Monitoring water-polluting pesticides at the catchment scale in the Ebro, Llobregat, Jucar and Guadalquivir Rivers

Transcription

1 Monitoring water-polluting pesticides at the catchment scale in the Ebro, Llobregat, Jucar and Guadalquivir Rivers Yolanda Picó, Ana Masia, Cristina Blasco and Pablo Vazquez Food and Environmental Safety Research Group, Faculty of Pharmacy, University of Valencia, Av. Vicent Andrés Estellés s/n, Burjassot, Valencia, Spain Agricultural pollution

2 Interfering compounds Low analyte level Simple and sensitive analytical techniques Purpose Monitoring pesticides residues in Ebro, Llobregat, Jucar and Guadalquivir River water

3 CARBOFURAN 3-HYDROXYCARBOFURAN METHIOCARB MOLINATE BUPROFEZIN IMIDACLOPRID PYRIPROXYFEN Target Pesticides ACETOCHLOR ALACHLOR METOLACHLOR PROPANIL AZINPHOS METHYL CHLORFENVINPHOS CHLORPYRIPHOS DIAZINON FENITROTHION FENTHION FENTHION SULFOXIDE FENTHION SULFONE FENOXON FENOXON SULFOXIDE FENOXON SULFONE MALATHION TOLCLOFOS-METHYL OMETHOATE DIMETHOATE DICHLOFENTHION PARATHION-METHYL PARATHION-ETHYL FENCHLORPHOS (Ronnel) ETHION AZINPHOS ETHYL ATRAZINE DEISOPROPYLATRAZINE DEETHYLATRAZINE SIMAZINE PROPAZINE TERBUTHRYN HEXYTHIAZOX IMAZALIL PROCHLORAZ DIURON ISOPROTURON Sampling sites 22/09/ /10/2010 Guadalquivir 25 points Ebro 24 points Júcar 15 points Llobregat 14 points 14/10/ /10/ /09/ /10/ /09/ /09/2010

4 Detail of the points at the Ebro River Basin EBR1 Reference OCA Contamination gradient SAMPLING SITES: 24 sampling site 4 references 2 contamination gradients 2 hydraulic impacts Gasteiz ZAD EBR2 EBR3 Logroño EBR4 NAJ Pamplona ARG Reference Sabiñánigo GAL1 - CIN1 ESE Huesca Tudela Hydraulic impact EBR5 Monzón CIN2 GAL2 Zaragoza Lleida HUE EBR6 SEG MAT EBR7 Contamination Hydraulic impact ALG gradient Reference MAR Tortosa EBR8 EBR9 RS Reference Extraction Preconditioning 5 ml methanol- Cl 2 CH 2 (20:80, v/v) 5 ml water Water Samples (250 ml) SPE LC MS/MS Oasis HLB, 200 mg, 6 cc Evaporate to dryness Redissolve in 1 ml methanol

5 LC-MS MS-MS Chromatogram SRM (80 pairs) 10 µg/l standard LC-ESI-QqQ-MS/MS Dimethoate-10 μg/l Dimethoate Cordoba in Atrazine-deethyl-10 μg/l Atrazine-deethyl Cordoba in Relative Abundance (%) Relative Abundance (%) Analytical Parameters Recoveries: 55 % to 102 % Precision (intraday and interday as RSD): < 18 % Linearity (over three orders of magnitude from the LOQ): r > 0.99 LOQs: 0.5 ng/l (imidacloprid, diazinon) 2 ng/l (omethoate, dimethoate, carbofuran and its metabolites, fenthion and its metabolites, propazine, methiocarb, malathion, azinphos ethyl, chlorfenvinphos, buprofezin, ethion, chlorpyriphos, hexythiazox). 4 ng/l (all other pesticides selected) Quality control Procedural blanks each 15 samples Blanks (deionized water treated as the samples) injected each 15 samples (Buprofezin, Chlorpyriphos, Hexythiazox, Pyriproxyfen and Ethion) Positive control samples (deionized water spiked at 40 ng/l) injected each 15 samples.

6 Results of the monitoring Of 43 selected pesticides, 21 were detected ATRAZINE DEISOPROPYLATRAZINE DEETHYLATRAZINE CARBOFURAN 3-HYDROXYCARBOFURAN CHLORFENVINPHOS CHLORPYRIPHOS DIAZINON DIURON FENTHION SULFONE FENOXON SULFOXIDE HEXYTHIAZOX IMAZALIL IMIDACLOPRID ISOPROTURON MALATHION METHIOCARB PROCHLORAZ PYRIPROXYFEN SIMAZINE TOLCLOFOS METHYL MOLINATE OMETHOATE DIMETHOATE PROPAZINE DICHLOFENTHION PARATHION-ETHYL TERBUTHRYN METOLACHLOR FREQUENCY OF THE DIFFERENT TYPES OF PESTICIDES

7 FREQUENCY OF TRIAZINES FREQUENCY OF ORGANOPHOSPHORUS

8 FREQUENCY OF CARBAMATES AND UREAS FREQUENCY OF OTHER TYPES OF PESTICIDES

9 Pesticide Concentration in Llobregat River Pesticide Concentration in Jucar River

10 Distribution of imazalil in the Jucar River Alberique WWTP Distribution of atrazine and its metabolites in the Jucar River

11 WWTP Alberique Pesticide Concentration in Ebro River

12 WWTP Lleida ~ Pesticide Concentration in Guadalquivir River

13 How representative are the selected pesticides? AB SCIEX TripleTOF 5600 System LIQUID CHROMATOGRAPHY - Mobil phase A: H 2 O (10mM NH 4 COO) B: Methanol (10mM NH 4 COO) -Column: Agilent EC-C18, 4.6x100 mm, 2.7µm Injection volume: 5 µl TOF-MS Thiabendazole in EBR-9

14 Screening of pesticides in a database containing 600 compounds CONCLUSIONS Almost 100 % of the samples contain several pesticide residues. Up to 21 pesticides were found in the samples. The pesticides most frequently detected were organophosphorus insecticides, triazine herbicides and fungicides. Highest concentrations were in the Jucar (imazalil 680 ng/l) and the Llobregat (malathion 321 ng/l) both surpassing the tolerance for drinking water. Data from the Jucar River demonstrated that WWTP could be an important source of pesticides to surface waters.

15 Acknowledgments Spanish Ministry of Science and Innovation through the project Consolider-Ingenio 2010 (CSD2009). P. Vazquez Roig is holder of FPI grant from the Ministry of Science and Innovation (MICINN, Spain). ICMAN Persons of the research groups from IDAEA and ICMAN for taking the samples of the Ebro, Llobregat and Guadalquivir Rivers. Thanks you for your attention