Thirty-year Monitoring of S-triazine Herbicide Contamination in the Aquifer North of Vicenza (north-east Italy)

The aquifer north of Vicenza, Italy, is one of the main and most studied drinking water reservoirs within the Veneto region. The area is an intensive cropland, and monitoring of s-triazine herbicides and metabolites has been carried out since the late eighties. This study analysed the trends of atrazine (ATR), terbuthylazine (TBZ), deethyl-atrazine (DEA), and deethyl-terbuthylazine (DET) concentrations from 1987 to 2016 and related the variations of agricultural land use, herbicide load, and pesticide regulations to the residence time of pollutants in the aquifer. In total, 785 water samples collected from 82 selected check wells were analysed with high-resolution gas chromatography combined with mass spectrometry. Non-detects were substituted by one-half the limit of detection. Over the 30 years of monitoring, concentrations of all of the pollutants decreased at all sampling sites. Since the beginning, TBZ and DET residues have been systematically lower than ATR and DEA, respectively, with more than 70% of the data below the limit of detection and never exceeding the European Maximum Acceptable Concentration (MAC) for a single pesticide (0.1 μg/L). The highest concentrations of ATR and DEA showed a spatial shift along the flow direction, suggesting an increase in groundwater residence time from the recharge zone to the accumulation zone of the aquifer. The last residues of ATR were found 27 years after its ban. Although all of the concentrations were lower than those found elsewhere in Europe, the sum of s-triazines overcame the MAC in 20% of the samples. Considering the structural and toxicological similarities of s-triazines, these findings confirm the necessity of better characterisation of the toxicological risk posed by mixtures.