Investigation of pesticides and their transformation products in the Júcar River Hydrographical Basin (Spain) by wide-scope high-resolution mass spectrometry screening.

The Water Framework Directive 2000/60/EC implemented by the European Union established as the main objectives to achieve a "good ecological and chemical status" of the surface water and a "good quantitative and chemical status" of groundwater bodies. One of the major pressures affecting water bodies comes from the use of pesticides and their potential presence in the water ecosystems. For this purpose, the reliable determination of pesticides and their transformation products (TPs) in natural waters (both surface and groundwater) is required. The high number of compounds potentially reaching the aquatic environment makes extraordinary difficult, if not impossible, to investigate all these compounds even using the most powerful analytical techniques. Among these, liquid chromatography coupled to high-resolution mass spectrometry is emphasized due to its strong potential for detection and identification of many organic contaminants thanks to the accurate-mass full spectrum acquisition data. This work focuses on wide-scope screening of many pesticides and their TPs in surface water and groundwater samples, collected between March and May 2017, in the Júcar River Hydrographical Basin, Spain. For this purpose, a home-made database containing more than 500 pesticides and TPs was employed. Analyses performed by liquid chromatography coupled to quadrupole-time of flight mass spectrometry (LC-QTOF MS) allowed the identification of up to 27 pesticides and 6 TPs. The most detected compounds in groundwater were the herbicides atrazine, simazine, terbuthylazine, and their TPs (atrazine-desethyl, terbumeton-desethyl and terbuthylazine-desethyl). Regarding surface water, the fungicides carbendazim, thiabendazole and imazalil, the herbicide terbutryn and the TP terbumeton-desethyl were also detected. These results illustrate the wide use of these compounds (in the present or in the recent past) in the area under study and the vulnerability of the water bodies, and are in accordance with previous findings in other water bodies of the different Spanish Hydrographic systems.

Using electrical resistivity tomography to assess the effectiveness of managed aquifer recharge in a salinized coastal aquifer.

Over 40 years, the detrital aquifer of the Plana de Castellón (Spanish Mediterranean coast) has been subjected to seawater intrusion because of long dry periods combined with intensive groundwater exploitation. Against this backdrop, a managed artificial recharge (MAR) scheme was implemented to improve the groundwater quality. The large difference between the electrical conductivity (EC) of the ambient groundwater (brackish water due to marine intrusion) and the recharge water (freshwater) meant that there was a strong contrast between the resistivities of the brackish water saturated zone and the freshwater saturated zone. Electrical resistivity tomography (ERT) can be used for surveying similar settings to evaluate the effectiveness of artificial recharge schemes. By integrating geophysical data with lithological information, EC logs from boreholes, and hydrochemical data, we can interpret electrical resistivity (ER) with groundwater EC values and so identify freshwater saturated zones. Using this approach, ERT images provided a high-resolution spatial characterization and an accurate picture of the shape and extent of the recharge plume of the MAR site. After 5 months of injection, a freshwater plume with an EC of 400-600 µS/cm had formed that extended 400 m in the W-E direction, 250 m in the N-S direction, and to a depth of 40 m below piezometric level. This study also provides correlations between ER values with different lithologies and groundwater EC values that can be used to support other studies.

Comprehensive monitoring of organic micro-pollutants in surface and groundwater in the surrounding of a solid-waste treatment plant of Castellón, Spain.

The solid-waste treatment plant of RECIPLASA is located in the municipality of Onda (Castellón province), which is an important agricultural area of Spain, with predominance of citrus crops. In this plant, all urban solid wastes from the town of Castellón (around 200,000 inhabitants) and other smaller towns as Almassora, Benicàssim, Betxí, Borriana, L'Alcora, Onda and Vila-Real are treated. In order to evaluate the potential impact of this plant on the surrounding water, both surface and groundwater, a comprehensive monitoring of organic pollutants has been carried out along 2011, 2012 and 2013. To this aim, an advanced analytical strategy was applied for wide-scope screening, consisting on the complementary use of liquid chromatography (LC) and gas chromatography (GC) coupled to mass spectrometry (MS) with quadrupole (Q)-time of flight analyser (TOF). A generic solid-phase extraction with Oasis HLB cartridges was applied prior to the chromatographic analysis. The screening included more than 1500 organic pollutants as target compounds, such as pesticides, pharmaceuticals, veterinary drugs, drugs of abuse, UV-filters, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), among others. Pesticides, mainly herbicides, were the compounds more frequently detected. Other compounds as antioxidants, cosmetics, drugs of abuse, PAHs, pharmaceuticals and UV filters, were also identified in the screening though at much lower frequency. Once the screening was made, quantitative analysis focused on the compounds more frequently detected was subsequently applied using LC coupled to tandem MS with triple quadrupole analyser. In this way, up to 24 pesticides and transformation products (TPs), 7 pharmaceuticals, one drug of abuse and its metabolite could be quantified at sub-ppb concentrations. Along the three years of study, ten compounds were found at concentrations higher than 0.1µg/L. Most of them were pesticides and TPs, a fact that illustrates that the main source of pollution seems to be the agricultural activities in this area.

The influence of nitrate leaching through unsaturated soil on groundwater pollution in an agricultural area of the Basque country: a case study.

The average nitrate concentration in the groundwater of the Vitoria-Gasteiz (Basque Country) quaternary aquifer rose from 50 mg NO3-/l during 1986 to over 200 mg/l in 1995, which represents an increase of some 20 mg NO3-/l per year. From 1995 to 2002, the nitrate concentration of the groundwater slightly decreased. Nitrate groundwater pollution during the period 1986-1993 was the result of the abusive use of fertilizers and of the modification in the recharge patterns of the aquifer from surface water sources. From 1993 onwards, apart from a possible rationalization in fertilizer use, the change in the origin of water for irrigation and wetland restoration (water is taken now from artificial pools outside the quaternary aquifer) must be explained in order to account for the observed decrease in nitrate concentration in the groundwater. The water of the aquifer and of the unsaturated zone were studied in two experimental plots (one of them cultivated and the other uncultivated) for 18 months (January 1993-June 1994), during the period of maximum contamination, to evaluate the effect of fertilizers on soil water and on the water in the saturated zone. The soil water was sampled using soil lysimeters at various depths. The volumetric water content of the soil was measured at the same depths using time domain reflectrometry (TDR) probes. Samples of groundwater were taken from a network of wells on the aquifer scale, two located close to the two experimental plots. The temporal evolution of nitrate concentrations in soil solutions depends on the addition of fertilizers and on soil nitrate leaching by rain. During episodes of intense rain (>50 mm in a day), the groundwater deposits are recharged with water coming from the leaching of interstitial soil solutions, causing an increase in the groundwater nitrate concentrations. The mass of nitrate leached from the cultivated zone is five times higher than that of the nitrate leached from the uncultivated zone (1147 kg NO3-/ha in the cultivated sector as against 211 kg NO3-/ha in the uncultivated sector), although part of the nitrate leached into the soil had been previously deposited by the rise of the water table. If we consider that the level of groundwater input is similar in both plots, we may conclude that 964 kg NO3-/ha circulated towards the groundwater in the cultivated zone during the period under study, representing 87% of the nitrate applied to the soil in the form of fertilizer during that period.