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The presence of the non-steroidal anti-inflammatory drugs (NSAIDs) in the environment is a fact, and aquatic and soil organisms are chronically exposed to trace levels of these emerging pollutants. This review presents the current state of knowledge on the metabolic pathways of NSAIDs in organisms at various levels of biological organisation. More than 150 publications dealing with target or non-target analysis of selected NSAIDs (mainly diclofenac, ibuprofen, and naproxen) were collected. The metabolites of phase I and phase II are presented. The similarity of NSAIDs metabolism to that in mammals was observed in bacteria, microalgae, fungi, higher plants, invertebrates, and vertebrates. The differences, such as newly detected metabolites, the extracellular metabolism observed in bacteria and fungi, or phase III metabolism in plants, are highlighted. Metabolites detected in plants (conjugates with sugars and amino acids) but not found in any other organisms are described. Selected, in-depth studies with isolated bacterial strains showed the possibility of transforming NSAIDs into assimilable carbon sources. It has been found that some of the metabolites show higher toxicity than their parent forms. The presence of metabolites of NSAIDs in the environment is the cumulative effect of their introduction with wastewaters, their formation in wastewater treatment plants, and their transformation by non-target wild-living organisms., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Passive sampling is an attractive technique for the long-term monitoring of pharmaceuticals in the water environment. The reliability of the received results depends on the properly performed calibration, namely the determination of analyte sampling rates. This step can be the source of a systematic error, as the sampling rate values are dependent on the water donor phase parameters. This is especially important for pharmaceuticals, since their chemical characteristics and ionic form change with pH. In this study, the cross-effect of pH (3, 7, and 9) and salinity (0, 7, and 35 practical salinity unit, using artificial sea water) on the passive sampling of 21 pharmaceuticals (antiparasitics, beta-blockers, non-steroidal anti-inflammatory drugs, sulfonamides) was tested. The primarily determined parameter was the sampling rate. In addition, the extraction efficiency, partitioning coefficient, and the concentration of the analytes on the sorbent were calculated. Generally, for the non-steroidal anti-inflammatory drugs, beta-blockers, and antiparasitics, the change both in pH and salinity had a negligible impact on the mentioned experimental parameters. In contrast, the extraction of sulfonamides was impacted by both pH and salinity, while lipophilicity was not a decisive parameter., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, an ASE (Accelerated Solvent extraction)-SPE (Solid Phase Extraction)-GC/MS(SIM) method for the simultaneous determination of five non-steroidal anti-inflammatory drugs (NSAIDs: ibuprofen (IBU), paracetamol (PAR), diclofenac (DIC), naproxen (NAP) and ketoprofen (KET)) and three natural estrogens (estrone (E1), 17β-estradiol (E2), estriol (E3)) in mussels was proposed, which is simple, cheap and easy for use in environmental laboratories. For the first time, the sorbents: PSA (Primary Secondary Amine) and FLORISIL®, placed directly inside the extraction cells, were used for the improvement of the ASE procedure for the isolation of these pollutants from mussel samples. The application of FLORISIL® especially allowed the purification of the extract to increase recovery, without the loss of analytes, or prolongation of the extraction time. The proposed ASE-SPE-GC/MS(SIM) method was validated (the method detection limit values were in the range of 1 ng/g dry weight (d.w.) for IBU to 7 ng/g d.w. for E1; the measurement intermediate precision was between 0.24% and 7.85%; the mean recovery was in the range of 80-118%) and used for the determination of NSAIDs and estrogenic hormones in whole tissue of the mussels Mytilus edulis trossulus collected from the Gulf of Gdansk (southern Baltic Sea). IBU, NAP, DIC and E1 were determined in these samples; however, the pharmaceuticals were found only in smaller (with a length of 2-3 cm) individuals. The observed differences in the concentrations of CEC in smaller and older mussel organisms were fully discussed. Summarizing, this method could be used for monitoring these CEC in such organisms in order to expand our knowledge of their influence on the water ecosystem, however, in such investigations smaller mussel organisms should be used., (Copyright © 2019. Published by Elsevier B.V.)

High salinity and a relatively high pH are two factors characterizing the marine water environment, which is one of the main final reservoirs receiving pharmaceutical residues. The same factors have an undeniable impact on the extraction efficiency and kinetics of uptakes of polar analytes from water by sorbent-based passive sampling techniques. Recently, we presented a novel passive sampling technique, in which ionic liquids are applied as receiving phases for pharmaceutical monitoring in water (the Passive Sampling with Ionic Liquids technique). In this paper we test the impact of salinity and pH on the PASSIL calibration (sampling rate determination) and the extraction efficiencies of sulfonamides, beta-blockers and nonsteroidal anti-inflammatory drugs selected as model contaminants. Trihexyl(tetradecyl)phosphonium dicyanamide ([P666-14][N(CN) 2 ]) was taken as the stable liquid receiving phase. It selectively extracted neutral and negatively charged analytes from donor solutions of different pH (1, 3, 7 and 9). The presence of salt (7, 20 and 35 PSU) decreased the efficiency (by 5-65%) and R s (by 0.017Lday -1 to 0.574Lday -1 ) of PASSIL for all target compounds. The general conclusion is that salinity and pH have a significant impact on the calibration of passive dosimeters for ionizable compounds, both for the new PASSIL technique and standard POCIS techniques., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Pharmaceuticals are continually being released into the environment. Because of their physical and chemical properties, many of them or their bioactive metabolites can accumulate in sediments, sludge and soils, and induce adverse effects in terrestrial organisms. However, due to the very limited methods permitting the detection of these low-level concentration compounds in such complex matrices, their concentrations in natural solids remain largely unknown. In this paper, an analytical method for the simultaneous determination of thirteen pharmaceuticals (eight non-steroidal anti-inflammatory drugs and five oestrogenic hormones) in solid matrices was developed. The proposed MAE-SPE-GC-MS(SIM) method has been successfully validated providing a linear response over a concentration range of 1(17)-1000(1200)ng/g, depending on the pharmaceuticals, with correlation coefficients above 0.991. The method detection limits were in the range of 0.3-5.7 ng/g, absolute recoveries above 50%, except estrone. The developed method was applied in the analysis of the target compounds in sediment, sludge and soils collected in Poland giving primary data on their concentrations in such matrices in Poland. The obtained results confirmed that the proposed method can be successfully used in the analysis of real environmental solid samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This paper discusses a new silylating reagent - dimethyl(3,3,3-trifluoropropyl)silyldiethylamine (DIMETRIS) - for the derivatisation of non-steroidal anti-inflammatory drugs (NSAIDs) prior to GC-MS analysis. DIMETRIS reacts with seven target compounds (diclofenac, ibuprofen, ketoprofen, naproxen, flurbiprofen and paracetamol, as well as salicylic acid, a degradation product of acetylsalicylic acid) at 30°C for 30min, producing mono-O-dimethyltrifluoropropylsilyl (mono-O-DMTFPS) derivatives. The mass spectra of these new derivatives are given and fully interpreted. The usefulness of mono-O-DMTFPS derivatives for the qualitative and quantitative analysis of NSAIDs using GC-MS is compared with that of trimethylsilyl and methyl analogues. Methyl derivatives are found to be less appropriate for this purpose because they yield the lowest detector responses during GC-MS measurements. Both silyl derivatives are more suitable for determining such NSAIDs, although the matrix effect with mono-O-DMTFPS derivatives is smaller. Finally, SPE-GC-MS(SIM) based on the derivatisation of NSAIDs by DIMETRIS is evaluated, validated and applied to the determination of these drugs in sea water (Baltic Sea) and wastewater samples collected in Poland. This work confirms that DIMETRIS is suitable for the trace analysis of NSAIDs in real samples and provides an interesting alternative to silylating and methylating reagents., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Non-steroidal anti-inflammatory drugs are the group of pharmaceuticals that is most often found in the environment, whereas estrogenic hormones are considered to be potent endocrine disruptors. However, the fate and persistence of these compounds in the environment are still unclear. In this study we propose two approaches for determining these compounds in environmental water samples: GC-MS using time windows and operating in selected ion-monitoring mode (SIM) and, for the first time, gas chromatography with electron capture detection (GC-ECD). The identification criteria of both methods fulfilled the requirements of Directive 2002/657/EC. The use of time windows improved the sensitivity of GC-MS measurements. In GC-MS analysis the pharmaceuticals were determined as trimethylsilyl, in GC-ECD as pentafluoropropionyl derivatives. The influence of such parameters as the type of reagent, type of solvent, reaction time, reaction temperature and microwave irradiation in a household microwave oven on the efficacy of silylation was investigated. Derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 1% trimethylchlorosilane (TMCS) in pyridine (1:1, v/v) for 30 min in 60 °C was found to be optimal. Optimization of the solid phase extraction procedure (SPE) confirmed that the application of Oasis HLB cartridges, the acidification of loading samples to pH2 and the use of methanol as eluent gave the best absolute recoveries (ARs) of the target compounds. The following ARs of all the compounds were achieved: 58.2-106.8% in influent wastewater, 77.8-103.4% in effluent wastewater and 81.2-101.9% in surface water samples. Validation of the SPE-GC-MS method enables 13 pharmaceuticals to be determined with MDLs between 3.3 and 343.6 ng/L, depending on the analytes and matrices. GC-ECD analysis enables the determination of 6 pharmaceuticals in surface water samples with MDLs between 0.7 and 5.4 ng/L. The proposed methods were successfully used for analyzing selected pharmaceuticals in wastewaters and river waters in Poland., (Copyright © 2012 Elsevier B.V. All rights reserved.)