Development and validation of an analytical method based on liquid chromatography–tandem mass spectrometry detection for the simultaneous determination of 13 relevant wastewater-derived contaminants in lettuce

Abstract

We present an analytical method developed and validated to study the potential uptake of 13 selected drugs (ten pharmaceuticals, one illicit drug, and two transformation products) into lettuce plants from contaminated water and soil. Some of the selected drugs (i.e., cocaine, methadone, cis-diltiazem, valsartan, and valsartan acid), which are commonly present in treated wastewater, were investigated for the first time in plant tissues. The method is based on ultrasonic solvent extraction with acetonitrile-methanol (1:1, v/v) and subsequent automated extract cleanup and analysis by means of online solid-phase extraction-liquid chromatography-tandem mass spectrometry. Optimum extraction conditions were selected after evaluation of analyte recoveries with four different extraction techniques (ultrasonic solvent extraction, solid-liquid extraction, pressurized liquid extraction, and a "quick, easy, cheap, effective, rugged, and safe" based method) and six different solvent mixtures. Furthermore, two different solid-phase extraction cleanup sorbents were evaluated. The method developed has high sensitivity (with limits of detection between 0.1 and 12.6 ng per gram dry weight and limits of quantification between 0.5 and 42.0 ng per gram dry weight), satisfactory accuracy (with analyte relative recoveries above 80% for all analytes but acridone and oxcarbazepine), and good repeatability (with relative standard deviations below 9% for all analytes). As part of the validation procedure, the analytical method was applied to the analysis of lettuce plants irrigated with water fortified with the selected compounds for the entire growing period. The results obtained evidenced the transfer of all the investigated drugs into lettuce leaves. Graphical Abstract ᅟ.

Analysis and fate of 14 relevant wastewater-derived organic pollutants in long-term exposed soil

“…Furthermore, their presence can contribute to the selection and proliferation of antibiotic-resistant bacteria [18][19][20]. Any pharmaceutical accumulated in soil could also potentially be uptaken by growing crops, which represents a potential risk to human health [4,[21][22][23][24][25][26][27]. In this regard, carbamazepine (CBZ), one of the drugs most frequently detected in soils [5], has been reported to translocate from soil to plant tissues [21].…”

“…198ology previously developed by the authors to analyze the target compounds in lettuce[21]. For soil analysis, a freezedried soil aliquot (0.5 g) was weighed into a 50-mL centrifuge tube and fortified with a known amount of the surrogate standard mixture (100 ng g −1 ).…”

“…MS acquisition was performed in the selective reaction monitoring (SRM) mode, by acquiring two SRM transitions per target analyte and one for the corresponding surrogate compound. A detailed description of the optimization of the LC-MS/MS conditions selectedhas been provided elsewhere[21]. The SRM transitions Analysis and fate of 14 relevant wastewater-derived organic pollutants in long-term exposed soil monitored for each analyte are summarized alongside with the optimal instrumental conditions set for their analysis in 252…”

Insights into the uptake, metabolization, and translocation of four non‐steroidal anti‐inflammatory drugs in cress (Lepidium sativum) by HPLC‐MS2

“…As an example, reclaimed wastewater counts for 50% of the total irrigation water used in Israel and also within the European Union, countries like Spain or Italy use substantial amounts of reclaimed water . For this reason the uptake, translocation and metabolization of xenobiotics by plants is the topic of a series of research projects reflected in a number of corresponding publications .…”

“…Focusing on the studies published so far, most of them can be categorized into two major groups, one of them devoted to the (ultra)‐trace analysis of the parent drug sometimes together with one or two of its major metabolites, and a second group dealing with the identification of metabolites produced in the plant upon treatment with (mostly higher concentrations) of the active pharmaceutical ingredients (API). Examples from the first group are the analysis of several pharmaceuticals in lettuce , the determination of 28 environmental contaminants (including several API´s) in lettuce, cabbage and tomato or investigations on the uptake of 19 common pharmaceuticals by celery, lettuce, cabbage, spinach, carrot, cucumber, bell pepper and tomato under field conditions . Studies devoted to the elucidation of the metabolization of the API´s by plants have for example focused on the transformation of carbamazepine in plant roots , or in tomato plants , on conjugation of amino acids with API´s , or on the metabolization of four non‐steroidal anti‐inflammatory drugs (NSAIDs) in cress .…”