7 thEuropean Conference on Pesticides andRelated Organic Micropollutants in the Environment

October 7-10, 2012Porto, Portugal

BOOK OF ABSTRACTS

13 thSymposium on Chemistry and Fateof Modern Pesticides

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“7th European Conference on Pesticides and Related Organic Micropollutants in the Environment”

“13th Symposium on Chemistry and Fate of Modern Pesticides”

October 7-10, 2012

Porto, Portugal

BOOK OF ABSTRACTS

Organized by IAREN - Water Institute of the Northern Region

ENEAP - European-Mediterranean Association for Environmental Education Assessment and Protection

IAEAC - International Association of Environmental Analytical Chemistry

With collaboration of NORMAN - Network of reference laboratories, research centres and related organisations for

monitoring of emerging environmental substances JRC-IES - Joint Research Centre- Institute for Environment and Sustainability

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Book of Abstracts

“7th European Conference on Pesticides and Related Organic Micropollutants in the Environment” and “13th Symposium on Chemistry and Fate of Modern Pesticides” October 7-10, 2012

Porto, Portugal

ISBN: 978-989-20-3262-7

Editor: Maria de Fátima Alpendurada / IAREN – Instituto da Água da Região Norte

Printing: ajnet, lda.

Design: ajnet, lda.

Disclaimer

This book was carefully produced from the author’s own submissions. Minor formal

modifications were made, which in no way interfere with their scientific content. The final

printing model was established by IAREN according to previous template. Nevertheless, we

do not warrant the information contained therein to be free of errors. Readers are advised to

keep in mind that statement, data, illustrations, procedural details or other items may

inadvertently be inaccurate.

(c) IAREN

All right reserved. No part of this document may be reproduced in any form or by any means

without written permissions of the editors.

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Scientific Committee Albaigés, Joan CID-CSIC, Barcelona, Spain Albanis, Triantafyllos University of Ioannina, Greece Alpendurada, Maria de Fátima Universidade do Porto, Portugal Amalric, Laurence BRGM, Orléans, France Bufo, Sabino Aurelio University of Basilicata, Potenza, Italy Cerejeira, Maria José ISA-UTL, Lisbon, Portugal Chiron, Serge University of Montpellier, France Dagnac, Thierry CIAM, A Coruña, Spain Dulio, Valeria NORMAN, Paris, France Fernández-Alba, Amadeo University of Almeria, Spain Gago-Martinez, Ana University of Vigo, Spain Gawlik, Bernd JRC-IES, Ispra, Italy Gonçalves, Carlos IAREN, Matosinhos, Portugal Hajslova, Jana Institute of Chemical Technology, Czech Rep. Jinno, Kiyokatsu Toyohashi University of Technology, Japan Konstantinou, Ioannis University of Ioannina, Greece Lacorte, Silvia IDAEA-CSIC, Barcelona, Spain Lambropoulou, Dimitra Aristotle University of Thessaloniki, Greece Llompart, María University of Santiago de Compostela, Spain Minero, Claudio University of Torino, Italy Muniategui-Lorenzo, Soledad University of A Coruña, Spain Papadopoulou-Mourkidou, Euphemia Aristotle University of Thessaloniki, Greece Prada-Rodriguez, Dario University of A Coruña, Spain Sakkas, Vasilis University of Ioannina, Greece Sinclair, Chris CSL, York, United Kingdom Slobodnik, Jaroslav WRI/EI, Slovakia Tadeo, Jose Luis INIA, Madrid, Spain Ternes, Thomas BFG, Koblenz, Germany Trevisan, Marco Catholic University, Piacenza, Italy

Honorary Committee Valeria Dulio (NORMAN) Bernd Gawlik (JRC-IES) Municipality of Matosinhos AMTC, Porto, Portugal

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Organizing Committee Prof. Maria de Fátima Alpendurada (Chairman - IAREN) Prof. Triantafyllos Albanis (Co-Chairman - ENEAP) Prof. Joan Albaigés (Co-Chairman - IAEAC) Dr. Carlos Gonçalves (Conference Secretary - IAREN) Vocals: Prof. María Llompart (University of Santiago de Compostela, Spain) Dr. Thierry Dagnac (CIAM, A Coruña, Spain) Prof. Soledad Muniategui-Lorenzo (University of A Coruña, Spain) Prof. Maria José Cerejeira (ISA-UTL, Lisbon, Portugal) Prof. Angelina Pena (University of Coimbra, Portugal) Eng. Paula Viana (INAG, Lisbon, Portugal) Dr. Vitor Vilar (University of Porto) Dr. Rui Boaventura (University of Porto) Augusta Sousa (University of Porto) Andreia Machado (IAREN, Matosinhos, Portugal) Ana Guimarães (IAREN, Matosinhos, Portugal) Conference address

IAREN – Water Institute of the Northern Region Rua Dr. Eduardo Torres, 229 4450-113 Matosinhos, Portugal phone: +351 22 9364210 / fax: +351 22 9364219 URL: www.iaren.pt/pesticides2012 / Email: pesticides2012@iaren.pt

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Session II: P64

OCCURENCE OF PESTICIDE RESIDUES IN GROUNDWATERS OF AGRICULTURAL AREAS IN THE ÁGUEDA RIVER BASIN

S. Sánchez-González, E. Pose-Juan,, A. Álvarez-Martín, E. Herrero-Hernández, M.S.

Rodríguez-Cruz, M.J. Sánchez-Martín

Instituto de Recursos Naturales y Agrobiología de Salamanca (IRNASA-CSIC), Cordel de Merinas 40-52, 37008 Salamanca, Spain

Summary

The environmental characterization of the cross-border Águeda river basin in relation to

the evaluation of the agricultural impact derived from the use of pesticides in unirrigated and irrigated crop areas and in small horticultural areas was carried out in this study. Sixteen pesticides were monitored in twenty-five groundwaters from Spain and in twenty-seven groundwaters from Portugal using a developed multi-residual analytical method based on SPE-LC-MS. Ten or eight compounds included in this study were detected in any Spanish or Portuguese water samples. These compounds were detected over the level of 0.1 �g L-1 in the Spanish samples, but only three compounds were over this limit in the Portuguese samples.

Introduction

The Águeda river basin of 2660 km2, which has more than 170 km long including 40 km in the border with Portugal (Figure 1), is affected by a series of different activities or impacts both natural or anthropogenic (mining industry, agriculture, hydraulic infrastructures, etc). These activities can contribute to its vulnerability, although this natural area is included in the Natura 2000 network. The environmental characterization of this cross-border basin is being

carried out by a multi-disciplinary project with the aim of identifying the environmental risks associated to the different activities developed in this area.

One of the aims of this project is the evaluation of the agricultural impact derived from the use of pesticides in unirrigated and irrigated crop areas and in small horticultural areas, which is dealt with in this work. In certain areas from the basin, the soil type is shallow and with coarse texture, and it could facilitate the leaching of these compounds to the waters, although there are not data about the levels of pesticides in soils and/or waters from this basin. Accordingly, several broad spectrum pesticides, with different functional groups and usually applied in agriculture were selected for the study. Some of them are included in the list of priority substances present in the Annex X of the Directive 2008/105/CE, which sets the maximum admissible individual pesticides concentration in groundwater 0.1 �g L-1. The presence of these pesticides in surface and ground waters has been also indicated by other authors [1, 2].

Figure 1. Map of the Águeda river basin in Spain-Portugal, indicating the sampling points.Figure 1. Map of the Águeda river basin in Spain-Portugal, indicating the sampling points.

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Materials and Methods

Fifty-two samples of groundwater corresponding to wells in the Águeda river basin from Spain and Portugal were collected between November and December 2011. The pesticides studied included herbicides, such as triazines (terbuthylazine, atrazine and their metabolites deethylatrazine, desethylterbutylazine and hydroxyterbuthylazine), ureas (isoproturon, linuron and diuron) and chloroacetamides (metolachlor), the insecticides diazinon, chlorpyrifos and dimethoate and the fungicides metalaxyl, cyprodinil, penconazole and tebuconazole. A method based on solid phase extraction (SPE) and quantification by liquid chromatography with mass spectrometric detection (LC–MS) was developed for determination of these compounds [3]. Different parameters were previously optimized, such as sorbent type (Oasis HLB and LiChrolut EN cartridges of polymeric sorbents, silica-based bonded C18 cartridges and graphitized carbon cartridges), elution solvent (methanol, acetonitrile, acetone and hexane) and sample volume (100, 250, 500 and 1000 mL). The validation and performance of the method were evaluated with several parameters as the influence of the matrix on the analysis, the linearity of the calibration curves, the accuracy (average recovery) and precision (reproducibility and repeatability) of the method, and also the limits of detection (LODs) and quantification (LOQs) were estimated.

Results and Discussion

Good recoveries were achieved with spiked water samples for a concentration of 0.1 �g

L�1, they were in the 65– 93 % range and the precisions were in the 7–18 % range under the optimal conditions. Calibration curves showed good linearity in the range of concentrations studied of 0.1–2 �g L�1 (r2 � 0.99) and low LOD (10–27 ng L�1) and LOQ (32-80 ng L�1) were achieved for the selected compounds, allowing their detection at the levels established by EU legislation. The highest recoveries in the SPE procedure were achieved when 500 mL of water were preconcentrated using an Oasis HLB cartridge and acetonitrile and acetone were used as the elution solvents. Matrix-matched standards were used to eliminate variable matrix effect.

In real samples, the number of pesticides over the level of 0.1 �g L�1 was higher in waters from Spain than from Portugal. Metolachlor and cyprodinil were detected in 100 % of samples from Spain, but only were over the limit of 0.1 �g L�1 in eight and three samples, respectively, for both pesticides. Desethylterbutilazine, linuron, diuron, diazinon, chlorpyrifos and dimethoate were not detected in any sample. The rest of pesticides were present in less than 25 % of samples, but only concentrations were over 0.1 �g L�1 in one sample, except hydroxyterbuthylazine, which was found in six samples. In waters of Portugal, the highest percentage of positive samples was for cyprodinil (74 %), followed by terbuthylazine (67 %), linuron (59 %); deethylatrazine (52 %), tebuconazole (56 %), atrazine and hydroxyterbuthylazine (7 %), and diuron (4 %), although pesticide concentration were only over 0.1 �g L�1 in ten samples, this was the case of linuron (7), terbuthylazine (2), and cyprodinil (1).

Conclusions

The developed methodology has been successfully applied to the analysis of 52 real groundwaters collected from the Águeda river basin. The results revealed the presence of some pesticides, herbicides and fungicides, in a significant number of samples, although only one or two pesticides were detected in concentrations over the EU limit in 36 % or 33 % of the samples collected in Spain and Portugal, respectively.

Acknowledgments

This work was funded by the EU co-financed by FEDER and POCTEP Program 2007-

2013 (Ref. CE: 0410_AGUEDA_3_E). E. Herrero-Hernández thanks CSIC for his JAE-Doc

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and E. Pose-Juan and A. Álvarez-Martín thank Spanish Ministry of Science and Innovation for their Juan de la Cierva contract and FPI fellowship respectively.

References [1] C. Postigo, M.J. López de Alda, D. Barceló, A. Ginebreda, T. Garrido, J. Fraile, JH

383, 83 (2010). [2] A. Hildebrant, M. Guillamon, S. Lacorte, R. Tauler, D. Barceló, WR 42, 3315 (2008). [3] E. Herrero-Hernández, M.S. Andrades, A. Álvarez-Martín, E. Pose-Juan, M.S.

Rodríguez-Cruz, M.J. Sánchez-Martín, JH submitted (2012).