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, 46100 Burjassot, Valencia, Spain

E-mail: Yolanda.Pico@uv.es

Agricultural pollution

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Low analytelevel

Interfering compounds

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Simple and sensitive analytical techniques

Monitoring pesticides residues in Ebro, Llobregat, Jucar and Guadalquivir River water

Purpose

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Target Pesticides

AZINPHOS METHYLCHLORFENVINPHOS

CHLORPYRIPHOSDIAZINON

FENITROTHIONFENTHION

FENTHION SULFOXIDEFENTHION SULFONE

FENOXONFENOXON SULFOXIDEFENOXON SULFONE

MALATHIONTOLCLOFOS-METHYL

OMETHOATEDIMETHOATE

DICHLOFENTHIONPARATHION-METHYLPARATHION-ETHYL

FENCHLORPHOS (Ronnel)ETHION

AZINPHOS ETHYL

BUPROFEZINIMIDACLOPRIDPYRIPROXYFEN

CARBOFURAN3-HYDROXYCARBOFURANMETHIOCARBMOLINATE

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ATRAZINEDEISOPROPYLATRAZINEDEETHYLATRAZINESIMAZINEPROPAZINETERBUTHRYN

ACETOCHLORALACHLORMETOLACHLOR

DIURONISOPROTURON

PROPANIL

HEXYTHIAZOXIMAZALILPROCHLORAZ

Sampling sites

Júcar15 points

Guadalquivir25 points

Llobregat14 points

Ebro – 24 points

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28/09/201007/10/2010

21/09/201023/09/2010

14/10/201020/10/2010

22/09/201005/10/2010

Detail of the points at the Ebro River Basin

GAL1

EBR6

EBR7

SEG

CIN2

ARGEBR2ZAD

EBR8

ALG

EBR3

EBR4

CIN1

GAL2HUE

ESE

NAJ

RS

Tortosa

LleidaZaragoza

Huesca

Monzón

Sabiñánigo

Pamplona

Logroño

Gasteiz

Tudela

-

EBR1

EBR5

MAR

EBR9

OCA

MATContamination gradient

ReferenceHydraulic impact

SAMPLING SITES:24 sampling site4 references2 contamination gradients2 hydraulic impacts

Reference

Reference

ReferenceHydraulic impact

Contamination gradient

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Extraction

SPE

Evaporate to drynessRedissolve in 1 mL methanol

Water Samples(250 mL)

Oasis HLB, 200 mg, 6 cc

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Preconditioning•5 mL methanol-Cl2CH2 (20:80, v/v)•5 mL water

LC‐MS/MS

LCLC--MSMS--MS ChromatogramMS Chromatogram

SRM (80 pairs) 10 µg/L standard LC-ESI-QqQ-MS/MS

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Dimethoate Cordoba in

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Atrazine-deethyl Cordoba in

Dimethoate-10 μg/L

Atrazine-deethyl-10 μg/L

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Analytical ParametersAnalytical Parameters

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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 controlQuality 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.

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Results of the monitoringATRAZINE

DEISOPROPYLATRAZINEDEETHYLATRAZINE

CARBOFURAN3-HYDROXYCARBOFURAN

CHLORFENVINPHOSCHLORPYRIPHOS

DIAZINONDIURON

FENTHION SULFONEFENOXON SULFOXIDE

HEXYTHIAZOXIMAZALIL

IMIDACLOPRIDISOPROTURON

MALATHIONMETHIOCARBPROCHLORAZ

PYRIPROXYFENSIMAZINE

TOLCLOFOS METHYLMOLINATE

OMETHOATEDIMETHOATEPROPAZINE

DICHLOFENTHIONPARATHION-ETHYL

TERBUTHRYNMETOLACHLOR

Of 43 selected pesticides, 21 were detected

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FREQUENCY OF THE DIFFERENT TYPES OF PESTICIDES

FREQUENCY OF TRIAZINES

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FREQUENCY OF ORGANOPHOSPHORUS

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FREQUENCY OF CARBAMATES AND UREAS

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FREQUENCY OF OTHER TYPES OF PESTICIDES

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Pesticide Concentration in Llobregat River

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Pesticide Concentration in Jucar River

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Distribution of imazalil in the Jucar River

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Distribution of atrazine and its metabolites in the Jucar River

AlberiqueWWTP

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WWTP AlberiqueWWTP AlberiqueIn

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Pesticide Concentration in Ebro River

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WWTP LleidaWWTP Lleida

~~

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Pesticide Concentration in Guadalquivir River

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How representative are the selected pesticides?

AB SCIEX TripleTOF™ 5600 System

- Mobil phaseA: H2O (10mM NH4COO) B: Methanol (10mM NH4COO)

-Column: Agilent EC-C18,4.6x100 mm, 2.7µm

Injection volume: 5 µL

TOF-MS

LIQUID CHROMATOGRAPHY

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Thiabendazole in EBR-9

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Screening of pesticides in a database containing 600 compounds

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CONCLUSIONSAlmost 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) andthe Llobregat (malathion 321 ng/L) both surpassing the tolerancefor drinking water.

Data from the Jucar River demonstrated that WWTP could be an important source of pesticides to surface waters.

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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).

Persons of the research groups from IDAEA and ICMAN for taking the samples of the Ebro, Llobregat and Guadalquivir Rivers.

ICMAN

Thanks you for your attention

Thanks you for your attention