwater. It did not include any glyphosate or AMPA data, but it was not certain these were included in the monitoring suite. Later reports from Emilia-Romagna (ARPA, 2003 and 2003a) refer to the absence of pesticides in groundwater but, again, the pesticides which were monitored were not listed.

15.2 Surface Water

Recent results of surface water monitoring of glyphosate were received for the Lombardy Region (data provided to Monsanto by Giuseppina Veraldi, Arpa Lombardia). The summarised results are presented in Table 15.1 below.

Table 15.1 Results of glyphosate monitoring in surface waters of the Lombardy Region of Italy, 2005-2007 (source: data provided to Monsanto by Giuseppina Veraldi, Arpa Lombardia)

Year No. of No. of No. of No. of % of No. of % of Max. water sites samples samples samples samples samples conc. courses > LoD > LoD > 1 g l-1 > 1 g l-1 g l-1 2005 - 126 148 560 90 16.1 7 1.3 3.57 2006 2007 43 58 154 52 33.8 6 4 11.0 Total 128 * 150 * 714 142 20.0 13 1.8 11.0 Note: LoD = limit of detection 0.1 g l-1 * 2 additional rivers (2 sites) monitored in 2007

From a total of over 700 samples (150 sites on 128 water courses), 142 samples (20%) were above the limit of detection (LoD 0.1 g l-1), with the maximum concentration at 11.0 g l-1 in 2007 and 3.6 g l-1 in 2005-06. In 2005-06, seven samples (1.3%) were above 1.0 g l-1 and six samples (4%) above this level in 2007.

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15.3 Groundwater

Recent results of glyphosate monitoring in groundwater from the Lombardy Region, Italy, were received via Monsanto (data kindly provided to Monsanto by Giuseppina Veraldi, Arpa Lombardia). The summarised results are shown Table 15.2 below.

Table 15.2 Results of glyphosate groundwater monitoring in the Lombardy Region of Italy, 2005-2007 (source: provided to Monsanto by Giuseppina Veraldi, Arpa Lombardia)

Date No. of No. of No. of % of LoD Max. conc -1 sites samples samples samples -1 g l -1 -1 g l > 0.1 g l > 0.1 g l Nov-Dec 2005 73 80 0 - 0.05 – 0.1 <0.1 May-Jun 2006 63 64 0 - 0.1 <0.1 Oct-Nov 2006 12 12 0 - 0.1 <0.1 May-Jun 2007 126 137 5 3.6 0.1 1.2 Oct-Nov 2007 105 111 0 - 0.1 <0.1 TOTAL 183* 404 5 1.2 0.1 1.2 2005-2007

Note: * sites not added where they may be overlap – Total number is best estimate

The total number of sites is estimated at 183. This figure was obtained by looking at each Province and counting the number of sites for each year. The highest figure for each province was then taken and all these added together to estimate the maximum.

In summary, glyphosate was detected in 5 samples (1.2%), all in the period May-June 2007, with a maximum concentration of 1.2 g l-1. All of these detections occurred at different sites. We have no further information, such as type of sampling well or borehole and groundwater depth.

15.4 Summary

There are no national pesticides monitoring programmes in Italy, nor is there a national collation of data. However, we have received recent glyphosate data for surface water and groundwater in the Lombardy region of Italy.

For surface water, from a total of over 700 samples from 150 sites, taken between 2005 - 2007, 20% were above the limit of detection (0.1 g l-1), and 1.8% above 1 g l-1, with the maximum concentration at 11 g l-1.

For groundwater, from a total of over 400 samples, taken from around 180 sites between November 2005 and November 2007, only 5 samples (1.2%) were above the detection limit (0.1 g l-1), with a maximum concentration of 1.2 g l-1.

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16. LATVIA

16.1 Introduction

National monitoring programmes are in place in Latvia, surface water monitoring includes pesticides, but not glyphosate and AMPA, whereas groundwater monitoring does not include any pesticides. A study of Latvian groundwater was undertaken in co-operation with Denmark.

16.2 Surface Water

Whilst there is a national monitoring programme for surface water, the focus is on ‘dangerous substances’, i.e. HCH, HHB, lindane, DDE, DDT, DDD, endosulfan and endrin (Iraida Lyulko, Head of Observation Network Department, State Hydrometeorological Agency, personal communication, 2008). We have not been able to establish whether anything has changed since this communication.

16.3 Groundwater

Pesticides are not routinely monitored in groundwater in Latvia (Iraida Lyulko, Head of Observation Network Department, State Hydrometeorological Agency, personal communication, 2008).

A paper by Gosk et al. (2007) states that the regional groundwater quality monitoring network in Latvia, established in the 1970s and 1980s, is based on 150 wells located within 45 monitoring stations. Until recently, the parameters analysed comprised major ions and nitrogen compounds, with no analyses of heavy metals or pesticides, with groundwater quality data from abstraction wells consisting mainly of information collected during drilling. However, a large amount of information on the youngest groundwater in shallow aquifers has been collected in the period 2003–2005 as part of the present project. About 800 groundwater samples were analysed for a wide spectrum of elements, including heavy metals and pesticides (Gosk et al. 2006). Unfortunately this 2006 paper was not available so we cannot determine if glyphosate or AMPA were among those monitored. However, the Latvian study was carried out as part of a co-operative project between Latvia and Denmark and in the Danish studies both glyphosate and AMPA were included (Svendsen, et al., 2005).

This study has resulted in a comprehensive overview of the status of Latvian groundwater. Vulnerable areas were identified and 111 groundwater samples from wells in these areas were analysed for a number of pesticides most likely to be found. At present, the report concludes, there is limited data on pesticides and on the age of groundwater, which do not allow an assessment of the extent of the pesticide problem in Latvian groundwater with sufficient accuracy (Gosk et al., 2007). No further results from this programme could be obtained.

16.4 Summary

No glyphosate or AMPA data were found for Latvia, although it may have been included in at least one study.

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17. LITHUANIA

17.1 Summary

There is no monitoring data available for glyphosate or AMPA in groundwaters or surface waters in Lithuania, as these substances are not included in the official monitoring programmes (Jurga Arustiene, Head of Groundwater Monitoring, Lithuanian Geological Survey, personal communication, 2009).

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18. LUXEMBOURG

18.1 Summary

Luxembourg has surface water and groundwater monitoring programmes that include pesticides. However, glyphosate and AMPA were not included in a surface water monitoring programme in Luxembourg in 2000-2002, which included some pesticides, as reported in Ministère de l’Intérieur (2003). Neither were they included in an extensive groundwater monitoring programme, which included a large number of pesticides (Ministère de l’Intérieur et de l’Aménagement du Territoire, 2006).

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19. MALTA

19.1 Introduction

Surface water and groundwater monitoring is carried out in Malta, however, we have not been able to obtain any information on surface water monitoring. Details of the groundwater monitoring programme are described below.

19.2 Groundwater

The groundwater monitoring programme, as established for the Water Framework Directive, includes a total of 35 sampling points. The number of samples collected from each groundwater body is as follows:

 Malta Mean Sea Level: 12  Gozo Mean Sea Level: 6  Rabat Perched: 4  All other water bodies (which have been grouped for the purpose of the WFD): 1 station each

The first 18 sampling points were tested in March 2009, whilst the others will be tested within the following 2 months (Miriam Micallef Sultana, Malta Resources Authority, personal communication, July 2009).

All results for groundwater samples tested so far for glyphosate were below the detection limit of 0.01 g l-1. No tests were carried out for AMPA.

19.3 Summary

Groundwater monitoring includes 35 sampling points. To date the results from 18 of these have been obtained, all were below the detection limit for glyphosate. No AMPA monitoring was carried out. No surface water data was obtained.

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20. NORWAY

20.1 Introduction

The environmental agricultural monitoring programme (JOVÅ), which includes pesticide monitoring, focuses on surface waters, because it represents the largest source of drinking water supplies. Although there are 566 waterworks using groundwater and 637 using surface water, the groundwater works are generally small (88% supplying less than 1000 population equivalents each) and, in total, supply only about 10% of the population. Moreover, the risk of groundwater contamination with pesticides is considered low, since only about 3% of land is arable (Haarstaad & Ludvigsen, 2007).

A relatively small number of pesticides are approved for use in Norway (134 active ingredients in 2004). Total sales are relatively low, having declined from about 1400 tonnes of active ingredients in the 1980s to about 800 tons average 1992-2004, but dominated by herbicides. Glyphosate is the most widely used substance, having increased from an average of 273 tonnes a year in the period 2002-2006 to 315 tonnes in 2006 (Ludvigsen and Lode, 2008). The main usage of glyphosate is agricultural (on grain fields, such as wheat, barley etc.) and it is usually applied in autumn after harvesting the crops.

In line with the above, there is surface water data for glyphosate and AMPA, and only a small amount of groundwater data, all focusing on agricultural areas with likely contamination; these are summarised below. Earlier data are presented in the previous WRc review (Horth et al., 2004).

20.2 Surface Water

The Agricultural and Environmental Monitoring Programme (JOVÅ) has been on-going since 1995, conducted by the Agricultural Research Institute (Jordforsk) – Centre for Soil and Environmental Research – and the Plant Research Institute (Planteforsk) in Norway. The latter two institutes were later combined into one named Bioforsk. The JOVÅ programme mainly covers drainage catchments of various agricultural systems, soil types and climatic regions. For some of the catchments, agricultural practices, including pesticide usage, are documented. The sites for the glyphosate and AMPA survey were all selected in catchments with cereal production and significant usage of glyphosate (autumn applications) (Bechmann et al., 1999; Ludvigsen & Lode, 2001 and 2008; Haarstaad & Ludvigsen, 2007; and Dr. G.H. Ludvigsen, Centre for Soil and Environmental Research Jordforsk, personal communications).

Accredited special analytical techniques were used for glyphosate and AMPA. Prior to 2002 these analyses were carried out by Miljø-Kemi in Denmark (qualified and tested laboratory, accepted by the Danish EPA for inclusion of results in their groundwater survey), and subsequently by the Bioforsk laboratory. A detection limit of 0.01 µg l-1 has been achieved.

The monitoring data from 1997-2006 have been summarised in the most recent available Bioforsk report (Ludvigsen & Lode, 2008); these are presented in Table 20.1. Both glyphosate and AMPA were detected in most samples, though it must be emphasised, that these studies focused on agricultural areas of likely contamination.

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Table 20.1 Glyphosate application in agricultural areas and glyphosate and AMPA detected in streams and rivers in Norway, 1997-2006 (source: Ludvigsen and Lode, 2008)

Stream / river /canal Year Area % of Dose Total Samples Samples Max. Samples Max. Week no. Week no. Week no. spray total used active analysed positive conc. positive conc. sprayed detected analysed -ed crop subst. Gly Gly AMPA AMPA area used ha % g ha-1 kg No. No. (%) µg l-1 No. (%) µg l-1 No. No. No. Kolstadbekken (stream) 97 54.5 26 1 060 58 2 (S/B) 1 (50) 0.03 1 (50) 0.01 38-40 41 41, 49 98 21.7 10 1 010 22 5 (B) 1 (20) 0.09 2 (40) 0.02 34-40 36, 46 36, 46 Mørdrebekken(stream) 97 95.9 22 1 300 125 2 (S/B) 2 (100) 0.93 2 (100) 0.20 16, 32-38 37, 47 37, 47 98 64.1 14 1 170 73 7 (1S/6B) 7 (100) 0.47 7 (100) 0.09 21-40 9-44 9-44 99 81.6 18 1 270 104 7 ((B) 7 (100) 0.77 7 (100) 0.13 33, 38-40 3-48 3-48 00 19.1 4 1 390 27 5 (2S/3B) 5 (100) 0.10 5 (100) 0.21 34-39 17-44 17-44 01 35.5 8 1 150 41 2 (S/B) 2 (100) 0.22 1 (50) 0.20 18-42 14, 36 14, 36 06 64.9 15 1 220 78.9 2 (S/B) 2 (100) 0.23 2 (100) 0.09 32-40 46, 47 46, 47 Skuterud-bekken 97 129.7 42 1 260 163 2 (S/B) 2 (100) 0.05 2 (100) 0.08 33-40 39, 47 39, 47 (stream) 98 18.6 4 1 190 22 8 (B) 8 (100) 0.60 8 (100) 0.14 39 12-48 12-48 99 125.7 46 1 190 150 8 (7B/1S) 8 (100) 0.31 8 (100) 0.13 17-41 8-46 8-46 00 53 19 1 140 75 5 (4B/1S) 5 (100) 0.87 5 (100) 0.17 36-42 17-45 17-45 01 130.4 47 1 220 158 3 (S) 3 (100) 0.25 3 (100) 0.11 19-43 14,37,49 14,37,49 02 129.7 48 1 260 164 3 (S) 3 (100) 0.49 3 (100) 0.17 14,16,30-38 33,40,49 33,40,49 03 95.6 35 1 560 149 1 (S) 1 (100) 0.34 1 (100) 0.54 16,33-39 39 39 06 117.4 43 940 110 2 S/B) 2 (100) 0.29 2 (100) 0.17 34-42 46,47 46,47 Heiabekken (stream) 03 52.3 15 1 000 52 1 (S) 1 (100) 0.07 1 (100) 0.38 17-39 33 17-51 Heia-jb 06 0 - - - 1 (S) 1 (100) 0.13 1 (100) 0.13 - 46 46 Storelva (river); Klopp 97 - - - - 2 (S) 2 (100) 0.15 2 (100) 0.09 - 37, 40 37, 40 Hotrankanalen (canal) 97 - - - - 2 (B) 2 (100) 0.07 2 (100) 0.06 - 37, 39 37, 39 06 - - - - 2 (B) 2 (100) 0.05 2 (100) 0.03 - 48 48 Finsalbekken (stream) 97 - - - - 2 (S) 1 (50) 0.12 1 (50) 0.06 - 36 36, 48 Hobølelva (river) 98 - - - - 1 (S) 1 (100) 0.01 1 (100) 0.02 - 38 38 06 - - - - 1 (S) 1 (100) 0.28 1 (100) 0.16 - 46 46 Skas-Heigre-kanalen 06 - - - - 2 (S/B) 2 (100) 0.90 2 (100) 0.07 - 47,48 47,48 (canal) Vasshaglona 06 - - - - 2 (S/B) 2 (100) 0.06 2 (100) 0.09 - 47,48 47,48 Total 97-06 80 74 (92.5) 0.93 74 (92.5) 0.54 Notes: B = composite samples S = spot samples - not sprayed or no data / not relevant

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Earlier studies (Ludvigsen, 2001; Ludvigsen and Lode, 2001; more details given in previous WRc review, Horth et al., 2004) concluded that pesticide occurrence in the studied areas correlated with intensive farming, but did not discuss this with respect to individual pesticides. In general terms, peak concentrations were observed during spraying seasons and following run-off events. With respect to glyphosate, it was observed that AMPA was found at all sites where glyphosate was present, indicating that degradation was taking place. The highest levels of glyphosate and AMPA were generally found in autumn after glyphosate application and during the winter months when temperatures are unfavourable to biodegradation. However, where samples were taken over the winter months, levels decreased gradually through the winter months. Nevertheless, glyphosate and AMPA were detected in water samples 6-12 months after the last recorded glyphosate application. Overall, the situation does not appear to have changed significantly (Ludvigsen and Lode, 2008; Haarstad & Ludvigsen, 2007).

20.3 Groundwater

The Agricultural and Environmental Monitoring Programme (JOVÅ) described above focuses on surface water (see Section 20.2) in agricultural drainage basins, although a small number of groundwater samples have been included. The most commonly used pesticides in Norwegian agriculture were selected for analysis, including glyphosate (and AMPA). Pesticide monitoring in groundwater focused on shallow groundwater near agricultural fields, farm wells and public water supply wells, and has been carried out since 1995 (Haarstad & Ludvigsen, 2007).

The results for glyphosate and AMPA are shown in Table 20.2. From the 8 samples, there were no detections of glyphosate (limit of detection 0.01 g l-1) and just one detection of AMPA (concentration = 0.02 g l-1) above the limit of detection (0.01 g l-1). Although the report (Ludvigsen and Lode, 2008) covers all pesticides data from 1995-2006, glyphosate data for groundwater is only included for 1999-2000.

Table 20.2 Glyphosate and AMPA in groundwater in agricultural areas in Norway (source: Ludvigsen and Lode, 2008)

Site Year Samples Samples positive Max. conc. Samples positive Max. conc. analysed Glyphosate Glyphosate AMPA AMPA (>0.01 g l-1) (>0.01 g l-1) Number Number µg l-1 Number (%) µg l-1 20M 1999 1 0 - 0 - Skarnes 2000 1 0 - 0 - 2D Enebakk 2000 1 0 - 0 - 5L Vale 2000 1 0 - 0 - 6G As 2000 2 0 - 1 0.02 9H Rakkestad 2000 1 0 - 0 - 17H Rakkestad 2000 1 0 - 0 - Total 99-00 8 0 - 1 0.02

A published paper by Haarstad & Ludvigsen (2007) seems to include a few extra samples, although it covers only the period 1995–2004. In total, glyphosate was analysed in 19 samples over this period and detected in one of three samples in 1999 at 0.1 g l-1; AMPA was analysed in a total of 14 samples and detected in one of two samples in 2000 at a

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concentration of 0.02 g l-1; the latter is probably the same sample as those reported in Ludvigsen and Lode (2008) (Table 20.2), but the total reported number of samples is higher.

The one glyphosate detection was at a waterworks, whereas the single AMPA detection was at a farm well. This compares with an overall detection of herbicides in 79% of all samples taken during the reporting period, although glyphosate had the highest usage. The authors concluded that shallow groundwaters near agricultural fields were at risk of pesticide contamination, but very few pesticides were detected at public waterworks intakes. On the whole detections occurred mainly during the growing season and early winter. Pesticide monitoring at waterworks intakes ceased in 2002, whilst monitoring of shallow groundwater and farm wells continued (Haarstad & Ludvigsen, 2007).

20.4 Summary

Glyphosate and AMPA were detected in small streams in agricultural areas in a high proportion of samples, mainly shortly after application in autumn and during the winter months when conditions would not be expected to favour biodegradation, although in some cases they were found up to 12 months after application. It must be noted that the survey focused on relatively small agricultural drainage basins where pesticide contamination was considered likely.

In the same survey, both glyphosate and AMPA were detected once each (1999 and 2000 at different sites) in a small number of samples analysed between 1995 and 2006. Glyphosate was found at 0.1 g l-1 and AMPA at 0.02 g l-1. Overall, it was concluded that Norwegian groundwater (public supplies) was not at risk of pesticide contamination, although there was a potential risk to shallow groundwater near agricultural fields and farm wells.

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21. POLAND

21.1 Summary

We have been unable to obtain any data for Poland.

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22. PORTUGAL

22.1 Summary

The study of pesticides in surface waters (and groundwater) in Portugal by Cerejeira and co-workers (2003) between 1983 and 1999 did not contain any data for glyphosate or AMPA.

We have been unable to obtain any further information or data from Portugal.

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23. ROMANIA

23.1 Summary

Glyphosate and AMPA are not monitored in Romanian waters, although there are water protection measures in place for herbicides (Dr. Otilia Mihail, Ministry of Environment, Water Management Department, personal communication, 2009).

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24. SLOVAK REPUBLIC

24.1 Introduction

We have received information and data from the Slovak Republic. Glyphosate is monitored in surface waters, but not in groundwater; there is no monitoring of AMPA (Lea Mrafkova, Slovak Hydrometeorological Institute, personal communication, 2009).

24.2 Surface Water

We have received surface water glyphosate data from the Slovak Republic (Lea Mrafkova, Slovak Hydrometeorological Institute, personal communication, 2009); it has been monitored since 2006, in a total of 40 sites, with 330 samples analysed.

The sampling sites are located on 29 rivers located in eleven different river basins, namely:  Bodrog  Hornád  Slaná  Hron  Tisa  Ipeľ  Nitra  Poprad  Váh  Dunaj (Danube) and  Morava.

Data received has been summarised by year in Table 24.1 below.

Table 24.1 Glyphosate in surface waters in Slovak Republic 2006 – 2008 (source: Lea Mrafkova, Slovak Hydrometeorological Institute, personal communication, 2009)

Year No. No. of No. of No. of % of No. of % of LoD Max. of rivers samples samples samples samples > samples > g l-1 conc sites > LoD > LoD 0.1 g l-1 0.1 g l-1 g l-1

2006 23 21 55 4 7.3 0 - 0.05 0.09

2007 31 27 136 57 41.9 24 17.6 0.05 3.6

2008 33 26 139 44 31.7 25 18.0 0.05 0.47

Total 40 29 330 105 31.8 49 14.9 0.05 3.6 2006-09

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24.3 Groundwater

Glyphosate and AMPA are not monitored in groundwaters in the Slovak Republic (Lea Mrafkova, Slovak Hydrometeorological Institute, personal communication, 2009).

24.4 Summary

Glyphosate has been monitored in surface waters since 2006, with 330 samples analysed between 2006 and 2008, from a total of 40 sites, located on 29 rivers. Over 30% (105 samples) of these samples had levels of glyphosate above the limit of detection (0.05 g l-1) and nearly 15% (49 samples) had levels above 0.1 g l-1. The maximum concentration of glyphosate reported in surface waters was 3.6 g l-1.

Glyphosate is not monitored in groundwaters.

There is no monitoring of AMPA in the Slovak Republic.

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25. SLOVENIA

25.1 Summary

Monitoring of groundwater and surface water in Slovenia did not include any analysis for glyphosate or AMPA prior to 2009. However, preliminary surface water monitoring has begun in 2009 at a few sampling sites, at a frequency of two samples a year, but the results are not yet available (Špela Kozak Legiša, Environmental Agency of the Republic of Slovenia, personal communication, 2009).

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26. SPAIN

26.1 Introduction

Glyphosate has recently been monitored in two river basins districts where there are water quality issues, as detailed below. No glyphosate monitoring is carried out on groundwater and there is no monitoring of AMPA.

26.2 Surface Water

We received around 750 analytical data of glyphosate in Spain (Javier Cachón de Mesa, Head of Environmental Information, Ministry of Environment, personal communication, 2009). Currently, there are no available data of its degradation product AMPA.

The provided data, summarised in Table 26.1, were all of continental surface water bodies, and were collected as part of the impact monitoring network, which is made up of stations where significant discharges are located. For that reason, these data are not considered representative of the general situation of the Spanish rivers, but they are representative of those places with important quality problems. This issue should be taken into account when comparing this dataset with other EU countries.

Year No. of No. of No. No. samples LoQ Max. sites* samples samples (%) > 0.1 g l-1 (g l-1) conc. (%) > LoQ (g l-1) 2006 17 101 23 (23%) 23 (23%) 0.003 2.9 2007 49 291 9 (3%) 8 (3%) 0.003 – 0.1 1.6 2008 107 356 64 (18%) 49 (14%) 0.003 – 0.1 15.3 TOTAL* 115 748 96 (13%) 80 (11%) 0.003 – 0.1 15.3 (2006-2008) * Total of sites not cumulative as includes where sites are monitored in more than one year.

The data, collected from July 2006 until September 2008, are from two river basin districts:  Mediterranean internal basins of Andalusia; and  Atlantic internal basins of Andalusia.

Glyphosate was detected in 96 (13%) of samples from 115 sites monitored between 2006 and 2008; 80 samples (11%) were found at concentrations above 0.1 g l-1 and the maximum concentration was 15.3 g l-1 (in 2008).

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26.3 Groundwater

Glyphosate and AMPA have not been monitored in groundwater in Spain (Mrs Alejandra Puig, Ministry of Environment, personal communication, 2009).

26.4 Summary

Glyphosate has only recently been monitored in the surface water of two river basins districts where there have been water quality issues. It was detected above the LoQ in 13% of samples and above 0.1 g l-1 in 11% of samples. The maximum concentration detected was 15.3 g l-1. However, it should be noted that these data are not representative of the general situation of Spanish rivers, but are representative of those places with important quality problems.

No glyphosate monitoring is carried out in groundwater, and there is no AMPA monitoring in Spain at present.

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27. SWEDEN

27.1 Introduction

Drinking water supplies in Sweden are provided about 50/50 from surface water and groundwater sources.

Glyphosate alone represents over a third of total Swedish sales of plant protection products. The main usage of glyphosate in Sweden is agricultural, but non-agricultural applications (private gardens, urban usage, railway lines etc.) are also of importance (Adielsson and Kreuger, 2006).

Environmental monitoring of pesticides in Sweden started during the mid-1980’s as short term, research based, investigations of possible occurrence of pesticides in streams and rivers. Long-term, systematic monitoring of different compartments of the aquatic environment has gradually evolved and now includes several monitoring sites with sampling in different matrixes such as surface water, ground water, sediments and precipitation. The Swedish Environmental Protection Agency (Swedish EPA) is the authority responsible for all the Swedish environmental monitoring programmes. The pesticide monitoring programme is performed by the Division of Water Quality Management, in collaboration with the Section of Organic Environmental Chemistry, at the Swedish University of Agricultural Sciences (SLU) (TemaNord, 2007).

There is also a Regional Pesticide Database (SLU Pesticides Database, 2008) available which includes data from all investigations of pesticide occurrence in the aquatic environment performed in Sweden (Törnquist et al., 2007). The database, set up in 1996, gives a nationwide picture of pesticides detected, or monitored but not detected, in the Swedish environment, based on investigations performed by local and regional authorities, e.g. the national county boards, waterworks and water conservation associations. The information now comprises a 23-year period (1985 – 2008) and contains information on more than 10 000 water samples covering all Swedish water districts and counties and 88% of the municipalities. The work is administrated by the Division of Water Quality Management at SLU and funded by the Swedish EPA.

The link to the database was provided by Dr Jenny Kreuger of the SLU (personal communication, 2008). The version was dated 19 September 2008 and was queried on 18 August 2009 and 03 September 2009 for glyphosate and AMPA in all regions, for surface water and groundwater (latest available data was 2008).

27.2 Surface Water

Glyphosate and AMPA detections in Swedish surface waters, as extracted from the SLU database (2008), are shown in Table 27.1 and Table 27.2. Both glyphosate and AMPA were frequently detected in surface waters. Surprisingly, glyphosate was detected more frequently (24.7% of samples) and at higher concentrations (maximum 13 µg l-1) than AMPA (13.6% of samples and a maximum concentration of 4.0 µg l-1).

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Table 27.1 Glyphosate in Swedish surface water, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se)

Region Number of Number (%) Maximum Median Average Code samples of samples concentration concentration concentration analysed detected µg l-1 µg l-1 µg l-1 AB 24 1 (4.2) 0.060 0.060 0.002 AC 4 0 - - - BD 29 2 (6.9) 0.730 0.030 0.026 C 67 40 (59.7) 0.120 0.030 0.021 D 27 0 - - - E 65 10 (15.4) 0.400 0.016 0.015 F 41 0 - - - G 41 0 - - - H 14 0 - - - I 26 5 (19.2) 0.110 0.110 0.004 K 22 0 - - - M 157 101 (64.3) 13.000 0.097 0.194 N 13 6 (46.2) 0.100 0.050 0.018 O 201 34 (16.9) 6.000 0.280 0.135 S 19 2 (10.5) 0.080 0.072 0.008 T 58 10 (17.2) 0.360 0.050 0.022 U 18 7 (38.9) 13.000 0.040 1.033 W 18 0 - - - X 25 0 - - - Y 5 0 - - - Z 7 0 - - - Total / maximum 881 218 (24.7) 13.000 0.280 1.033

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Table 27.2 AMPA in Swedish surface water, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se)

Region Number of Number (%) Maximum Median Average Code samples of samples concentration concentration concentration analysed detected µg l-1 µg l-1 µg l-1 AB 24 3 0.200 0.070 0.014 AC 4 0 - - - BD 28 0 - - - C 62 2 0.200 0.200 0.003 D 27 0 - - - E 65 9 0.200 0.035 0.009 F 39 0 - - - G 41 0 - - - H 14 0 - - - I 26 0 - - - K 22 0 - - - M 156 69 (44.2) 3.000 0.100 0.083 N 13 1 (7.69) 0.000 (?) - 0.000 O 201 26 (12.9) 4.000 0.300 0.067 S 19 1 (5.26) 0.070 - 0.004 T 58 5 (8.6) 0.200 0.010 0.006 U 14 2 (14.3) 0.200 0.130 0.024 W 18 0 - - - X 25 0 - - - Y 5 0 - - - Z 7 0 - - - Total / maximum 868 118 (13.6) 4.000 0.300 0.083 Note: ? = not clear, i.e. the maximum concentration is given as 0.000 µg l-1, although one detection is listed

The most frequently detected pesticides in surface water in 2003 were bentazone, glyphosate, MCPA, clopyralid, IPU, mecoprop and fluroxypyr as shown in Figure 27.1. In sediments, it is mostly glyphosate that is detected (Kreuger & Adielsson, 2006).

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Figure 27.1 Detection frequency in surface water (>10%), 2003 data (source: Kreuger & Adielsson, 2006)

27.3 Groundwater

The available data extracted from the SLU Pesticides database (2009) for glyphosate and AMPA in 2000 – 2008 is shown in Tables 27.3 to 27.5. Glyphosate was detected in four regions on a few occasions, only in one of these at concentrations above 0.1 µg l-1. For the regions where glyphosate was detected, a breakdown by year is also shown (Table 27.4). This shows that glyphosate at or above 0.1 µg l-1 in Region M were reported in 2001, 2002, 2004 and 2006. None of the detections occurred after 2006, indicating no persistent contamination of groundwaters. (See also more detailed comments in the WRc Drinking Water Report, Horth and Gendebien, 2008).

AMPA showed a similar pattern of detections in Regions M and S, with the highest number in Region M and somewhat higher concentrations. The other detections were in different regions (T and X) than the glyphosate detections (C and O).

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Table 27.3 Glyphosate in Swedish groundwater, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se)

Region Number of Number (%) Maximum Median Average Code samples of samples concentration concentration concentration analysed detected µg l-1 µg l-1 µg l-1 AB 41 0 - - - AC 143 0 - - - BD 94 0 - - - C 231 1 (0.43) 0.020 0.020 0.000 D 111 0 - - - E 82 0 - - - F 190 0 - - - G 85 0 - - - H 88 0 - - - I 65 0 - - - K 70 0 - - - M 774 9 (1.16) 0.170 0.100 0.001 N 81 0 - - - O 240 4 (1.67) 0.080 0.030 0.001 S 132 2 (1.52) 0.085 0.020 0.001 T 29 0 - - - U 52 0 - - - W 171 0 - - - X 188 0 - - - Y 192 0 - - - Z 4 0 - - - Total / maximum 3 063 16 (0.52) 0.170 0.100 0.001

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Table 27.4 Glyphosate detection in groundwater in Regions M, C, O and S, 2000 – 2008 * (source: SLU Pesticides Database, 2008, http://pesticid.slu.se)

Year Number of Number of Maximum Median Average samples samples concentration concentration concentration analysed detected µg l-1 µg l-1 µg l-1 Region M 2008 8 0 - - - 2007 20 0 - - - 2006 192 2 0.170 0.120 0.002 2005 198 1 0.010 0.010 0.000 2004 118 2 0.110 0.100 0.002 2003 61 0 - - - 2002 85 2 0.100 0.080 0.002 2001 45 2 0.140 0.021 0.001 2000 47 0 - - - Region C 2007 10 0 2001 1 1 0.020 - - Region 0 2007 5 0 2003 3 3 0.080 0.030 0.050 2002 1 1 0.035 - - Region S 2005 1 1 0.020 - - 2004 1 1 0.085 - - Note: shown only for years analysed

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Table 27.5 AMPA in Swedish groundwater, 2000 - 2008 (source: SLU Pesticides Database, 2008, http://pesticid.slu.se)

Region Number of Number (%) Maximum Median Average Code samples of samples concentration concentration concentration analysed detected µg l-1 µg l-1 µg l-1 AB 38 0 - - - AC 143 0 - - - BD 94 0 - - - C 223 0 - - - D 111 0 - - - E 82 0 - - - F 190 0 - - - G 85 0 - - - H 89 0 - - - I 65 0 - - - K 70 0 - - - M 753 11 (1.46) 0.680 0.059 0.002 N 81 0 - - - O 237 0 - - - S 131 1 (0.76) 0.020 0.020 0.000 T 28 1 (2.73) 0.010 0.010 0.000 U 52 0 - - - W 171 0 - - - X 173 5 0.350 0.130 0.005 Y 189 0 - - - Z 4 0 - - - Total / maximum 3 009 18 (0.60) 0.680 0.130 0.005

27.4 Summary

Glyphosate and AMPA data were obtained on line from the Swedish database where all data obtained at national, regional and local level is collated.

Glyphosate and AMPA were frequently detected in surface waters, though unlike in most countries, glyphosate was found more frequently and at higher concentrations than AMPA.

Both substances were occasionally detected in groundwater, but indicating no persistent contamination of groundwaters.

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28. SWITZERLAND

28.1 Introduction

Glyphosate and AMPA have recently been monitored in groundwater in Switzerland as part of a special national pesticide monitoring programme. There seems to be no comparable national surface water monitoring programme, or no collation of recent data, but a few results have been obtained from a published paper.

28.2 Surface water

28.2.1 National Data

There does not seem to be an up-to-date collation of surface water monitoring data. The most recent available surface water quality report (BUWAL, 2000) covers the years 1997-98 and does not include any pesticides monitoring data. However, a small amount of regional data was available in a published paper (provided by Christian Leu, Federal Environment Agency - BAFU, personal communication, 2009) – see below.

28.2.2 Regional Study

Swiss Plateau

A few lake and river water results for the ‘Swiss Plateau’, an area of high agricultural activity and in parts densely populated (i.e. likely contributions from urban sources) were obtained from a published paper, which focused on analytical method development (Hanke et al., 2008).

The method of analysis was based on derivatisation with 9-fluorenylmethylchloroformate (FMOC-Cl), solid-phase extraction and liquid chromatography followed by electrospray tandem mass spectrometry (LC-ESI-MS/MS). AQC was carried out with all environmental sample analyses. The limits of detection (LoD) and limits of quantification (LoQ) were very low, established as follows for surface water samples:

Glyphosate LoD 0.2 ng l-1 LoQ 0.7 ng l-1 AMPA LoD 0.2 ng l-1 LoQ 0.8 ng l-1

Samples were taken in summer and the stratified lakes were sampled at different depths (two samples from the epilimnion, i.e. warmer upper layer; and three samples from the hypolimnion, i.e. cold bottom layer). Samples were also taken from the main tributaries of the two lakes, as well as from the river Rhine.

The results are summarised in Table 28.1. In view of the loads from the tributaries and the residence time of the water in the lakes, the lower levels in the lakes were attributed to likely degradation and/or sorption.

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Table 28.1 Glyphosate and AMPA in surface water in Switzerland (source: Hanke et al., 2008)

Location Description Glyphosate AMPA µg l-1 µg l-1 Murtensee Lake - epilmnion nd 0.004 – 0.005 Lake - hypolimnion 0.015 0.060 Tributary 0.100 0.290 Greifensee Lake - epilmnion nd – 0.005 0.004 – 0.010 Lake - hypolimnion 0.035 0.060 Tributary 0.030 – 0.390 0.100 – 0.170 Rhine River 0.025 – 0.055 0.055 – 0.065

28.3 Groundwater

28.3.1 National Collation of Data

Until recently, there was no national groundwater monitoring programme in Switzerland, mainly because of its Federal structure, where the Cantons have their own monitoring programmes without centralised co-ordination. However, an investigation was undertaken on behalf of the Swiss Federal Agency for the Environment, Forests and Landscape (Bundesamt für Umwelt, Wald und Landschaft – BUWAL) to collate data from regional monitoring programmes carried out by the Cantonal authorities. This was followed in 2002 by the establishment of a national groundwater monitoring programme in Switzerland, whereby Cantonal authorities receive funding from Federal Government to carry out monitoring according to criteria set by BUWAL (now Federal Department of the Environment – Bundesamt fur Umwelt BAFU), and the requirement to provide the results to the Federal authorities for analysis. Glyphosate was not included initially (Dr Benjamin Meylan, BUWAL, Sektion Grundwasserschutz (Groundwater Protection Division), Bern, personal communication, 2004).

Glyphosate and AMPA have been included since 2005 as part of a programme, additional to the standard national monitoring programme for pesticides in groundwater (BAFU, 2009, report provided by Sybille Kilchmann, BAFU, personal communication, 2009). The standard programme includes around 500 monitoring stations, representative of Swiss groundwaters, whereas the additional programme involved about 115 monitoring stations, selected on the basis of likely pesticide presence, as determined in earlier pilot studies. Samples were generally taken four times per year. AQC procedures are in place, including participation of laboratories in ring tests and evaluation of the results by BAFU. As the detection limits (LoD) may vary among different laboratories, the evaluation is normally based on the maximum reported LoD.

Glyphosate and AMPA data for the years 2005 and 2006 are presented in Table 28.2 (BAFU, 2009). Whilst glyphosate was detected at four of the 117 sites in 2005, with three of these at concentrations above 0.1 µg l-1, none was detected in the following year. AMPA, however, was detected in both years and at higher concentrations than glyphosate. There is no specific

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information about the type of groundwater, depth or sampling sites, where glyphosate and AMPA were found, although aquifers include solid rock (Karst, limestone, granite) and loose rock formations, and monitoring sites comprise mainly water abstraction wells and springs and a small number of piezometers. Short-term shallow ground water contamination therefore seems a likely scenario.

Table 28.2 Glyphosate and AMPA in groundwater in Switzerland (BAFU, 2009)

Substance Year LoD Number of sites % sites Statistics relating to results >LoD (µg l-1)

µg l-1 n >LoD >0.1 >LoD >0.1 Min. 1st Median 3rd Max. µg l-1 µg l-1 quartile quartile

Glyphosate 2005 0.05 117 4 3 3 3 0.077 0.109 0.133 0.162 0.210

2006 0.05 117 0 0 ------

AMPA 2005 0.05 117 10 6 9 5 0.054 0.089 0.109 0.137 0.219

2006 0.05 115 7 5 6 4 0.059 0.105 0.133 0.277 0.456 LoD = Detection limit

28.3.2 Regional Studies

Swiss Plateau

Groundwater samples from 10 sites in the ‘Swiss Plateau’, an area of high agricultural activity and in parts densely populated (i.e. likely contributions from urban sources), were analysed as part of a limited survey following an analytical method development (Hanke et al., 2008) (see Section 28.2 above for a brief description of the analytical technique).

The limits of detection (LoD) and limits of quantification (LoQ) were established as follows for groundwater samples:

Glyphosate LoD 0.5 ng l-1 LoQ 1.8 ng l-1 AMPA LoD 0.1 ng l-1 LoQ 0.5 ng l-1

Glyphosate or AMPA were not detected in any of the samples.

County of Solothurn

Some earlier data, collated from regional (Cantonal) programmes (1995/96), where glyphosate was monitored and detected once in 1998 but not in any follow-up samples (Olschewski and Würsten, 1999; and Würsten, personal communication, 2004), is included in the previous WRc report (Horth et al., 2004).

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28.4 Summary

A small number of detections of glyphosate and AMPA in surface water revealed relatively low levels of glyphosate (maximum at 0.39 µg l-1) and AMPA (maximum at 0.29 µg l-1) in lakes and rivers, whereas a small number of detections in groundwater analyses may be attributable to short-term contamination of shallow ground water or spring water.

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29. THE NETHERLANDS

29.1 Introduction

In the Netherlands, a high proportion of drinking water is derived from surface water or indirectly from bank filtrate. The drinking water regulations in the Netherlands (Waterleidingsbesluit of 7 June 1960, as amended 1994) also included surface water quality criteria in relation to treatment requirements. Therefore, although glyphosate is likely to be removed during drinking water treatment, it is considered relevant to know its occurrence in water intakes, and therefore the 0.1 µg l-1 value is often used in relation to glyphosate in surface water (but not AMPA, which is not considered ‘relevant’ for drinking water).

Glyphosate is widely used for agricultural (about 80% of total usage) and non-agricultural (~20%) purposes (Van der Linden et al., 2007).

Data for surface water and groundwater at national level, as well as additional data for the river Rhine, the Netherlands’ part of the Maas river basin district, and Levoland are summarised below.

Earlier data are included in the previous WRc review (Horth et al., 2004). This includes a study of surface water and drainage water in fruit growing areas, with data for 1996-2001 (ZHEW, 2002). It also includes a study of run-off from hard surfaces (Puijker and Janssen, 1999), for which the main conclusion was that run-off from hard surfaces could contribute significant amounts of glyphosate to surface waters.

29.2 Surface Water

29.2.1 National data from the pesticides atlas

The Pesticides Atlas (2008) which is available on line provides a comprehensive picture of the national situation on pesticides in surface water (www.bestrijdingsmiddelenatlas.nl, link provided by Leo Puijker, KIWA Water Research, personal communication, 2008).

All the pesticide monitoring data used in the Pesticides Atlas are derived from the water quality databases owned and administered by 28 water boards responsible for monitoring pesticides in surface waters of the Netherlands, with prior checks being made on data quality and quantity. The main feature of the Pesticides Atlas is a large set of maps (with grid cells of either 5×5 km or 1×1 km) and histograms summarising measured concentrations of individual pesticides in relation to quality standards in force in the Netherlands:

 the European drinking water standard;

 the ecological standard Maximum Tolerable Risk (MTR); and

 the pesticide authorisation standard applied by the Dutch Board for the Authorisation of Pesticides (CTB).

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The first of these standards has been set at 0.1 µg l-1 for most individual pesticides and some relevant metabolites, while the other two are pesticide-specific and vary (De Snoo et al., 2006).

Glyphosate and AMPA are included in the database, which was queried on line on 20-08-2009, (database version 13-12-2008), and the information for the most recent available information (2006) is summarised below.

Glyphosate was listed among the top ten pesticides in terms of exceeding the 0.1 µg l-1 drinking water standard in surface waters, whilst there were no exceedances of the MTR, set at 77 µg l-1, or the CTB at 64 µg l-1. It is worth noting that AMPA is not considered a ‘relevant’ metabolite in terms of the drinking water standard in the Netherlands, and results can therefore not be queried against the 0.1 µg l-1 standard; the only available standard is the MTR, which has been set at 79.7 µg l-1 for AMPA, although there is also a target value (TV) of 8 µg l-1 (MTR divided by 100).

In 2006, a total of 1 384 samples from 300 sites were analysed for glyphosate, and 1 410 samples from 305 sites for AMPA. The sampling pattern varied throughout the year in terms of sites and samples analysed, with the highest number being taken in the summer (May to September). The results for AMPA and glyphosate are summarised in Table 29.1 and, for glyphosate, shown in Figure 29.1. Actual concentrations are not available; the database can only be queried against given standards; thus the 0.1 µg l-1 drinking water standard was used for glyphosate and the MTR of 79.7 µg l-1 for AMPA.

Table 29.1 Glyphosate and AMPA in surface water in the Netherlands in 2006 (source: Pesticides Atlas, 2008, last updated 13 Dec. 2008)

Compound Concentration range Number of sites % of total

Glyphosate Not detected or not quantifiable 85 28.3 (300 sites) < 0.1 µg l-1 106 35.3 ≤ 1.0 µg l-1 75 25 > 1.0 µg l-1 34 11.3 AMPA (305 sites) < TV of 8 µg l-1 255 83.6 >TV ≤ MTR of 79.7 µg l-1 50 16.4 ≥MTR 0 - MTR = Maximum Tolerable Risk TV = ‘target value’ = MTR/100

The number of detections of glyphosate were highest in the summer months, as shown in terms of sites exceeding 0.1 µg l-1 (see Figure 29.2), co-inciding with the higher sampling frequency during this period; the patterns are similar (not shown). A similar general pattern applies to AMPA.

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Notes: blue = <0.1 µg l-1, grey = below limit of quantification, yellow = <1.0 µg l-1, red = >1.0 µg l-1

Figure 29.1 Glyphosate in surface water in the Netherlands in 2006, in terms of sites and the 0.1 µg l-1 drinking water standard (source: Pesticides Atlas, 2008, last updated 13 Dec. 2008)

Figure 29.2 Glyphosate in surface water in the Netherlands in 2006, in terms of sites exceeding the 0.1 µg l-1 drinking water standard on a monthly basis (source: Pesticides Atlas, 2008, last updated 13 Dec. 2008)

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The database also includes trend analyses. It was suggested that the concentrations have been increasing over the years from an average of 0.085 µg l-1 in 1997 to 0.16 µg l-1 in 2006. However, there was wide variability in the annual averages over the years and the number of sites and samples analysed has also increased from 57 sites and 312 samples in 1997, to 300 sites and 1 384 samples in 2006.

29.2.2 National data from surface water intakes for drinking water supplies

Since the drinking water quality reports include monitoring data for glyphosate and AMPA at surface water intakes (Versteegh et al., 2002 - 2008 and undated), these are also summarised in Table 29.2 (groundwater intakes are not reported, as standards do not apply to these). Only detections are reported, not the total number of sites and samples analysed. It is clear from these data that glyphosate and AMPA were detected in a number of samples and frequently found above the drinking water standard at surface water intakes for drinking water supplies in the years 2000 – 2006; in general, AMPA was detected more frequently and at higher concentrations than glyphosate. (The 2006 data are likely to be included in the Pesticides Atlas (see Section 29.2.1).

More details for 2000-2006 are presented in the ‘Drinking Water Report’ (Horth and Gendebien, 2008).

Table 29.2 Glyphosate and AMPA detections in raw water intakes (surface water) in the Netherlands, 2000-2007 (source: Drinking water quality reports 2000 - 2006, Versteegh et al., 2002 - 2008 and undated)

Year Substance Number of Number of Minimum Maximum sites* detections (g l-1) (g l-1) 2000 Glyphosate 2 14 <0.05 0.15 AMPA 3 21 0.06 1.3 2001 Glyphosate 1 8 <0.05 0.14 AMPA 2 15 <0.03 0.92 2002 Glyphosate 1 13 <0.05 0.25 AMPA 2 17 0.03 0.82 2003 Glyphosate 2 17 <0.05 0.38 AMPA 5 28 <0.1 1.9 2004 Glyphosate 2 25 <0.05 0.45 AMPA 5 46 <0.05 1.2 2005 Glyphosate 4 47 <0.10 0.36 AMPA 6 67 <0.10 1.20 2006 Glyphosate 3 65 <0.05 0.43 AMPA 5 91 <0.05 1.4 2007 Glyphosate 3 71 <0.03 0.26 AMPA 3 71 <0.03 1.6 TOTAL* Glyphosate 9 260 <0.03-<0.1 0.45 2000-2007 AMPA 12 356 <0.03-<0.1 1.9 Notes: * Total of sites not cumulative as includes where sites monitored in more than one year

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29.2.3 Zuiderzeeland Water Authority

A small amount of glyphosate and AMPA data for 2006-2007 has been published by the Water Authority of Zuiderzeeland (Waterschap Zuiderzeeland, 2008; report provided by M-A. Reding, Monsanto Europe, personal communication, 2009). There are three different pesticide monitoring programmes in Flevoland, one at pumping stations, one at horticultural sites (glass houses), and the third is an agricultural monitoring network. Glyphosate and AMPA were listed among the top 20 detected in all three networks combined, in terms of detection frequency, with glyphosate at number 13 and AMPA at number 9. In total, during 2006-2007, glyphosate was detected at 49 sites, with a maximum concentration of 8.2 µg l-1; AMPA was detected at 57 sites with a maximum concentration of 1.4 µg l-1. It should be noted that the above monitoring results for 2006 are probably included in the Pesticides Atlas (2008) as summarised in Section 29.2.1.

In the agricultural network, glyphosate was detected at 34 sites (or 40% of sites) and AMPA at 36 or 42% of sites during the same period. Concentrations were not presented.

An attempt was made to look at trends, but glyphosate data were available for 2003-2007 only (see Figure 29.3). The darker line shows average glyphosate concentrations, the lighter line shows detection limits (LoDs) in µg l-1 (it is surprising that LoDs should have increased from 2005-2007 to 0.2 µg l-1). Overall there may be a downward trend, but the data are inadequate to demonstrate this.

Note: dark line = average glyphosate concentration; lighter line = limit of detection

Figure 29.3 Glyphosate concentrations in surface waters in Flevoland, 2003-2007 (from Waterschap Zuiderzeeland, 2008)

29.2.4 Maas River Basin District

Some additional surface water data for the Netherlands’ part of the Maas River Basin District (RBD) in 2007 has been published in Verhagen et al. (2008) (report provided by M-A. Reding, personal communication, 2009) and is summarised below.

Glyphosate and AMPA were reported as being among the 20 substances most frequently detected; AMPA was in 6th position with about 200 detections (samples), and glyphosate in 20th position with about 100 detections. They were also reported as being among the top ten with the highest maximum concentrations; AMPA with 4.5 µg l-1 found in the Peel and Maasvallei Water Authority, and glyphosate with 7.1 µg l-1 in the De Dommel Water Authority.

The authors suggested that a higher proportion of AMPA and glyphosate exceedances of 0.1 µg l-1 occurred at monitoring sites influenced by urban areas and wastewater treatment

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effluents, although the data as presented is not convincing; the comparison is between a very small number of sites influenced by wastewater treatment effluent (7 versus 81 in total) or urban areas (5 versus 83 in total). In the latter comparison the percentage exceedance for glyphosate was lower for sites with urban influence (4% of samples analysed versus 6% for the total number). For AMPA, however, the percentage exceedance was higher for sites with urban influence (17% of samples versus 9% for the total number); in the case of AMPA it is likely that the difference was due mainly to sources other than glyphosate. The report does refer to an earlier publication (Volz, 2007) which concluded that 40% of AMPA input into the river Maas was derived from such sources.

Overall, the authors of the report concluded that there were significant sources of glyphosate and AMPA from non-agricultural use. They recommended that citizens should be advised at provincial level about appropriate glyphosate usage. They also indicated that wastewater treatment effluents could contribute to glyphosate inputs into surface waters.

29.2.5 River Rhine Studies

Glyphosate and AMPA data for the River Rhine at Lobith have been published by RIWA (Association of River Waterworks) for 1999-2000 (RIWA, no date) and for 2001-2002 (RIWA, no date – a). Table 29.3 shows a summary of these data, whilst Table 29.4 shows the data in terms of monthly observations. Additional data for other monitoring stations on the Rhine are summarised in Table 29.5 in terms of maximum concentrations found (2001 and 2002 only).

Whilst AMPA was consistently present, glyphosate was mainly detected in the period April to August, although sometimes later in the year as well, but never from January to March. Glyphosate concentrations were considerably lower than AMPA concentrations, with the maximum concentrations at 0.2 µg l-1 for glyphosate and 0.73 µg l-1 for AMPA. Somewhat higher maximum concentrations of glyphosate were observed at other monitoring stations on the Rhine, i.e. 0.41 µg l-1 at Nieuwegein and 0.25 µg l-1 at Nieuwersluis in 2002 (see Table 29.5).

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Table 29.3 Glyphosate and AMPA in the River Rhine at Lobith in the Netherlands, summary of results, 1999-2002 (sources: RIWA, no date and no date - a)

Year / No. Concentration (µg l-1) Substance samples LoD Min. Av. Max. p10 p50 p90 1999 Glyphosate 13 0.05 < < 0.08 <0.05 <0.05 0.06 AMPA 13 ? 0.09 0.25 0.43 0.12 0.19 0.39 2000 Glyphosate 13 0.05 < 0.05 0.11 <0.05 0.05 0.09 AMPA 13 ? 0.10 0.25 0.40 0.11 0.27 0.36 2001 Glyphosate 11 0.05 < 0.06 0.13 <0.05 <0.05 0.13 AMPA 11 ? 0.11 0.27 0.45 0.11 0.28 0.41 2002 Glyphosate 12 0.05 < 0.09 0.2 <0.05 0.08 0.19 AMPA 12 ? 0.15 0.30 0.73 0.16 0.26 0.49 Total 1999-2002 Glyphosate 49 0.05 <0.05 <0.05- 0.2 <0.05 <0.05- 0.06- 0.09 0.08 0.19 AMPA 49 ≤0.09 0.09 0.25- 0.73 0.11- 0.19- 0.36- 0.30 0.16 0.26 0.49 Notes: LoD = limit of detection p10, p50, p90 = 10, 50, 90 percentiles < = not detected - = not appropriate ? = no information

Table 29.4 Glyphosate and AMPA in the River Rhine at Lobith in the Netherlands, monthly results, 1999-2002 (sources: RIWA, no date and no date - a)

Subst. / Concentration (µg l-1) Year Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 1999 Gly < < < 0.05 0.06 < 0.06 0.07 < < 0.08 < AMPA 0.18 0.13 0.09 0.16 0.19 0.18 0.31 0.43 0.39 0.43 0.34 0.19 2000 Gly < < < 0.11 < 0.09 0.06 0.05 0.07 0.09 < < AMPA 0.15 0.10 0.16 0.27 0.11 0.30 0.40 0.28 0.39 0.34 0.20 0.23 2001 Gly < < < < 0.13 0.12 0.06 0.08 - < < 0.13 AMPA 0.19 0.15 0.11 0.11 0.23 0.39 0.34 0.45 - 0.32 0.27 0.31 2002 Gly < < < 0.08 0.11 0.17 0.19 0.08 0.2 0.06 < 0.08 AMPA 0.2 0.16 0.24 0.27 0.26 0.30 0.43 0.38 0.73 0.25 0.15 0.26 Notes: < not detected - no data

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Table 29.5 Maximum concentrations of glyphosate and AMPA in the River Rhine in the Netherlands, 2001 and 2002 (source: RIWA, no date – a)

Monitoring Glyphosate (µg l-1) AMPA (µg l-1) station 2001 2002 2001 2002 Lobith * 0.13 0.20 0.45 0.73 Nieuwegein 0.12 0.41 - - Nieuwersluis - 0.25 0.38 - Andijk - - 0.27 0.17 Notes: * results included in Tables 29.1 and 29.2 - no data

29.3 Groundwater

29.3.1 National Data

Groundwater monitoring data for glyphosate and AMPA has become available for the years 2003 – 2006 (Van der Linden et al., 2007); the results were collated and analysed in the context of surveying groundwater quality for reporting under the Water Framework Directive (WFD) (2000/60/EC). The results are summarised in Table 29.6.

Glyphosate was detected in a small number of samples (4 of 691 samples, or 0.6%), with a maximum concentration of 4.74 µg l-1. AMPA was detected in a higher number of samples, i.e. 21 samples or 3%, with a slightly higher maximum concentration of 5.12 µg l-1. Groundwater samples were taken at several different depths; all the glyphosate detections occurred in samples taken at less than 2 m depth, whereas AMPA was found in shallow and deeper groundwater.

Groundwater contamination was also modelled and compared with actual monitoring data; from this it was concluded that glyphosate was not considered significant in terms of groundwater contamination (Van der Linden et al., 2007).

Table 29.6 Glyphosate and AMPA in groundwater in the Netherlands in 2003 - 2006 (source: Van der Linden et al., 2007)

Number (%) of samples Concentration - µg l-1 Total >LoD >0.1 µg l-1 Maximum Average* P50 P90 P95 P99 Glyphosate 691 4 (0.58) 4 (0.58) 4.74 0.01 <0.20 <0.20 <0.20 <0.20 AMPA 691 21 (3.0) 21 (3.0) 5.12 0.02 <0.20 <0.20 <0.15 <0.43 Note: *Average concentration calculated from all values, using zero where not detected

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29.3.2 Maas River Basin District

A small amount of additional groundwater data for the Netherlands’ part of the Maas River Basin District (RBD) in 2007 has been published in Verhagen et al. (2008) (report provided by M-A. Reding, personal communication, 2009) and is summarised in Table 29.7.

Table 29.7 Glyphosate and AMPA in the Maas RBD, 2007 (from Verhagen et al., 2008)

Number of samples >0.1 µg l-1 per substance and >0.5 µg l-1 for all pesticides Noord- Brabant Limburg WML Total Brabant Water Province (Water Substance Province supplier) Glyphosate 1 1 4 0 6 AMPA 0 2 4 1 7

The total number of exceedances of 0.1 µg l-1 for glyphosate was given as six or 3.2% of all monitoring points, suggesting that the exceedances were observed at six different points, of a total of 188 points.

Samples were taken at different level of groundwater depth, classified as shallow, medium depth and deep groundwater, and also included springs and some at unknown depth. With reference to all substances monitored, it was commented that the highest percentage of exceedances of the 0.1 µg l-1 drinking water standard, in terms of samples and monitoring sites, was observed in the shallow groundwater. No specific details were given for glyphosate and AMPA in relation to groundwater depth, except that the maximum concentration of glyphosate of 0.62 µg l-1 at Brabant Water on 1st October 2007 was observed in shallow ground water. Glyphosate was not included in the substances exceeding 0.1 µg l-1 at ten spring water sampling points (Figure 5-1 in Verhagen et al., 2008). The latter figure showed the only glyphosate exceedances of 0.1 µg l-1 in about 4% (2 sampling points) of 46 points in dry agricultural land areas, and AMPA exceedances in 33% (2 samples) of six sampling points in urban areas, although not all monitoring points seemed to be included in this figure, which tried to show the relationship between exceedances for some pesticides and relatively homogeneous types of land use areas.

It was noted that glyphosate and AMPA were not detected in groundwater in a survey in 2003, although included in the screening programme in the Maas RBD.

In the summary the authors listed glyphosate among four pesticides ‘regularly leading to exceedance of the standard in surface water and groundwater’. This seems somewhat exaggerated in view of the small number of exceedances of glyphosate in groundwater (see also conclusion from national data in Section 29.3.1).

29.4 Summary

There is a considerable body of information on surface waters, where glyphosate and AMPA have been monitored. Glyphosate was listed among the top ten pesticides in terms of exceeding the 0.1 µg l-1 drinking water standard in surface waters (standard not relevant for AMPA). In 2006 glyphosate was found at concentrations between 0.1 µg l-1 and 1 µg l-1 in 25%

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of samples, and above 1 µg l-1 in 11.3% of samples. AMPA was generally found more frequently and at higher concentrations than glyphosate, but may be derived from sources other than the degradation of glyphosate (e.g. detergents).

Whilst the trend analysis on the Pesticides Atlas indicated an upward trend in glyphosate concentrations in surface waters, a regional study (Flevoland) suggested a possible downward trend. However, any such trends would seem to require further data and statistical analyses.

Other data showed similar patterns of glyphosate and AMPA findings in surface waters. Monthly results from the river Rhine showed that, whilst AMPA was consistently present throughout the year, glyphosate was detected mainly between April and August, and never from January to March, and it was found at considerably lower concentrations than AMPA.

It was also concluded that a significant amount of glyphosate input was due to non-agricultural usage and it was recognised that AMPA inputs were not only derived from the degradation of glyphosate. It was indicated that wastewater treatment effluents could contribute to glyphosate inputs into surface waters, but this may need to be investigated further.

Both glyphosate and AMPA have been detected in a small number of groundwater samples and, where known, the detections were in shallow waters. Glyphosate and AMPA do not seem to be considered significant in terms of groundwater contamination at national level.

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30. UNITED KINGDOM

30.1 Introduction

Glyphosate analyses, but not AMPA, were included in monitoring programmes and special investigations from 1993 onwards, as outlined in Sections 30.2 and 30.3 below. Surface water and groundwater monitoring data for glyphosate were obtained from the Environment Agency database (extracts purchased from the Environment Agency, 2009). These data cover the years 2000-2007 and were gathered as part of a variety of monitoring programmes, i.e.:

 Routine controlled monitoring;  Harmonised monitoring;  Special surveys and investigations; and  Pollution incidents.

Earlier databases, covering monitoring data for the years 1993 – 2002 had been supplied for previous reports by Jackie Maud (EHS National Centre, Environment Agency, Wallingford) and Tony Chapman (EA Thames Region). In general, the overlap of data was consistent. However, where there were slight discrepancies the more up to date data were used. No AMPA data was included in the EA pesticides database.

30.2 Surface Water

Glyphosate monitoring in surface water started in 1993 as part of a special survey in the Anglian Region, and was incorporated into other monitoring programmes in other regions. The results are summarised in Table 30.1. Initially, the limits of detection were relatively high, varying from 0.02 to 1 µg l-1, although the majority were at 0.1 and 0.4 µg l-1; these are shown in the table together with the results, as appropriate. For the more recent data, detection limits of 0.1 g l-1 normally apply. The results listed in Table 30.1 were mainly derived from routine and harmonised monitoring programmes. Some special investigations in response to pollution incidents are listed in Table 30.2.

In the planned and routine monitoring, glyphosate was detected in 10.6% of all samples. There were a couple of samples, part of planned investigations, with very high concentrations (1 600 and 4 040 g l-1) which may have been part of a pollution incident, or possibly a data input error. No further details were available. Apart from those two samples maximum concentrations ranged from 8.18 g l-1 in pre 2000, to 1.77 g l-1 after 2000 (Table 30.1).

In the investigations of pollution incidents, a similar proportion of positives (11.4%) were found. In a pollution incident in Wales in 1998 the maximum concentration of glyphosate was 698 µg l-1 and in the North West Region in 2004 it was apparently 91 600 g l-1. It must be noted that ‘pollution incidents’ are not necessarily connected with glyphosate occurrence. However, as also indicated in Table 30.1, a high maximum concentration was found in Wales in 1999, there seems to have been a particular problem in Wales, such as spillages (see also Section 30.3). Maximum concentrations in subsequent years in Wales were much lower, i.e. all below 1.5 µg l-1 (Table 30.1).

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Table 30.1 Glyphosate in surface water in the UK, 1993 - 2007 (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009)

Date Region Number of Number of Number % LoD Max. sites samples > LoD > LoD (µg l-1) (µg l-1) 1993 Anglia 21 42 0 - 0.02 - 1994 Anglia 16 16 0 - 0.1 - North East 6 9 0 - 0.4 - 1995 North East 13 59 1 1.7 0.1-0.4 1.4 1996 Midlands 12 40 3 7.5 0.1-0.4 1.15 North East 10 51 0 0.1-0.4 - 1997 Anglia 16 26 0 0.1 - Midlands 12 134 0 0.1 - North East 11 47 0 0.1 - North West 1 2 0 - 0.1 - 1998 Midlands 3 15 0 0.1 - Wales 40 485 9 1.9 0.1 1.45 1999 North East 12 102 2 2.0 0.1 0.885 Thames 1 1 0 0.1 - Wales 39 284 5 1.8 0.1 8.18 2000 North East 17 62 0 0.1 - Wales 22 214 5 2.3 0.1 or 1 0.327 at 5 sites 2001 Wales 16 114 12 10.5 0.1 0.265 Anglia 1 1 0 0.1 - North East 11 50 7 14.0 0.1 0.15 2002 Wales 13 141 21 14.9 0.1 0.6 at 9 sites North East 17 161 21 13.0 0.1 1.5 at 7 sites 2003 Midlands 10 10 5 50 1000 4040? at 5 sites North East 7 73 17 23.3 0.1 1.27 at 4 sites Wales 11 127 19 15.0 0.1 0.891 at 9 sites 2004 North East 4 15 3 20.0 0.1 0.282 at 3 sites Wales 10 136 35 25.7 0.1 0.989 at 9 sites 2005 Anglian 12 130 49 37.7 0.1 0.850 at 10 sites North East 2 25 12 48.0 0.1 1.77 at 2 sites North West 1 9 8 88.9 1000 1600? Wales 13 124 48 38.7 0.1 1.48 at 12 sites 2006 Anglian 10 19 1 5.3 0.1 0.156 North East 1 3 0 - 0.1 - Wales 5 49 5 10.2 0.1 0.354 at 2 sites 2007 Wales 4 33 9 27.2 0.1 0.702 at 4 sites Total 6 Regions ≥ 92 2809 297 10.6 Mostly 0.1 8.2 1993 -2007*

Notes: LoD = limit of detection * sites not added where there may be overlap ? Results need further investigation and excluded from overall maximum value

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Table 30.2 Investigations of pollution incidents in surface water 1996 - 2007 (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009)

Date Region Number of Number of Number % LoD Max. Conc. Sites* samples > LoD > LoD (µg l-1) (µg l-1) 1996 North East 1 1 1 100 0.1 0.2 1997 North East 2 3 0 - 0.1 - 1998 Midlands 3 19 0 - 0.1 - Wales 15 82 3 3.6 0.1 698 1999 Wales 10 50 1 2 0.1 0.17 North East 4 4 0 - 0.1 - Midlands 3 3 0 - 0.1 - 2001 North East 4 4 0 - 0.1 - Midlands 2 3 1 33.3 0.1 2.89 2002 None ------2003 Anglian 2 12 8 66.6 0.1 5.52 Wales 1 9 0 - 0.1 - 2004 North West 1 1 1 100 91600? 2005 Anglian 1 10 8 80 0.1 387.3 2006 None ------2007 None ------Total 5 Regions ≥ 25 201 23 11.4 0.1 698 1996 -2007*

Notes: LoD = limit of detection * sites not added where there may be overlap ? Results need further investigation and excluded from overall maximum value

An earlier investigation of a glyphosate result of 1.4 µg l-1 (North East Region in 1995) showed no detections in follow-up samples (details in the previous WRc review, Horth et al., 2004).

30.3 Groundwater

There are about half as many groundwater monitoring data for glyphosate as there are for surface water (1 500 groundwater samples compared to nearly 3 000 surface water samples). Glyphosate analyses were included in the monitoring programme of the North East Region for the first time in 1995 (79 sites). Monitoring in Wales was between 1999 and 2000 and in the Southern Region it began in 2001. Only a small amount of data is available for the Anglian and Thames Regions.

Table 30.3 summarises the results. Glyphosate was detected in 3 samples (at 3 different sites) in Wales in 2000, and at a number of sites in the Southern Region in 2004, 2005 and 2006 but not in 2007. The limit of detection was relatively high initially (0.4 µg l-1 in 1995) but subsequently at 0.1 µg l-1 or lower, as indicated in Table 30.3. In total, 1 509 samples from over 200 sites were analysed, the 13 positives represent 0.9% of all samples analysed.

Special investigations of pollution incidents are listed in Table 30.4. All relate to Wales, where glyphosate was detected in 6.5% of samples, with a maximum concentration of 9.40 µg l-1. There appears to be a problem of some contamination in Wales, which should be further investigated (see also Section 30.2 – Surface Water). We do not have any further detail at present, concerning these results. Recent results have seen the maximum concentration decline to just over 0.1 g l-1 since 2005.

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Table 30.3 Glyphosate analyses in groundwater monitoring programmes 1995-2007 in the UK (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009)

Date Region Number of Number of Number % LoD Max. sites samples > LoD > LoD (µg l-1) (µg l-1) 1995 North East 79 79 0 - 0.4 - 1996 North East 6 6 0 - 0.1 - 1997 North East 1 1 0 - 0.1 - 1998 No data 1999 North East 36 65 0 - 0.1 - Wales 2 9 0 - 0.1 - 2000 North East 31 31 0 - 0.1 - Wales 20 20 3 15 0.1 0.467 at 3 sites 2001 Southern 9 16 0 - 0.1 - Anglia 1 1 0 - 0.1 - North East 1 4 0 - 0.1 - 2002 Southern 8 16 0 - 0.1 North East 1 2 0 - 0.1 2003 Southern 8 16 0 - 0.1 - North East 1 2 0 - 0.1 - 2004 South 109 362 6 1.7 0.02 0.086 at 5 sites North East 1 2 0 - 0.1 - 2005 Southern 106 334 1 0.3 0.02 0.027 2006 Southern 110 332 3 0.9 0.02 0.047 at 3 sites 2007 Southern 49 198 0 - 0.014 - Thames 7 13 0 - 0.014 - Total * 5 Regions ≥ 217 1509 13 0.9 0.014-0.4 0.467 1995-2007 Notes: LoD = limit of detection * sites not added where there may be overlap

Table 30.4 Investigation of pollution incidents in groundwater in Wales (source: EA database: EA 2001; EA 2002; EA 2003; EA, 2009)

Date Region Number of Number of Number % LoD Max. sites samples > LoD > LoD (µg l-1) (µg l-1) 2000 Wales 21 56 12 21 0.1 0.961 at 4 sites 2001 Wales 25 107 3 2.8 0.1 0.471 2002 Wales 25 96 4 4.1 0.1 9.40 at 1 site 2003 Wales 25 91 5 5.5 0.1 0.943 at 4 sites 2004 Wales 8 48 4 8.3 0.1 0.625 at 2 sites 2005 Wales 8 47 2 4.3 0.1 0.125 at 2 sites 2006 Wales 8 40 1 2.5 0.1 0.142 2007 Wales 2 10 1 10.0 0.1 0.113 Total * 1 Region 25 495 32 6.5 0.1 9.40 1995-2007 Notes: LoD = limit of detection * Total of sites not cumulative as includes where sites monitored in more than one year

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An investigation (Palmer and Holman, 1997) of an earlier incident of possible contamination of spring water with glyphosate at Llanthony in Gwent is described in the previous WRc review (Horth et al., 2004), where it was concluded that it should be regarded as an insignificant incident of contamination, either short-term at the site or sample contamination.

30.4 Summary

A considerable amount of glyphosate monitoring in surface water (2 800 samples) and a smaller amount of groundwater monitoring (1 500 samples) has been carried out in the UK. In addition, some special investigations were carried out. No AMPA data is included in the EA pesticide database.

Glyphosate was found in 5 Regions in 10.6 % of all surface water samples. For groundwater, glyphosate was only detected in Wales and the Southern Region and in 0.9% (13 samples) of all groundwater samples. The maximum concentration in surface waters (excluding special investigations of incidents and possible suspect results of 1600 and 4040 g l-1) was 8.2 µg l-1. The maximum concentration in groundwater (excluding special investigations of incidents) was below 0.5 µg l-1 in 2000; no values above 0.1 µg l-1 were detected in subsequent years. A number of positive samples and high maximum concentrations were found in Wales where there seems to be a particular problem, as indicated also by the special investigations of pollution incidents.

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31. CONCLUSION

Glyphosate and or AMPA data have been obtained for a total of 16 countries (surface water data for 13 and groundwater data for 13 with most countries including both). Data were mainly at national level, but in some cases regional, as from Belgium (two regions), Italy (one region), and Germany (surface water data for several Länder). In two countries (Czech Republic and Slovenia) monitoring has started in 2009 but data are not available as yet; six countries have confirmed that there is no monitoring of glyphosate and AMPA (Bulgaria, Hungary, Latvia, Lithuania, Luxembourg, Romania), whilst we have been unable to obtain any information from the remaining five countries (Cyprus, Estonia, Greece, Poland and Portugal).

Surface water

Some countries have proposed various environmental quality standards (EQS) or objectives for glyphosate in surface water, ranging from a proposed EQS of 28 µg l-1 in Mecklenburg- Vorpommern (Germany) and 60 µg l-1 in Ireland, to a proposed no effect concentration (PNEC) of 10 µg l-1 and a maximum admissible concentration (MAC) of 100 µg l-1 in Belgium - Flanders, and a Maximum Tolerable Risk (MTR) standard at 77 µg l-1, and a pesticide authorisation standard of 64 µg l-1 the Netherlands, whilst some professionals (Belgium – Wallonia and Rheinland-Pfalz (Germany) suggested that an EQS should be set. However, none of these standards have been exceeded on a regular basis. Perhaps more importantly, the Netherlands apply the drinking water standard of 0.1 µg l-1 for pesticides to surface water intakes at waterworks, and LAWA in Germany has set a target value of 0.1 µg l-1 for the same purpose.

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Groundwater

Glyphosate and AMPA have been increasingly analysed and occasionally detected in groundwater. Glyphosate has been analysed in about 36 000 samples from about 9 000 sites (1993-2009) and detected in about 1% of samples and 0.7% above 0.1 µg l-1; AMPA has been analysed in about 28 000 samples from 8 000 sites (1993-2008) and detected in 1.7% of samples and 0.9% above 0.1 µg l-1. These seem to occur in shallow water or springwater, which is often included in groundwater surveys, sometimes associated with contamination incidents (where the information is available), and even unsuitable sampling sites and analytical techniques (investigations in France and Germany).

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Horth, H. and Gendebien, A. (2008) Review of Glyphosate and AMPA in drinking water in selected European countries, WRc Report UC7729.04, WRc plc, Frankland Road, Blagrove, Swindon, Wiltshire, SN5 8YF, England (Confidential report to Monsanto Europe).

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Lange, F.T. and Post, B. (2000) Occurrence of glyphosate and AMPA in German rivers and their behaviour in drinking water treatment, in: Seminar on Glyphosate and Water, 19-20 September, 2000, Brussels, published by Monsanto, Belgium.

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RIWA (no date) Annual Report 1999-2000, Rhine and Scheldt, Association of River Waterworks, Nieuwegein, The Netherlands.

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Verhagen, F.Th., de Coninck, H.L. Vervest, F. (2008) Breded screening Bestrijdingsmiddelen Maasstroomgebied 2007 (Pesicide screening in the Maas river basin district), Project 9T3398, Royal Haskoning, The Netherlands (in Dutch).

Versteegh, J.F.M. and Dik, H.H.J. (2008) De kwaliteit van het drinkwater in Nederland in 2007 (The quality of drinking water in the Netherlands in 2007), Rijksintituut voor Volksgezondheid en Milieu, VROM Inspectie, Ministerie van VROM, RIVM Report 703719034, The Hague, The Netherlands (in Dutch) www.rivm.nl or www.vrom.nl.

Versteegh, J.F.M. and Dik, H.H.J. (2007) De kwaliteit van het drinkwater in Nederland, in 2006 (The quality of drinking water in the Netherlands in 2006), Rijksintituut voor Volksgezondheid en Milieu (RIVM), Inspectiereeks VROM/VI no. 2007/7420, The Hague, The Netherlands (in Dutch) www.rivm.nl.

Versteegh, J.F.M. and Dik, H.H.J. (no date) De kwaliteit van het drinkwater in Nederland, in 2005 (The quality of drinking water in the Netherlands in 2005), Rijksintituut voor Volksgezondheid en Milieu (RIVM), RIVM report no. 703719 014, VROM Inspectie, The Hague, The Netherlands (in Dutch) www.rivm.nl.

Versteegh, J.F.M. and Dik, H.H. (2006) De kwaliteit van het drinkwater in Nederland, in 2004 (The quality of drinking water in the Netherlands in 2004), Rijksintituut voor Volksgezondheid en Milieu (RIVM), Inspectiereeks VROM/VI no. 2006/5260, The Hague, The Netherlands (in Dutch) www.rivm.nl.

Versteegh, J.F.M. and Te Biesebeek, J.D. (2005) De kwaliteit van het drinkwater in Nederland, in 2003 (The quality of drinking water in the Netherlands in 2003), Rijksintituut voor Volksgezondheid en Milieu (RIVM), Inspectiereeks VROM/VI no. 2005/4233, The Hague, The Netherlands (in Dutch) www.rivm.nl.

Versteegh, J.F.M. and Te Biesebeek, J.D. (2004) De kwaliteit van het drinkwater in Nederland, in 2002 (The quality of drinking water in the Netherlands in 2002), Rijksintituut voor Volksgezondheid en Milieu (RIVM), Inspectiereeks VROM/VI no. 2004/3272, The Hague, The Netherlands (in Dutch) www.rivm.nl.

Versteegh, J.F.M. and Te Biesebeek, J.D. (2003) De kwaliteit van het drinkwater in Nederland, in 2001 (The quality of drinking water in the Netherlands in 2001), Rijksintituut voor Volksgezondheid en Milieu (RIVM), Inspectiereeks VROM/VI no. 2003/3134, The Hague, The Netherlands (in Dutch) www.rivm.nl.

Versteegh, J.F.M. and Te Biesebeek, J.D. (2002) De kwaliteit van het drinkwater in Nederland, in 2000 (The quality of drinking water in the Netherlands in 2000), Rijksintituut voor Volksgezondheid en Milieu, VROM Report No. 2002/01, VROM-Inspectie, Nieuwegein, The Netherlands (in Dutch) www.rivm.nl.

Volz (2007) Glyfosaat en AMPA in het stroomgebied van de Maas; Resultaten van een meetcampagne in het jaar 2006 (Glyphosate and AMPA in the Maas river basin district; Results of a monitoring campaign in 2006), RIWA Maas (in Dutch).

Waterschap Zuiderzeeland (2008) Bestrijdingsmiddelen in het opperflaktewater (Pesticides in surface water), Rapportage 2006-2007, Waterschap Zuiderzeeland, Leylstad, The Netherlands, (in Dutch) www.zuiderzeeland.nl.

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ZHEW (2002) Meetnet fruitteelt 1996-2001 en onderzoech drainagewater (Monitoring network in fruit plantations and investigation of drainage water), Zuiveringsschap Hollandse Eilanden en Waarden, Dordrecht (in Dutch).

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APPENDIX A PROFESSIONALS / ORGANISATIONS CONTACTED

Country Contact Organisation Austria Martin Wimmer Bundesministerium für Land - und Forstwirtschaft, Umwelt und Wasserwirtschaft (BMLF – Federal Ministry of Agriculture, Forestry, Environment and Water Management)

Dr Rudolf Philippitsch Bundesamt für Wasserwirtschaft (Federal Agency for Water Management) Belgium Ir Denis Godeaux MRW-DGRNE - Direction Eaux de Surfaces, Namur Bob Peeters VMM - Vlaamse Milieumaatschappij

Bénédicte Bastin VMM - Vlaamse Milieumaatschappij

Bulgaria Misho Mollov, National Focal Point for Water (EIONET), Bulgarian Executive Environment Agency (BEEA)

Cyprus Irene Constantinou Environment Service, Ministry of (EIONET contact) Agriculture, Natural Resources and Environment

C Kosta Department of Agriculture

Czech Republic Vít Kodes Department of Water Quality Czech Hydrometeorological Institute Prague

Denmark Dr Walter Brüsch, GEUS - Geological Survey of Denmark and Senior Geologist/Scientist/Adviser Greenland, Copenhagen

Susanne Boutrup NERI - National Environmental Research Institute, Copenhagen

Estonia Ago Jaani, Ministry of Environment, Karin Kroon Water Department

Finland Mira Grönroos Finnish Environment Institute SYKE Jaakko Mannio Tapani Säynätkari France Ariane Blum IFEN - Institut Français de l'Environnement / BRGM – Bureau de Recherches Géologique et Minière, Orléans Sophie Valjavec IFEN Publications Department

WRc Ref: UC8073.02/15276-0 111 November 2009 Monsanto

Country Contact Organisation Germany Dr Markus Lehmann LUBW Landesanstalt für Umwelt, Claudia Früh Messungen und Naturschutz Baden-Württemberg, Referat 41 - Fließgewässer, Integrierter Gewässerschutz, Karlsruhe

Dr. Jens Götzinger LAWA-Geschäftsstelle, currently at Saarbrücken

Dr. Kay Hamer Senator für Umwelt, Bau, Verkehr und Obmann des LAWA-Ausschusses Europa des Landes Bremen Grundwasser und Wasserversorgung

Bettina Thiel Ministerium Für Umwelt, Forsten Und Referentin Verbraucherschutz Rheinland-Pfalz, LAWA-AO-Geschäftsstelle Mainz Beate Zedler Hessisches Ministerium für Umwelt, LAWA - Berichterstattung Stoffe Energie, Landwirtschaft und Verbraucherschutz, Wiesbaden

Dr. Peter Seel Hessisches Landesamt für Umwelt und Dez. W2 Gewässergüte Geologie, Wiesbaden

Dr. René Schenk Ministerium für Ländliche Entwicklung, Umwelt und Verbraucherschutz des Landes Brandenburg

Dr. Ruediger Wolter Fachgebiet - Grundwasser, Umweltbundesamt – UBA (Federal Environment Agency), Dessau

Katrin Blondzik Fachgebiet II 2.4 – Oberflächengewässer, Umweltbundesamt – UBA (Federal Environment Agency), Dessau

Dr. Volker Mohaupt Fachgebiet II UBA, Dessau 2.4 (Oberflächengewässer) Greece Mata Aravantinou Ministry for the Environment P. Pantelopoulus S. Vanikioti

Hungary János Fehér “VITUKI" Environmental and Water Management Research Institute

Ireland Dr Ciaran O’Donnell, EPA Regional Chemist

WRc Ref: UC8073.02/15276-0 112 November 2009 Monsanto

Country Contact Organisation Italy Claudio Maricchiolo NFP/EIONET ANPA (Federal Environment Agency) Rome

Latvia Iraida Lyulko, State Hydrometeorological Agency Head of Observation Network Department

Lithuania Jurga Arustiene, Lithuanian Geological Survey Head of Groundwater Monitoring

Luxembourg Monique Reichard Ministère de L’Intérieur, Marie-France Speck Services de la Gestion l’Eau

Malta Yvette Rizzo Malta EPA

John Mangion, Director – Water Malta Resources Authority (MRA) Miriam Micallef Sultana

Norway Dr G H Ludvigson Bioforsk / Centre for Soil and Environmental Research (Jordforsk), Ås

Poland Regina Solova, International Commission for the Protection Agnieszka Olszewska, of the Odra, Wroclaw Secretariat

Przemyslaw Gruszecki (responsible Glowny Inspektorat, Warsaw for monitoring in Poland)

Portugal Regina Vilão NFP/EIONET Agência Portuguesa do Ambiente Amadora

Romania Dorina Mocanu Atmosphere Protection Directorate Director Ministry of Environment and Sustainable Development EEA EIONET National Focual Point

Gheorghe Constantin Ministry of Environment and Sustainable Director General Development, Water Management Department

Dr. Otilia Mihail Ministry of Environment and Sustainable Development, Water Management Department

Slovak Republic Dr. Igor Liska Secretariat ICPDR (International Technical Expert in Water Commission for the Protection of the Management / Water Quality Danube River), Vienna

Lea Mrafkova Slovak Hydrometeorological Institute

Slovenia Špela Kozak Legiša, Environmental Agency of the Republic of Slovenia, Monitoring Office

WRc Ref: UC8073.02/15276-0 113 November 2009 Monsanto

Country Contact Organisation Spain Javier Cachón de Mesa, NFP/EIONET Head of Environmental Information Ministerio de Medio Ambiente (Ministry of Environment) Mrs Alejandra Puig Ministerio de Medio Ambiente (Ministry of Environment), Water Directorate Javier Ruza Rodríguez General Directorate for Water Deputy General Subdirector Ministry of the Environment and Rural and Integrated Management of the Marine Affairs, Madrid Public Water Domain

C Coleto General Directorate for Water Ministry of the Environment and Rural and Marine Affairs, Madrid

Sweden Jenny Kreuger Swedish University of Agriculture (SLU), Stina Adielsson Dep. Soil Sciences, Div. Water Quality Management, Uppsala Switzerland Dr Benjamin Meylan Bundesamt für Umwelt – BAFU Dr Sybille Kilchmann (Federal Agency of Environment), Abteilung Wasser (Department for Water), Sektion Grundwasserschutz (Division Groundwater Protection)

Christian Leu Bundesamt für Umwelt – BAFU Ulrich Sieber (Federal Agency of Environment) Sektion Oberflächengewässer-qualität (Division Surface Water Quality)

Dr. Ueli Sieber Bundesamt für Umwelt - BAFU, Head of Surface Water Quality Abteilung Wasser Section Sektion Oberflächengewässerqualität Christian Leu (Division Surface Water Quality)

Ing. Martin Würsten, Swiss Cantonal Authority Solothurn Head of Water Protection The Netherlands Ir Ans Versteegh RIVM (Rijksinstituut voor Volksgezondheid en Milieu – State Institute for Public Health and Hygiene) Bilthoven Dr Leo Puijker KIWA Water Research, Nieuwegein

UK Ian Marshall EA Information Enterprise Centre Simon Dimbylow

Andrew Croxford Environment Agency Jackie Maud EHS National Centre Wallingford

WRc Ref: UC8073.02/15276-0 114 November 2009