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.

• Keywords
• Biochar, Earthworms, MALDI-MS, Mass spectrometry, Pharmaceutical uptake, QuEChERS, Liquid chromatography, Soil pollution,
• MeSH
• Biological Availability MeSH
• Charcoal * chemistry   MeSH
• Liquid Chromatography-Mass Spectrometry MeSH
• Soil Pollutants * MeSH
• Pharmaceutical Preparations metabolism   MeSH
• Oligochaeta * MeSH
• Soil * chemistry   MeSH
• Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization MeSH
• Animals MeSH
• Check Tag
• Animals MeSH
• Publication type
• Journal Article MeSH
• Names of Substances
• biochar MeSH Browser
• Charcoal * MeSH
• Soil Pollutants * MeSH
• Pharmaceutical Preparations MeSH
• Soil * MeSH

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.

• Keywords
• Liquid chromatography, Mass spectrometry, Multiresidual analytical methods, Pharmaceutical pollution, QuEChERS, Solid-phase extraction,
• MeSH
• Chromatography, Liquid MeSH
• Solid Phase Extraction MeSH
• Soil Pollutants * analysis   MeSH
• Pharmaceutical Preparations analysis   MeSH
• Oligochaeta * MeSH
• Soil * chemistry   MeSH
• Lactuca * chemistry   MeSH
• Tandem Mass Spectrometry MeSH
• Animals MeSH
• Check Tag
• Animals MeSH
• Publication type
• Journal Article MeSH
• Names of Substances
• Soil Pollutants * MeSH
• Pharmaceutical Preparations MeSH
• Soil * MeSH

Global climate changes cause water scarcity in many regions, and the sustainable use of recycled water appears crucial, especially in agriculture. However, potentially hazardous compounds such as pharmaceuticals can enter the food chain and pose severe risks. This paper aims to study the presence of selected pharmaceutical active compounds (PhACs) and their metabolites in crops grown in aeroponic conditions and evaluate the potential of PhAC plant uptake. A solvent extraction with an acidified mixture of acetonitrile and water followed by LC-HRMS was developed and validated for quantifying nine pharmaceuticals and their nine metabolites in three plants. We aimed for a robust method with a wide linear range because an extensive concentration range in different matrices was expected. The developed method proved rapid and reliable determination of selected pharmaceuticals in plants in the wide concentration range of 10 to 20,000 ng g-1 and limit of detection range 0.4 to 9.0 ng g-1. The developed method was used to study the uptake and translocation of pharmaceuticals and their metabolites in plant tissues from an aeroponic experiment at three different pH levels. Carbamazepine accumulated more in the leaves of spinach than in arugula. On the other hand, sulfamethoxazole and clindamycin evinced higher accumulation in roots than in leaves, comparable in both plants. The expected effect of pH on plants' uptake was not significant.

• Keywords
• Extraction, Pharmaceutical, Plant uptake, Soil pollution,
• MeSH
• Hydrogen-Ion Concentration MeSH
• Pharmaceutical Preparations MeSH
• Water MeSH
• Crops, Agricultural * MeSH
• Agriculture * methods   MeSH
• Publication type
• Journal Article MeSH
• Names of Substances
• Pharmaceutical Preparations MeSH
• Water MeSH

The accumulation of six pharmaceuticals of different therapeutic uses has been thoroughly investigated and compared between onion, spinach, and radish plants grown in six soil types. While neutral molecules (e.g., carbamazepine (CAR) and some of its metabolites) were efficiently accumulated and easily translocated to the plant leaves (onion > radish > spinach), the same for ionic (both anionic and cationic) molecules seems to be minor to moderate. The maximum accumulation of CAR crosses 38,000 (onion), 42,000 (radish), and 7000 (spinach) ng g-1 (dry weight) respectively, in which the most majority of them happened within the plant leaves. Among the metabolites, the accumulation of carbamazepine 10,11-epoxide (EPC - a primary CAR metabolite) was approximately 19,000 (onion), 7000 (radish), and 6000 (spinach) ng g-1 (dry weight) respectively. This trend was considerably similar even when all these pharmaceuticals applied together. The accumulation of most other molecules (e.g., citalopram, clindamycin, clindamycin sulfoxide, fexofenadine, irbesartan, and sulfamethoxazole) was restricted to plant roots, except for certain cases (e.g., clindamycin and clindamycin sulfoxide in onion leaves). Our results clearly demonstrated the potential role of this accumulation process on the entrance of pharmaceuticals/metabolites into the food chain, which eventually becomes a threat to associated living biota.

• Keywords
• Metabolism, Pharmaceutical accumulation, Pharmaceuticals, Plant-dependent transformation of pharmaceuticals, Plants, Root uptake, Soils, Translocation of pharmaceuticals in plant,
• MeSH
• Onions MeSH
• Clindamycin metabolism   MeSH
• Soil Pollutants * analysis   MeSH
• Pharmaceutical Preparations metabolism   MeSH
• Soil chemistry   MeSH
• Raphanus * metabolism   MeSH
• Plants metabolism   MeSH
• Spinacia oleracea metabolism   MeSH
• Publication type
• Journal Article MeSH
• Names of Substances
• Clindamycin MeSH
• Soil Pollutants * MeSH
• Pharmaceutical Preparations MeSH
• Soil MeSH

Food contamination is a major worldwide risk for human health. Dynamic plant uptake of pollutants from contaminated environments is the preferred pathway into the human and animal food chain. Mechanistic models represent a fundamental tool for risk assessment and the development of mitigation strategies. However, difficulty in obtaining comprehensive observations in the soil-plant continuum hinders their calibration, undermining their generalizability and raising doubts about their widespread applicability. To address these issues, a Bayesian probabilistic framework is used, for the first time, to calibrate and assess the predictive uncertainty of a mechanistic soil-plant model against comprehensive observations from an experiment on the translocation of carbamazepine in green pea plants. Results demonstrate that the model can reproduce the dynamics of water flow and solute reactive transport in the soil-plant domain accurately and with limited uncertainty. The role of different physicochemical processes in bioaccumulation of carbamazepine in fruits is investigated through Global Sensitivity Analysis, which shows how soil hydraulic properties and soil solute sorption regulate transpiration streams and bioavailability of carbamazepine. Overall, the analysis demonstrates the usefulness of mechanistic models and proposes a comprehensive numerical framework for their assessment and use.

• MeSH
• Bayes Theorem MeSH
• Pisum sativum MeSH
• Carbamazepine analysis   MeSH
• Soil Pollutants * analysis   MeSH
• Humans MeSH
• Soil * MeSH
• Animals MeSH
• Check Tag
• Humans MeSH
• Animals MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Names of Substances
• Carbamazepine MeSH
• Soil Pollutants * MeSH
• Soil * MeSH