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A monitoring program of pesticides was implemented in the "ZV1" vulnerable zone (Directive 91/676/EEC) in Portugal, in order to assess the impact of intensive horticulture practices on groundwater contamination. The monitoring network comprised 23 sampling points sampled every 3 months during a 2-year period. Forty-two pesticides belonging to varied chemical families, including current pesticides, persistent organic pollutants (POPs), and degradation products, were analyzed by solid-phase microextraction (SPME) and gas chromatography with electron-capture detection-thermoionic specific detection (GC-ECD-TSD) or mass spectrometry (GC-MS). Statistical treatment was performed by descriptive analysis followed by chemometric multivariate analysis. The latter included cluster analysis, linear discriminant analysis, and factor analysis. Twenty-two pesticides were quantitated, 20 pesticides were not detected, and metalaxyl, benalaxyl, quinalphos, pirimicarb, and prometryn were only qualitatively detected. The most frequently detected pesticides (% of samples analyzed) were lindane (53%), pendimethalin (49%), endosulfan sulfate (44%), and endosulfan (38%) while those that most frequently exceeded the 0.1 microgram L-1 European Union (EU) limit were pendimethalin (13%), endosulfan (12%), endosulfan sulfate (11%), and atrazine (9%). 45% of the samples exceeded the EU limit for individual pesticides while 27% exceeded the limit set to the sum of pesticides (0.5 microgram L-1). Principal component analysis revealed five principal components that were attributed to environmental/agrochemical managing factors. The broad range of pesticides investigated combined with the intensive character of the local agriculture contributed to the diversity of pesticides that were detected. However, the frequency of pesticides above the EU regulatory limit is comparable to that found in the literature concerning different Portuguese and European regions.
