Fast determination of 40 drugs in water using large volume direct injection liquid chromatography–tandem mass spectrometry

This work describes a rapid analytical method based on direct sample injection of water samples for the simultaneous identification/quantification of 40 emerging compounds, including pharmaceuticals and drugs of abuse. The water samples were analyzed by ultra-high-performance liquid chromatography coupled to hybrid triple quadrupole mass spectrometer (UHPLC–MS/MS QqQ). Taking profit of the increasing sensitivity of nowadays tandem mass spectrometers, direct sample injection of large volumes has been an attractive alternative to pre-concentration steps. In this work, the developed methodology has been validated at three concentration levels (10, 100 and 1000 ng/L) in 10 different water samples of different types (5 effluent wastewater and 5 surface water samples). The majority of compounds could be satisfactory validated at these concentrations, showing good recoveries and precision. With only few exceptions, the limits of quantification (LOQs), estimated from the sample chromatogram at lowest spiked level tested, were below 3 ng/L. The method was applied to the analysis of 10 effluent wastewater and 10 surface water samples. Venlafaxine was the compound most frequently detected (80%) in surface water, followed by acetaminophen (70%). Regarding effluent wastewater, valsartan and 4-acetyl aminoantipyrine were detected in 9 out of 10 samples analyzed. These two compounds together with 4-formyl aminoantipyrine and naproxen showed the highest concentrations (>2000 ng/L). In these cases, a dilution step was required for a correct quantification. As an additional evaluation of the method performance, the same water samples were analyzed in another laboratory by a second analytical methodology, based on on-line solid-phase-extraction coupled to LC–MS/MS (QqQ).The authors are very grateful to Serveis Centrals d׳Instrumentació Científica (SCIC) of University Jaume I for using the Xevo TQS mass spectrometer. The financial support of the Centro de Desarrollo Tecnológico Industrial (CDTIIDI-20110823/EXP00044257), of the Spanish Ministry of Education and Science (Ref CTQ2012-36189) and of Generalitat Valenciana (research group of excellence PROMETEO/2009/054; Collaborative Research on Environment and Food Safety, ISIC/2012/016) is acknowledged

Hydrogeological, hydrodynamic and anthropogenic factors affecting the spread of pharmaceuticals and pesticides in water resources of the Granada plain (Spain)

The anthropogenic organic contaminants contemplated in the environmental legislation, as well as those of emerging concern, threaten the quality of water resources to a degree that remains largely unknown. Contaminant exposure in the aquatic environment is a crucial element if a full understanding of the risk is pursued. There are still many uncertainties about the occurrence of organic pollutants and behavior in the hydro(geo)logical media in large scale areas. The case study of the unconfined aquifer of the Granada Plain (approximately 200 km2) is presented here. Two surface and groundwater monitoring campaigns were conducted (March 2017 and June 2018). In total, 41 out of 171 target organic pollutants were detected, at least once: 17 pharmaceuticals or drugs of abuse, 21 pesticides or their metabolites and three polyaromatic hydrocarbons. In addition, physico-chemical parameters were measured during the monitoring campaigns and hydrochemical parameters and stable isotopes (δ2H, δ18O, δ13C) were analyzed. Statistical tests confirmed the significance of seasonal changes for some of these parameters (e.g., EC, Cl-, F-, δ18O, δ13C), revealing the influence from snowmelt water input on streams and the intensification of irrigation. In March 2017, the group of pesticides (largely represented by triazines) predominated, whereas the frequency of detection of pharmaceuticals increased substantially in June 2018. Results suggest four main factors affecting the spatial and seasonal variation of organic pollutants in the aquifer: the anthropogenic factor determining the period of contaminant release throughout the year (pesticide application period and growth of tourism) along with irrigation practices that include reclaimed wastewater; unsaturated zone thickness; hydraulic gradient and river-groundwater hydraulic connection. The latter can be especially important in the case of those contaminants whose main path of entry into the aquatic environment occurs through wastewater discharge into streams (i.e., pharmaceuticals).This article is a contribution to the Research Groups RNM-308 and RNM 128 of the “Junta de Andalucía” and the project “Study, detection and behavior of emerging contaminants in anthropized watersheds in Andalusia-EMAN (P20_397)”