Occurrence of Banned and Currently Used Herbicides, in Groundwater of Northern Greece: A Human Health Risk Assessment Approach.

The presence of pesticide residues in groundwater, many years after their phase out in European Union verifies that the persistence in aquifer is much higher than in other environmental compartments. Currently used and banned pesticides were monitored in Northern Greece aquifers and a human health risk assessment was conducted. The target compounds were the herbicides metolachlor (MET), terbuthylazine (TER), atrazine (ATR) and its metabolites deisopropylatrazine (DIA), deethylatrazine (DEA) and hydroxyatrazine (HA). Eleven sampling sites were selected to have representatives of different types of wells. Pesticides were extracted by solid-phase extraction and analyzed by liquid chromatography. MET was detected in 100% of water samples followed by ATR (96.4%), DEA and HA (88.6%), DIA (78.2%) and TER (67.5%). ATR, DIA, DEA, HA, MET and TER mean concentrations detected were 0.18, 0.29, 0.14, 0.09, 0.16 and 0.15 µg/L, respectively. Obtained results were compared with historical data from previous monitoring studies and temporal trends were assessed. Preferential flow was the major factor facilitating pesticide leaching within the month of herbicide application. Moreover, apparent age of groundwater and the reduced pesticide dissipation rates on aquifers resulted of long-term detection of legacy pesticides. Although atrazine had been banned more than 18 years ago, it was detected frequently and their concentrations in some cases were over the maximum permissible limit. Furthermore, human health risk assessment of pesticides was calculated for two different age groups though drinking water consumption. In all examined wells, the sum of the HQ values were lower than the unity. As a result, the analyzed drinking water wells are considered safe according to the acute risk assessment process. However, the presence of atrazine residues causes concerns related with chronic toxicity, since ATR R values were greater than the parametric one of 1 × 10-6 advised by USEPA, for both age groups.

Environmental monitoring and risk assessment in a tropical Costa Rican catchment under the influence of melon and watermelon crop pesticides.

A monitoring network was established in streams within a catchment near the Costa Rican Pacific coast (2008-2011) to estimate the impact of pesticides in surface water (84 samples) and sediments (84 samples) in areas under the influence of melon and watermelon production. A total of 66 (water) and 47 (sediment) pesticides were analyzed, and an environmental risk assessment (ERA) was performed for four taxa (algae, Daphnia magna, fish and Chironomus riparius). One fungicide and seven insecticides were detected in water and/or sediment; the fungicide azoxystrobin (water) and the insecticide cypermethrin (sediments) were the most frequently detected pesticides. The insecticides endosulfan (5.76 µg/L) and cypermethrin (301 µg/kg) presented the highest concentrations in water and sediment, respectively. The ERA revealed acute risk in half of the sampling points of the melon-influenced area and in every sampling point from the watermelon-influenced area. Safety levels were exceeded within and around the crop fields, suggesting that agrochemical contamination was distributed along the catchment, with potential influence of nearby crops. Acute risk was caused by the insecticides chlorpyrifos, cypermethrin and endosulfan to D. magna, fish and C. riparius; the latter was the organism with the overall highest/continuous risk. High chronic risk was determined in all but one sampling point, and revealed a higher number of pesticides of concern. Cypermethrin was the only pesticide to pose chronic risk for all benchmark organisms. The results provide new information on the risk that tropical crops pose to aquatic ecosystems, and highlight the importance of including the analysis of sediment concentrations and chronic exposure in ERA.

Pesticide monitoring and ecotoxicological risk assessment in surface water bodies and sediments of a tropical agro-ecosystem.

A pesticide monitoring study including 80 and 60 active ingredients (in surface waters and sediments, respectively) was carried out in a river basin in Costa Rica during 2007-2012. A special emphasis was given on the exceptional ecological conditions of the tropical agro-ecosystem and the pesticide application strategies in order to establish a reliable monitoring network. A total of 135 water samples and 129 sediment samples were collected and analyzed. Long-term aquatic ecotoxicological risk assessment based on risk quotient in three trophic levels was conducted. Short-term risk assessment was used to calculate the toxic unit and prioritization of sampling sites was conducted by the sum of toxic units in both aquatic and sediment compartments. Dimethoate (61.2 µg/L), propanil (30.6 µg/L), diuron (22.8 µg/L) and terbutryn (4.8 µg/L) were detected at the highest concentrations in water samples. Carbendazim and endosulfan were the most frequently detected pesticides in water and sediment samples, respectively. Triazophos (491 µg/kg), cypermethrin (71.5 µg/kg), permethrin (47.8 µg/kg), terbutryn (38.7 µg/kg), chlorpyrifos (18.2 µg/kg) and diuron (11.75 µg/kg) were detected at the highest concentrations in sediment samples. The pesticides carbendazim, diuron, endosulfan, epoxyconazole, propanil, triazophos and terbutryn showed non-acceptable risk even when a conservative scenario was considered. Sum TUsite higher than 1 was found for one and two sampling sites in water and sediment compartments, respectively, suggesting high acute toxicity for the ecosystem. MAIN FINDING OF THE WORK: Exceptional ecological conditions of the tropical agro-ecosystem affect the fate of pesticides in water and sediment environment differently than the temperate one.

Accelerated biodegradation of selected nematicides in tropical crop soils from Costa Rica.

Degradation and mineralization behavior of selected nematicides was studied in soil samples from fields cultivated with banana, potato, and coffee. Degradation assays in most of the studied soils revealed shorter half-lives for carbofuran (CBF) and ethoprophos (ETP) in samples with a history of treatment with these compounds, which may have been caused by enhanced biodegradation. A short half-life value for CBF degradation was also observed in a banana field with no previous exposure to this pesticide, but with a recent application of the carbamate insecticide oxamyl, which supports the hypothesis that preexposure to oxamyl may cause microbial adaptation towards degradation of CBF, an observation of a phenomenon not yet tested according to the literature reviewed. Mineralization assays for CBF and terbufos (TBF) revealed that history of treatment with these nematicides did not cause higher mineralization rates in preexposed soils when compared to unexposed ones, except in the case of soils from coffee fields. Mineralization half-lives for soils unexposed to these pesticides were significantly shorter than most reports in the literature in the same conditions. Mineralization rates for soils with a previous exposure to these pesticides were also obtained, adding to the very few reports found. This paper contributes valuable data to the low number of reports dealing with pesticide fate in soils from tropical origin.