Pesticides in the Ebro River basin: Occurrence and risk assessment

In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 21% of the samples, respectively). The only pesticide detected in biota was chlorpyrifos (up to 840.2 ng g−1). Ecotoxicological risk assessment through RQs showed that organophosphorus and azol presented high risk for algae; organophosphorus, benzimidazoles, carbamates, juvenile hormone mimic and other pesticides for daphnia, and organophosphorus, azol and juvenile hormone mimics for fish. The sum TUsite for water and sediments showed values < 1 for the three bioassays. In both matrices, daphnia and fish were more sensitive to the mixture of pesticide residues present.This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects NET-SCARCE project (CTM2015-69780-REDC); “Evaluation of Emerging Contaminants in the Turia River Basins: From Basic Research to the Application of Environmental Forensics (EMERFOR)” (GCL2011- 29703-C02-02, http://mefturia.es) and European Communities 7th Framework Programme funding under Grant Agreement No. 603629-ENV-2013-6.2.1-Globaqua. A, Ccanccapa gratefully acknowledges the Conselleria DEducaci o, Cultura y Sport de Valencia for the financial support through “Santiago Grisolía” Scholarship Program.Peer reviewe

Spatio-temporal patterns of pesticide residues in the Turia and Júcar Rivers (Spain)

A study was conducted on the occurrence of 50 pesticides in water and sediments of Turia and Júcar Rivers (Valencian Community, Eastern Spain) for a period of two consecutive years each, 2010/2011 and 2012/2013, respectively to assess the contribution of agriculture and urban activities on pesticide pollution. The results showed that mean concentrations of pesticides ranged from <. LOQ up to 200. ng/L. Chlorpyrifos was the most frequent pesticide whereas imazalil, thiabendazole, tolclofos methyl, ethion and carbofuran were those found at higher concentrations. Ubiquitous pesticides are those with long half-lives. The most polluted parts of the rivers were the headwaters and the mouth, which could be related to the agricultural practices and rainfall. Contrarily, in the abrupt part of the rivers of difficult access the contamination is low. Other quality parameters monitored in this study also corroborate the worst water quality in the alluvial plains that coincides with higher anthropic pressure. The temporal variations also indicated a strong relation of pesticide concentrations with hydrology, the higher the river flow, the higher number and frequency of pesticides but at lower concentrations. On the contrary, at lower river flows higher pesticide concentrations were detected. The risk assessment for aquatic biota pointed out that organophosphorus and fungicides are a threat to fish and daphnia and herbicides and fungicides are hazards for algae. Thus, the strict control of pesticide concentrations is important to preserve the aquatic ecosystems health.This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects “Assessing and Predicting Effects on Water Quantity and Quality in Iberian Rivers Caused by Global Change (SCARCE)” (No. CSD2009-00065, http://www.scarceconsolider.es) and “Evaluation of Emerging Contaminants in the Turia River Basins: From Basic Research to the Application of Environmental Forensics (EMERFOR)” (GCL2011-29703-C02-02, http://mefturia.es). A. Ccanccapa gratefully acknowledges the Conselleria D'Educació, Cultura y Sport de la Generalitat Valenciana for the financial support through “Santiago Grisolía” Scholarship Program.Peer Reviewe

Comparison of green sample preparation techniques in the analysis of pyrethrins and pyrethroids in baby food by liquid chromatography–tandem mass spectrometry

A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method was developed for simultaneous analysis of natural pyrethrins and synthetic pyrethroids residues in baby food. In this study, two sample preparation methods based on ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) and salting-out assisted liquid–liquid extraction (SALLE) were optimized, and then, compared regarding the performance criteria. Appropriate linearity in solvent and matrix-based calibrations, and suitable recoveries (75–120%) and precision (RSD values ≤ 16%) were achieved for selected analytes by any of the sample preparation procedures. Both methods provided the analytical selectivity required for the monitoring of the insecticides in fruit-, cereal- and milk-based baby foods. SALLE, recognized by cost-effectiveness, and simple and fast execution, provided a lower enrichment factor, consequently, higher limits of quantification (LOQs) were obtained. Some of them too high to meet the strict legislation regarding baby food. Nonetheless, the combination of ultrasound and DLLME also resulted in a high sample throughput and environmental-friendly method, whose LOQs were lower than the default maximum residue limit (MRL) of 10 μg kg−1 set by European Community for baby foods. In the commercial baby foods analyzed, cyhalothrin and etofenprox were detected in different samples, demonstrating the suitability of proposed method for baby food control.M.H. Petrarca and H.T. Godoy are grateful to CNPq – National Council for Scientific and Technological Development, for financial support and for the scholarship awarded to the first author (Process n° 140271/2013-9). This work has been co-supported by the Spanish Ministry of Economy and Competitiveness and the ERDF (European Regional Development Fund) through the project CGL2015-64454-C2-1-R as well as by the University of Valencia through the project UV-INV-AE15-348995.Peer reviewe

Intra-annual trends of fungicide residues in waters from vineyard areas in La Rioja region of northern Spain

The temporal trends of fungicides in surface and ground water in 90 samples, including both surface waters (12) and ground waters (78) from an extensive vineyard area located in La Rioja (Spain), were examined between September 2010 and September 2011. Fungicides are used in increasing amounts on vines in many countries, and they may reach the water resources. However, few data have been published on fungicides in waters, with herbicides being the most frequently monitored compounds. The presence, distribution and year-long evolution of 17 fungicides widely used in the region and a degradation product were evaluated in waters during four sampling campaigns. All the fungicides included in the study were detected at one or more of the points sampled during the four campaigns. Metalaxyl, its metabolite CGA-92370, penconazole and tebuconazole were the fungicides detected in the greatest number of samples, although myclobutanil, CGA-92370 and triadimenol were detected at the highest concentrations. The highest levels of individual fungicides were found in Rioja Alavesa, with concentrations of up to 25.52 g L1, and more than 40 % of the samples recorded a total concentration of &gt;0.5 g L1. More than six fungicides were positively identified in a third of the ground and surface waters in all the sampling campaigns. There were no significant differences between the results obtained in the four sampling campaigns and corroborated a pattern of diffuse contamination from the use of fungicides. The results confirm that natural waters in the study area are extremely vulnerable to contamination by fungicides and highlight the need to implement strategies to prevent and control water contamination by these compounds. © 2016 Springer-Verlag Berlin Heidelber