Validation and application of a multiresidue method based on liquid chromatography-tandem mass spectrometry for evaluating the plant uptake of 74 microcontaminants in crops irrigated with treated municipal wastewater

Abstract

Reuse of treated wastewater for agricultural purposes can mitigate water stress in some regions where the lack of water is an extended problem. However, the environmental long-term consequences of this practice are still unknown. It is demonstrated that using reclaimed water for irrigation lead to accumulation and translocation of some microcontaminants (MCs) in soil and crops. However, so far, only a small group of contaminants has been investigated. This study aims to develop and validate a simple and efficient multiresidue method based on QuEChERs (Quick, Easy, Cheap, Effective and Rugged) extraction coupled to liquid chromatography tandem mass spectrometry (LC-MS/MS). The novelty of the study relays in the large number of MCs analyzed (74), some of them not previously investigated, in three commodities (lettuce, radish and strawberry). Optimized conditions yielded good results for the three commodities under study. Up to 84% of the compounds were recovered within a 70-120% range, with good repeatability (relative standard deviations below 20% in most cases). Method detection (MDLs) and quantification limits (MQLs) ranged from 0.01 to 2 ng/g. The proposed method was successfully applied to assess the potential uptake of MCs by lettuce and radish crops irrigated with wastewater under controlled conditions for 3 and 1.5 months, respectively. 12 compounds were detected in the crops with concentrations ranging from 0.03 to 57.6 ng/g. N-Formyl-4-aminoantipyrine (4FAA) was the most concentrated compound. The application of this method demonstrated for the first time the accumulation of 5 contaminants of emerging concern (CECs) not previously reported: 4FAA, N-Acetyl-4-aminoantipyrine (4AAA), hydrochlorothiazide, mepivacaine and venlafaxine.

Identification of transformation products of carbamazepine in lettuce crops irrigated with Ultraviolet-C treated water

“…CBZ-d10 was used as extraction quality control check. Martínez-Piernas et al, 2018b. 90 propylene pots (9 × 9 × 10 cm) were filled with sterilized peat (autoclaved using autoclave-bags at 121 ºC during 15 min in batches of 5 kg of peat).…”

“…For this reason, broad spectrum extraction methodologies are required to obtain efficient recoveries in a wide range of compounds . QuEChERS (Quick, Easy,Cheap, Effective, Rugged and Safe) and pressurized liquid extraction (PLE) have demonstrated to be good alternatives even in these complex environmental matrices (Martínez-Piernas et al, 2018b) (Jelić et al, 2009). Besides, the application of screening methodologies accomplished by liquid chromatography coupled to high resolution mass spectrometry (HRMS), have undoubtedly improved the identification of unexpected or not previously validated compounds by the application of non-target and suspect screening approaches ( Martínez-Piernas et al, 2018a).…”

Development of Methods for the Determination of PhACs in Soil/Earthworm/Crop System Irrigated with Reclaimed Water

“…However, the skip of this step could improve the recoveries of some compounds that are retained by the SPE adsorbents. LC-MS is usually the instrumental analysis performed, thanks to its ability to achieve low limits of quantification and detection, good repeatability, and reproducibility [7,121]. Indeed, LC-MS/ MS have been the instrumental analysis with great confidence to confirm the analytes and its capability to reach very low limits of detection and quantification [122,123].…”

“…Sometimes, for dry, dehydrated, or fat-rich samples, water is added up to the minimum quantity required for the extraction [35,139,140]. Acidification of the organic solution, majorly with acetic acid or formic acid, has shown to improve the recoveries of compounds susceptible to pH [121,141]. The main difference with the other extraction methods consists in the use of salts which force the analytes to pass from the aqueous phase to the organic phase, known as the salting out process [142].…”

“…However, current studies suggest that the original salt kit is the most used salt mix to extract pharmaceutical residues from plant tissues, with excellent results [45,140,143]. On the other hand, AOAC salts and EN salts were widely used providing more stability to the target compounds [7,121]. Aside from the extraction phase, Anastassiades and colleagues also developed a new clean-up methodology to remove any interferents based on a solid-phase extraction in the dispersive phase (d-SPE) [19].…”