Context. Implementation of the Water Framework Directive (2000/60/EC) Objective: achieve or maintain a good environmental status by 2015

Transcription

1 Interest of passive sampling to improve Water Framework Directive monitoring network: Example of 40 polar pesticides monitoring by POCIS on an agricultural watershed in France Gaëlle Poulier a, b, *, Sophie Lissalde b, Adeline Charriau b, Rémy Buzier b, Patrice Fondanèche b, Karine Cléries b, Nicolas Mazzella a, François Delmas a, Gilles Guibaud b a : Irstea de Bordeaux, 50 avenue de Verdun, Gazinet-Cestas b : Groupement de Recherche Eau Sol Environnement, Université de Limoges, 123 avenue Albert Thomas

2 Context Implementation of the Water Framework Directive (2000/60/EC) Objective: achieve or maintain a good environmental status by 2015 List of 41 priority substances, including 14 pesticides (8 herbicides and 6 insecticides) Environmental Quality Standards (EQS) expressed as Annual Average (AA-EQS) and as Maximal Allowable Concentration (MAC-EQS) Water monitoring network: - surveillance control - operational control - nvestigative control

3 Context 12 grab samples per year Biological monitoring Chemical monitoring Surveillance monitoring Physico-chemical monitoring Good or high quality Water body quality status Failing chemical status Additional information Failing biological status Operational monitoring Additional information 4 grab samples per year Investigative tasks, (e.g. locate source of contamination) Investigative monitoring Investigative tasks, (e.g. indentify contamination) Grab sampling is questionable Iterative review Understanding of the situation Remediation strategy selection and implementation The three different types of control in the WFD (Allan et al, 2006b)

4 ng/l Context Grab sampling Real concentration Jours Grab sampling: Lack of reliability because of low sampling frequency Automated sampling with high frequency: Better reliability but Time consuming Expensive incompatible with routine analysis

5 Context ng/l Jours Grab sampling Contamination Real concentration réelle Passive sampling Passive sampling: Acquisition of a time weighted average concentrations, because devices are continuously exposed Lower quantification limits because analytes are concentrated in situ

6 Question Can passive sampling be used to improve the WFD monitoring network? Determination of the possible applications of passive samplers for: Screening? Identifying sources of contamination? Reporting trends? Deployment on the field Compliance with WFD requirements (compatibility with EQS, quantification limits, ) Comparison of data collected via passive sampling to those collected via grab sampling in the traditionnal monitoring network

7 Methodology : POCIS Sorbent (Oasis HLB) Membrane (PES) Support ring (inox) View of a POCIS POCIS exposed in situ POCIS after deployment C twa C k pocis u t All the parameters are known except the k u = kinetic constant of the accumulation that is specific for each compound. A calibration step is needed

8 Methodology : POCIS calibration Compound Action Use Carbaryl Insecticide forbidden Carbendazime Insecticide forbidden Carbofuran Insecticide forbidden Methomyl Insecticide Pyrimicarb Insecticide Dimethanamid herbicide forbidden Acetochlor Herbicide forbidden Alachlore Herbicide forbidden Dimetachlor Herbicide Metazachlor Herbicide Metolachlor Herbicide Norflurazon Herbicide forbidden Spiroxamin Fongicide Azoxystrobin Fongicide Atrazin Herbicide forbidden Irgarol Algicide Simazin Herbicide forbidden Terbuthylazin Herbicide forbidden Hexazinon Herbicide forbidden Cyproconazol Fongicide Epoxyconazol Fongicide Flusilazol Fongicide Tebuconazol Fongicide Chlortoluron Herbicide Diuron Herbicide forbidden Isoproturon Herbicide Linuron Herbicide Metoxuron Herbicide forbidden Flurtamone Herbicide Dimetomorph Fongicide Imidacloprid Insecticide Dimethoat Insecticide Choice of the compounds : POCIS : suited for neutral compounds, logp < 4 Study of the historic of the contamination of the watershed where the POCIS would be deployed List of 40 compounds : 33 pesticides 8 metabolites DEA DET DIA DCPMU DCPU IPPMU IPPU Metabolites Norflurazon desméthyl

9 Methodology : POCIS calibration

10 Methodology : POCIS calibration Concentration factor (L/g) Acetochlor y = x R 2 = Azoxystrobin : linear over 28 days DEA : curvilinear after 20 days Concentration Factor (L/g) y = R 2 = DEA

11 Methodology : POCIS calibration Carbaryl Carbendazime Carbofuran Chlortoluron Cyproconazol DCPMU DCPU DEA DET DIA Dimetachlor Dimethanamid Dimethoate Dimetomorph Diuron Epoxyconazol Flurtamone Flusilazol Hexazinone Imidacloprid IPPMU IPPU Irgarol Isoproturon Linuron Metazachlor Methomyl Metolachlor Metoxuron Norflurazon-desméthyl Pyrimicarb Simazine Spiroxamine Tebuconazol Terbuthylazin (DIA) < k u < (Terbuthylazin) k e (DIA-d5) = 0.08 Acetochlor Alachlor Atrazin Azoxystrobin ku 2012 (L/g/j)

12 Methodology : POCIS calibration A previous POCIS laboratory calibration was made in 2010 by Lissalde The conditions used for the calibration were quite different so : k e 2010 = k e 2012 = 0.08 k u 2012 was corrected to account for differences related to calibration conditions. k u 2012 corrected k u 2012 k k e e

13 Methodology : POCIS calibration Acetochlor Alachlor Atrazin Azoxystrobin Carbaryl Carbendazime Carbofuran Chlortoluron Cyproconazol DCPMU DCPU DEA DET DIA Dimetachlor Dimethanamid Dimethoate Dimetomorph Diuron Epoxyconazol Flurtamone Flusilazol Hexazinone Imidacloprid IPPMU IPPU Irgarol Isoproturon Linuron Metazachlor Methomyl Metolachlor Metoxuron ku (L/g/j) Norflurazon-desméthyl Pyrimicarb Simazine Spiroxamine Tebuconazol Terbuthylazin k u 2012 are very similar to those obtained by Lissalde (2010) Our experimental design gives very repeatable results ku 2012 corrected ku Lissalde 2010

14 Field deployment and laboratory analysis Choice thetrec-canaule watershed due to a high risk of failing good status : Operational control implemented by the French Water Agency Remediation strategies (training days for volunteers farmers, reduction of the use of herbicides ) Area of cereal crops Strong agricultural pressure, with worrying levels of pesticides Marmande Trec Manet Canaule POCIS deployment One POCIS per site exposed successively from March to December 2012 in three different rivers of the watershed. Laboratory analysis LC/MS/MS Trec-Canaule watershed

15 Results : Trec Peaks of pesticides occur : Trec April 10th May 21th November 19th Précipitations Rainfall (mm) (mm) Flow (m3/s) Peaks are very related to rainfall and flow. 17 Dec Dec Nov Nov Oct Oct Sep Sep Aug Aug Jul Jul Jul Jun Jun May May Apr Apr Mar Mar 12 mm m3/s Metolachlor DEA Atrazin Acetochlor Dimathanamid Isoproturon DIA Alachlor Tebuconazol Imidacloprid Azoxystrobin Chlortoluron Metazachlor Others 2 Jul 4 Jun 9 May 10 Apr 12 Mar 30 Jul 27 Aug 17 Dec 19 Nov 22 Oct 24 Sep µg/l

16 µg/l Results : Trec Metolachlor DEA Atrazin Acetochlor TrecDimathanamid Isoproturon DIA Alachlor Tebuconazol Imidacloprid Azoxystrobin Chlortoluron Metazachlor Pyrimicarb Carbaryl Diuron Others Peaks of pesticides occur : April 10th May 21th November 19th Mar 10 Apr 9 May 4 Jun 2 Jul 30 Jul 27 Aug 24 Sep 22 Oct 19 Nov 17 Dec Mostly herbicides, used for corn and sunflower treatment Two different cocktails of compounds: Spring : metolachlor, acetochlor, alachlor, dimethenamid Autumn: Isoproturon, chlortoluron, imidaclopride Atrazine and DEA: present all over the year

17 1.2 Results : Trec Trec Manet µg/l Metolachlor DEA Atrazin Acetochlor Dimathanamid Isoproturon DIA Alachlor Tebuconazol Imidacloprid Azoxystrobin Chlortoluron Metazachlor Pyrimicarb Carbaryl Diuron Others Trec Canaule µg/l Manet Canaule The contamination patterns are very similar for the three rivers Manet Metazaclor: unexpected in July (used for winter crops like colza) Probably accidental contamination occurring on the upstream part (Manet river) µg/l Mar 10 Apr 9 May 4 Jun 2 Jul 30 Jul 27 Aug 24 Sep 22 Oct 19 Nov 17 Dec

18 Results : The Water Agency data What about the efficiency of the remediation strategy implemented since 2009? µg/l Mar-09 May-09 Jul-09 Sep-09 Nov-09 Jan-10 Mar-10 May-10 Jul-10 Sep-10 Nov-10 Jan-11 Mar-11 May-11 AMPA Atrazin Glufosinate Iprodione Metazachlor Pyrimethanyl Others Glyphosate DEA Imidacloprid Isoproturon Metolachlor Sulfosate Jul-11 Sep-11 Nov-11 Jan-12 Mar-12 May-12 Jul-12 Sep-12 Nov-12 Concentrations of pesticides measured on Trec by the Water Agency from 2009 to 2012 Its seems that there is no improvement of the water quality, but : Very few sampling dates (16 in 3 years) The LOQs for the grab sample analysis is quite high (20 ng/l) It s difficult to conclude

19 Results : The Water Agency data AMPA Glyphosate Atrazin AMPA Glyphosate DEA Glufosinate Atrazine DEA Imidacloprid Iprodione Glufosinate Imidaclopride Isoproturon Metazachlor Iprodione Isoproturon Métazachlore Métolachlore Metolachlor Pyrimethanyl Sulfosate Others Autres Mar-09 Apr-09 May-09 Jun-09 Jul-09 Aug-09 Sep-09 Oct-09 Nov-09 Dec-09 Jan-10 Feb-10 Mar-10 Apr-10 May-10 Jun-10 Jul-10 Aug-10 Sep-10 Oct-10 Nov-10 Dec-10 Jan-11 Feb-11 Mar-11 Apr-11 May-11 Jun-11 Jul-11 Aug-11 Sep-11 Oct-11 Nov-11 Dec-11 Jan-12 Feb-12 Mar-12 Apr-12 May-12 Jun-12 Jul-12 Aug-12 Sep-12 Oct-12 Nov-12 Dec-12 µg/l Sum of the concentrations of pesticides measured on Trec by the Water Agency from 2009 to 2012 The most abundant compounds : Glyphosate AMPA Sulfosate, Glufosinate Metolachlor Very polar compounds (logp < 0) don t adsorb onto the POCIS No passive sampler suited for these compounds

20 Results : The Water Agency data Only the compounds both analyzed by the Water Agency and calibrated for the POCIS were kept 2 1 Mar-09 May-09 Jul-09 Sep-09 Nov-09 Jan-10 Mar-10 May-10 Jul-10 Sep-10 Nov-10 Jan-11 Mar-11 µg/l May-11 Jul-11 Sep-11 Nov-11 Jan-12 Mar-12 May-12 Jul-12 Sep-12 Nov-12 0 Metolachlor DEA Atrazin Acetochlor Imidacloprid Isoproturon Metazachlor Chlortoluron DIA Dimethanamid Tebuconazol Others Zoom on 2012 POCIS data

21 µg/l Results : comparison between the Water Agency and the POCIS data POCIS 12-Mar 10-Apr 9-May 4-Jun 2-Jul 30-Jul 27-Aug 24-Sep 22-Oct 19-Nov 17-Dec Water Agency o POCIS data correlate well with those from the operational monitoring network in March, April, and May. o In December, the difference between the two types of sampling is higher: The Water Agency measured the concentration just at the moment of the peak whereas POCIS measures a TWA Moreover, the peak may has been quite fleeting The POCIS can be used to: Determine the most risky periods for an agricultural watershed, and then to choose the best dates for a further grab sampling strategy Identify the geographical origin of a contamination, thus to facilitate the choice of the sampling sites

22 Results : comparison between the Water Agency and the POCIS data µg/l Mar 10-Apr 9-May 4-Jun POCIS 2-Jul 30-Jul 27-Aug Water Agency 24-Sep 22-Oct 19-Nov 17-Dec Calculation of the quantification frequencies : Four POCIS chosen close to the sampling periods of the Water Agency in 2012.

23 Results : comparison between the Water Agency and the POCIS data 100 % Quantification 50 Water Agency 2009 Water Agency 2011 Water Agency 2012 POCIS 2012 (4 dates) 0 Alachlor Atrazin Chlortoluron DIA Dimethanamid Epoxiconazol Fluzilazol Imidacloprid Tébuconazol Quantification frequencies are always enhanced with the POCIS, in comparison with grab samples Chlortoluron : % 75% with the POCIS (atrazin, DIA, dimethanamid, imidacloprid, tebuconazol) Alachlor was never detected since 2009, but present in 50% of the POCIS samples (epoxyconazol, fluzilazol) The low limits of quantification of the POCIS permit detection of many compounds at trace level Very useful for screening and investigative monitoring

24 Conclusions and further studies Our work showed that the POCIS can be a very usefull tool for: The operationnal monitoring To help determine the best period for a relevent monitoring The investigative monitoring For screening However, the POCIS cannot be used yet for surveillance monitoring because of two challenging issues at least: The data are still considered as semi-quantitative, and field calibrations or the use of PRCs must be achieved or validated The POCIS measures only the dissolved part of the compounds, whereas EQS for organic pollutants are given for the raw/total water

25 Thanks for listening!