Abstract
Purpose
To assess groundwater exposure to pesticides, in agricultural areas of ‘Ribatejo’ region (Portugal), and the influence of some key factors in that exposure, field, laboratory and modelling studies were carried out.
Methods
The study was performed in maize, potato, sugar beet, tomato and vegetables agricultural areas, located in a shallow aquifer, with pesticides use and, in most cases, with irrigation practices. Pesticides used in the studied agricultural areas and having leaching potential were selected, being considered also other pesticides included in priority lists, defined in Europe. Evaluation of groundwater exposure to pesticides was carried out by successively: (1) groundwater sampling in seven campaigns over the period 2004–2006; (2) pesticide analysis [including isolation and concentration from the groundwater samples and further determination by gas chromatography–mass spectrometry (GC–MS) of 14 herbicides, four insecticides and two metabolites]; and (3) analysis and discussion of the results by applying joint correspondence analysis (JCA).
Results
From the 20 pesticides and metabolites selected for the study, 11 were found in groundwater. Pesticides and metabolites most frequently detected were atrazine, alachlor, metolachlor, desethylatrazine, ethofumesate, α-endosulfan, metribuzine, lindane and β-endosulfan. The results showed that groundwater exposure to pesticides is influenced by local factors—either environmental or agricultural, as precipitation, soil, geology, crops and irrigation practices. Spring and autumn were more associated with the detection of pesticides being more likely to observe mixtures of these compounds in a groundwater sample in these transition seasons.
Conclusions
This work evidences the importance of models, which evaluate pesticides environmental behaviour, namely their water contamination potential (as Mackay multicompartimental fugacity model) and, specially, groundwater contamination potential (as GUS and Bacci and Gaggi leaching indices), in pesticide selection. Moreover, it reveals the importance to adapt proper statistical methods according to level of left-censored data. Using JCA was still possible to establish relations between pesticides and their temporal trend in a case study where there were more than 80% of data censored. This study will contribute to the Tagus river basin management plan with information on the patterns of pesticide occurrence in the alluvial aquifer system.
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References
AGROTEJO (2006) União Agrícola do Norte do Vale do Tejo. Estudo de impacte ambiental do estudo prévio do emparcelamento rural integrado de Azinhaga, Golegã e Riachos - Resumo não técnico, Golegã
Andrade AIASS, Stigter TY (2009) Multi-method assessment of nitrate and pesticide contamination in shallow alluvial groundwater as a function of hydrogeological setting and land use. Agr Water Manage 96(12):1751–1765
Antweiler RC, Taylor HE (2008) Evaluation of statistical treatments of left-censored environmental data using coincident uncensored data sets: I. Summary statistics. Environ Sci Technol 42(10):3732–3738
Aryal S, Bhaumik DK, Santra S, Gibbons RD (2009) Confidence interval for random-effects calibration curves with left-censored data. Environmetrics 20(2):181–189
Bacci E (1994) Ecotoxicology of organic contaminants. CRC Press/Lewis Publishers Inc, Boca Raton
Bacci E, Gaggi C (1993) Simple models for ranking pesticide mobility from soils. In: Paper presented at the IX symposium on pesticide chemistry. Mobility and degradation of xenobiotics, Piacenza, Italy, 12-13 October
Barbash JE, Resek EA (1997) Pesticides in groundwater. Distribution, trends, and governing factors. CRC Press, Boca Raton
Batista S (2003) Exposição da água subterrânea a pesticidas e nitratos em ecossistemas agrícolas do Ribatejo e Oeste e da Beira Litoral. Ph.D. Dissertation, Technical University of Lisbon
Batista S, Silva E, Cerejeira MJ, Silva-Fernandes AM (2001) Exposure of ground water to alachlor, atrazine and metolachlor in maize areas of Ribatejo and Oeste (Portugal). Toxicol Environ Chem 79(3):223–232
Batista S, Silva E, Galhardo S, Viana P, Cerejeira MJ (2002) Evaluation of pesticide contamination of ground water in two agricultural areas of Portugal. Int J Environ An Ch 82(8–9):601–609
Benzécri J-P (1973) Analyse des Données. T2 (leçons sur l'analyse factorielle et la reconnaissance des formes et travaux du Laboratoire de statistique de l'Université de Paris 6. T. 2: l'analyse des correspondances). Dunod: Paris
Berthouex PM, Brown LC (2002) Statistics for environmental engineers. CRC Press, Boca Raton
Cerejeira MJ (1993) Estudo da distribuição e destino final dos pesticidas no ambiente numa abordagem integrada. Caso da atrazina na Zona Agrária da Chamusca. Ph.D. Dissertation, Technical University of Lisbon
Cerejeira MJ, Silva-Fernandes A, Bacci E, Matos J (1995a) Atrazine and nitrates in the drinking ground water of the Chamusca agricultural area (Portugal). Toxicol Environ Chem 51(1):153–160
Cerejeira MJ, Silva-Fernandes A, Viana P, Bacci E (1995b) Atrazine and nitrate levels in the ground water of irrigation wells in the agricultural area of Chamusca (Portugal). Toxicol Environ Chem 49(1):123–128
Cerejeira MJ, Silva E, Batista S, Trancoso A, Centeno MSL, Silva-Fernandes A (2000) Simazine, metribuzine and nitrates in ground water of agricultural areas of Portugal. Toxicol Environ Chem 75(3):245–253
Cerejeira MJ, Viana P, Batista S, Pereira T, Silva E, Valério MJ, Silva A, Ferreira M, Silva-Fernandes AM (2003) Pesticides in Portuguese surface and ground waters. Water Res 37(5):1055–1063
CIS (2009) Common implementation strategy for the water framework directive (2000/60/EC). Technical report—2009-026, guidance document no. 18 guidance on groundwater status and trend assessment. Office for Official Publications of the European Communities: Luxembourg http://ec.europa.eu/environment/water/water-framework/groundwater/scienc_tec/cis/pdf/gw_trend_assessment.pdf. Accessed 30 September 2011
EC (2000) Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000, establishing a framework for community action in the field of water policy. Official Journal L 327 of 22.12.2001, pp. 0001–0073
EC (2002) Commission decision 2002/657/EC implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results. Official Journal L 221 of 17.08.2002, pp 8–36
EC (2006) Directive 2006/118/EC of the European Parliament and of the Council of 12 December 2006 on the protection of groundwater against pollution and deterioration. Official Journal L 372 of 27.12.2006, pp. 19–31
EEC (1991a) Council Directive 91/414/EEC of 15 July 1991 concerning the placing of plant protection products on the market. Official Journal L 230 of 19.8.1991, pp 1–32
EEC (1991b) Council Directive 91/676/EEC of 12 December 1991 concerning the protection of waters against pollution caused by nitrates from agricultural sources. Official Journal L 375 of 31.12.1991, pp 1–8
EFSA (2010) European Food Safety Authority. Management of left-censored data in dietary exposure assessment of chemical substances. EFSA Journal 8(3):1557
Europa (2011) Summaries of EU legislation. Protection of groundwater against pollution. http://europa.eu/legislation_summaries/environment/water_protection_management/l28139_en.htm. Accessed 30 September 2011
Farnham IM, Singh AK, Stetzenbach KJ, Johannesson KH (2002) Treatment of nondetects in multivariate analysis of groundwater geochemistry data. Chemometr Intell Lab 60(1–2):265–281
Fielding M, Barceló D, Helweg SA, Galassi S, Torstensson L, van Zoonen P, Wolter R, Angeletti G (1991) Pesticides in ground and drinking water. Water Pollution Research Report, 27, Commission of the European Communities: Brussels, Belgium
FOOTPRINT (2011) The FOOTPRINT pesticide properties database. http://sitem.herts.ac.uk/aeru/footprint/. Accessed 30 September 2011
Funari E et al (1995) Occurrence in groundwater and use of pesticides. In: Vighi M, Funari E (eds) Pesticide risk in groundwater. CRC, Boca Raton, pp 3–44
Gibbons RD, Coleman DE (2001) Statistical methods for detection and quantification of environmental contamination. Wiley, New York
Gibbons RD, Bhaumik DK, Aryal V (2009) Statistical methods for groundwater monitoring-second edition. Wiley, New Jersey
Gilbert RO (1987) Statistical methods for environmental pollution monitoring. Wiley, New York
Greenacre MJ (1984) Theory and applications of correspondence analysis. Academic, London
Greenacre M (2005) From correspondence analysis to multiple and joint correspondence analysis. In: Economics Working Papers 883, Department of Economics and Business, Universitat Pompeu Fabra
Greenacre MJ (2007) Interdisciplinary statistics. Correspondence analysis in practice-second edition. Chapman & Hall, Boca Raton
Greenacre MJ (2010) Correspondence analysis. Wiley Interdiscip Rev Comput Stat 2(5):613–619
Guéguin M, Roux E, Hernández Al, Porée F, Mabo P, Graindorge L, Carrault G (2007) Clustering follow-up time-series recorded by cardiac implantable devices. Conf. Proc. IEEE Eng Med Biol Soc: 3848–3851
Gustafson DI (1989) Groundwater ubiquity score: a simple method for assessing pesticide leachability. Environ Toxicol Chem 8(4):339–357
Helsel DR (1990) Less than obvious—statistical treatment of data below the detection limit. Environ Sci Technol 24(12):1766–1774
Helsel DR (2005) More than obvious: better methods for interpreting nondetect data. Environ Sci Technol 39(20):419A–423A
Helsel DR, Hirsch RM (1992) Statistical methods in water resources. Elsevier Science Publishers, Amsterdam
Hornsby AG, Wauchope RD, Herner AE (1996) Pesticide properties in the environment. Springer, New York
Jaskulké E et al (1999) Evaluation of pesticide residues in water. In: Brooks GT, Roberts TR (eds) Pesticide chemistry and bioscience. The food-environment challenge. The Royal Society of Chemistry, Cambridge, pp 368–385
Kolpin DW, Barbash JE, Gilliom RJ (1998) Occurrence of pesticides in shallow groundwater of the United States: initial results from the national water-quality assessment program. Environ Sci Technol 32(5):558–566
Liu S, Lu J-C, Kolpin DW, Meeker WQ (1997) Analysis of environmental data with censored observations. Environ Sci Technol 31(12):3358–3362
Lobo Ferreira JPC, Oliveira MM (1995) Caracterização dos recursos hídricos subterrâneos e mapeamento DRASTIC da vulnerabilidade dos aquíferos de Portugal. In: Lobo Ferreira JPC, Oliveira MM, Ciabatti P (eds) Desenvolvimento de um inventário das águas subterrâneas de Portugal, LNEC, DH, GIAS: Lisbon, pp I.7–I.315
Mackay D (2001) Multimedia environmental models: the fugacity approach-second edition. Lewis Publishers, Boca Raton
Mendes MP, Ribeiro L (2010) Nitrate probability mapping in the northern aquifer alluvial system of the river Tagus (Portugal) using Disjunctive Kriging. Sci Total Environ 408(5):1021–1034
Navarro A, Tauler R, Lacorte S, Barceló D (2010) Occurrence and transport of pesticides and alkylphenols in water samples along the Ebro River Basin. J Hydrol 383(1–2):18–29
Nenadić O, Greenacre M (2007) Correspondence analysis in R, with two- and three-dimensional graphics: the ca package. J Stat Softw 20(3)
Paralta EA, Oliveira MM, Batista SB, Francés AP, Ribeiro LF, Cerejeira MJ (2001) Aplicação de SIG na avaliação da vulnerabilidade aquífera e cartografia da contaminação agrícola por pesticidas e nitratos na região do Ribatejo. In: Paper presented at the Seminário sobre a Hidroinformática em Portugal, Lisbon, Portugal, 15-16 November
RGA (2011) Recenseamento Geral da Agricultura. Principais Resultados - Ribatejo e Oeste. www.ine.pt. Accessed 30 September 2011
Scheidleder A, Grath J, Winkler G, Strk U, Koreimann C, Gmeiner C, Nixon S, Casillas J, Leonard J, Elvira M, Lack TJ (1999) Groundwater quality and quantity in Europe. European Environmental Agency, Copenhagen
Silva E, Batista S, Viana P, Antunes P, Serôdio L, Cardoso AT, Cerejeira MJ (2006) Pesticides and nitrates in groundwater from oriziculture areas of the ‘Baixo Sado’ region (Portugal). Int J Environ An Ch 86(13):955–972
Silva E, Batista S, Caetano L, Cerejeira MJ, Chaves M, Jacobsen S-E (2011) Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal). Environ Monit Assess 176(1–4):331–341
Tomlin CDC (ed) (2006) The Pesticide Manual, 14th edn. BCPC, Hampshire
Travis CC, Land ML (1990) Estimating the mean of data sets with nondetectable values. Environ Sci Technol 24(7):961–962
van der Schriek T, Passmore DG, Rolão J, Stevenson AC (2007) Estuarine-fluvial floodplain formation in the Holocene Lower Tagus valley (Central Portugal) and implications for Quaternary fluvial system evolution. Quat Sci Rev 26(22–24):2937–2957
Acknowledgements
The authors wish to thank the Instituto Nacional de Investigação Agrária e das Pescas (INIAP) of the Ministry for Agriculture, Rural Development and Fisheries of Portugal for the financial support of the project AGRO no. 530 ‘Intervention Plan and Support Decision System Development for the Northern Tagus Alluvium’.
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Silva, E., Mendes, M.P., Ribeiro, L. et al. Exposure assessment of pesticides in a shallow groundwater of the Tagus vulnerable zone (Portugal): a multivariate statistical approach (JCA). Environ Sci Pollut Res 19, 2667–2680 (2012). https://doi.org/10.1007/s11356-012-0761-z
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DOI: https://doi.org/10.1007/s11356-012-0761-z