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Pharmaceuticals released into the aquatic and soil environments can be absorbed by plants and soil organisms, potentially leading to the formation of unknown metabolites that may negatively affect these organisms or contaminate the food chain. The aim of this study was to identify pharmaceutical metabolites through a triplet approach for metabolite structure prediction (software-based predictions, literature review, and known common metabolic pathways), followed by generating in silico mass spectral libraries and applying various mass spectrometry modes for untargeted LC-qTOF analysis. Therefore, Eisenia fetida and Lactuca sativa were exposed to a pharmaceutical mixture (atenolol, enrofloxacin, erythromycin, ketoprofen, sulfametoxazole, tetracycline) under hydroponic and soil conditions at environmentally relevant concentrations. Samples collected at different time points were extracted using QuEChERS and analyzed with LC-qTOF in data-dependent (DDA) and data-independent (DIA) acquisition modes, applying both positive and negative electrospray ionization. The triplet approach for metabolite structure prediction yielded a total of 3762 pharmaceutical metabolites, and an in silico mass spectral library was created based on these predicted metabolites. This approach resulted in the identification of 26 statistically significant metabolites (p < 0.05), with DDA + and DDA - outperforming DIA modes by successfully detecting 56/67 sample type:metabolite combinations. Lettuce roots had the highest metabolite count (26), followed by leaves (6) and earthworms (2). Despite the lower metabolite count, earthworms showed the highest peak intensities, closely followed by roots, with leaves displaying the lowest intensities. Common metabolic reactions observed included hydroxylation, decarboxylation, acetylation, and glucosidation, with ketoprofen-related metabolites being the most prevalent, totaling 12 distinct metabolites. In conclusion, we developed a high-throughput workflow combining open-source software with LC-HRMS for identifying unknown metabolites across various sample types., (© 2024. The Author(s).)

Microplastics, pervasive contaminants in freshwater ecosystems, have raised ecological concerns. Efforts are underway to substitute conventional plastics with biodegradable alternatives that should be more easily decomposed in the environment. However, the biodegradation of these alternatives depends on specific conditions such as temperature, humidity, pH, and microorganisms, which are not always met. Consequently, these biodegradable alternatives can also fragment and generate microplastics, which can be ingested and affect biota. In this study, we investigated the acute, chronic, and multigenerational effects of two fractions (particles <63 μm and particles <125 μm) of biodegradable poly-3-hydroxybutyrate (P3HB) at varying concentrations on the inhibition, mortality, reproduction activity, and growth of the freshwater invertebrate Daphnia magna . No acute effects were observed for either size fraction. However, during chronic and multigenerational experiments, an increase in the concentration of P3HB microplastics corresponded with increased mortality, reduced reproductive activity, and slower growth among the mother organisms. Given the important role of D. magna in the food chain, these findings suggest that biodegradable microplastics may indeed negatively affect freshwater ecosystems., Competing Interests: 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., (© 2024 The Authors.)

In the European circular economy, agricultural practices introduce pharmaceutical (PhAC) residues into the terrestrial environment, posing a potential risk to earthworms. This study aimed to assess earthworm bioaccumulation factors (BAFs), the ecotoxicological effects of PhACs, the impact of biochar on PhAC bioavailability to earthworms, and their persistence in soil and investigate earthworm uptake mechanisms along with the spatial distribution of PhACs. Therefore, earthworms were exposed to contaminated soil for 21 days. The results revealed that BAFs ranged from 0.0216 to 0.329, with no significant ecotoxicological effects on earthworm weight or mortality (p > 0.05). Biochar significantly influenced the uptake of 14 PhACs on the first day (p < 0.05), with diminishing effects over time, and affected significantly the soil-degradation kinetics of 16 PhACs. Moreover, MALDI-MS analysis revealed that PhAC uptake occurs through both the dermal and oral pathways, as pharmaceuticals were distributed throughout the entire earthworm tissue without specific localization. In conclusion, this study suggests ineffective PhAC accumulation in earthworms, highlights the influence of biochar on PhAC degradation rates in soil, and suggests that uptake can occur through both earthworm skin and oral ingestion., (© 2024. The Author(s).)

The presence of human and veterinary pharmaceuticals (PhACs) in the environment poses potential risks. To comprehensively assess these risks, robust multiresidual analytical methods are essential for determining a broad spectrum of PhAC classes in various environmental compartments (soil, plants, and soil organisms). This study optimized extraction methods for analyzing over 40 PhACs from various matrices, including soil, lettuce, and earthworms. A four-step ultrasonic extraction method with varying extraction conditions and subsequent solid phase extraction was developed for soil samples. QuEChERS methods were optimized for extracting PhACs from lettuce and earthworm samples, addressing a literature gap in these less-studied matrices. The quantification of PhACs in soil, lettuce, and earthworm extracts was performed using a single LC-MS/MS method. Following thorough method validation, earthworms and lettuce were exposed to a mixture of 27 pharmaceuticals in a soil environment. The method validation results demonstrated the robustness of these methods for a broad spectrum of PhACs. Specifically, 29 out of 42 PhACs were extracted with an average efficiency > 50% and RSD < 30% from the soil; 40 out of 42 PhACs exhibited average efficiency > 50% and %RSD < 30% from the earthworms, while 39 out of 42 PhACs showed average efficiency > 50% and RSD < 30% from the lettuce. Exposure experiments confirmed the viability of these methods for quantifying a diverse range of PhACs in different environmental compartments. This study presents three thoroughly validated methods for determining more than 40 PhACs in diverse matrices, enabling a comprehensive assessment of PhAC dissemination in the environment., (© 2024. The Author(s).)

From the physical point of view, soil is a heterogenic polydisperse system. It often becomes a place of a secondary contamination during extinguishing uncontrolled areal fires in nature. Foam extinguishing agents (FEAs), used at these events, basically contain surface active substances and perfluorinated compounds. These tend to be captured in the soil matrix due to their specific properties. Contaminants could be partly flushed out with rainwater, which causes several times dilution of contamination and lower ecotoxic activity. However in the dry season, foam solution infiltrates into the bed soil without any dilution. This study deals with the direct influence of soil the sorption complex on ecotoxicity of five selected FEAs, i.e. Expyrol F 15, Finiflam F 15, Moussol APS F 15, Pyrocool B and Sthamex F 15. The substances tested were prepared in concentration of work solution and then applied on standard soil matrix LUFA 2.3. For experimental purposes, a column infiltration apparatus was designed and compiled. Filtrates were collected and then tested using the plant organisms Sinapis alba and Allium cepa L. The study compared ecotoxicologic effects of filtrates with an original work solution. Moussol APS F 15 seems to be the least ecotoxic of the FEAs tested. A direct influence of soil sorption complex onto ecotoxicity reduction was also established. This finding demonstrates the sorption ability of soil particles and ion exchange activity of the soil matrix. It is a positive finding for biota of aquatic environment, yet at the expense of those in soil.