Most cited article - PubMed ID 27044290
Development of fast and robust multiresidual LC-MS/MS method for determination of pharmaceuticals in soils
The use of pharmaceuticals entails a significant risk of environmental contamination. Wastewater treatment plants (WWTPs) are considered to be the main contributors to contamination as they ineffectively eliminate these compounds from wastewater. Simultaneously, they produce solid waste, sludge, which often contains a variety of retained pollutants, including pharmaceuticals. Since sewage sludge is frequently applied to agricultural soil due to its rich nutrient content, pollutants are introduced into the environment in this way. Only a few studies have been carried out on the topic of the analysis of pharmaceuticals in sludge. Therefore, information on the occurrence of pharmaceuticals in sludge is limited. The present study employed quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) analysis to establish a simple and reliable procedure for determining 16 pharmaceuticals (antibiotics, anticonvulsants, antidepressants and β-blockers) in sewage sludge. The method has been thoroughly validated, and parameters such as linear range, accuracy, precision, matrix effects and detection and quantification limits were assessed. Our method achieved low limits of quantification (0.5-9.0 µg kg-1) and satisfactory recoveries (51-101%). Forty sludge samples from different WWTPs across the Czech Republic were analysed. Fourteen compounds were detected and quantified in most samples, with antidepressants having the highest detection frequency and overall content. Sertraline, with a mean concentration of 521.0 µg kg-1, was notably prevalent alongside its metabolite norsertraline (mean concentration 204.9 µg kg-1). The antibiotic azithromycin was also found at higher levels (mean concentration 185.1 µg kg-1).
- Keywords
- LC–MS/MS, Micropollutants, Pharmaceuticals, QuEChERS, Sewage sludge,
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Chromatography, Liquid MeSH
- Liquid Chromatography-Mass Spectrometry MeSH
- Pharmaceutical Preparations analysis MeSH
- Environmental Monitoring methods MeSH
- Wastewater chemistry MeSH
- Sewage * chemistry MeSH
- Tandem Mass Spectrometry * MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- Czech Republic MeSH
- Names of Substances
- Water Pollutants, Chemical MeSH
- Pharmaceutical Preparations MeSH
- Wastewater MeSH
- Sewage * 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
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
Soils can be contaminated by pharmaceuticals. The aim of this study was to evaluate the impact of soil conditions (influencing sorption and persistence of pharmaceuticals in soils) and plant type on the root uptake of selected pharmaceuticals and their transformation in plant-soil systems. Four plants (lamb's lettuce, spinach, arugula, radish) planted in 3 soils were irrigated for 20 days (26) with water contaminated by one of 3 pharmaceuticals (carbamazepine, atenolol, sulfamethoxazole) or their mixture. The concentrations of pharmaceuticals and their metabolites in soils and plant tissues were evaluated after the harvest. Sulfamethoxazole and atenolol dissipated rapidly from soils. The larger concentrations of both compounds and an atenolol metabolite were found in roots than in leaves. Sulfamethoxazole metabolites were below the limits of quantifications. Carbamazepine was stable in soils, easily uptaken, accumulated, and metabolized in plant leaves. The efficiency of radish and arugula (both family Brassicaceae) in metabolizing was very low contrary to the high and moderate efficiencies of lamb's lettuce and spinach, respectively. Compounds' transformations mostly masked the soil impact on their accumulation in plant tissues. The negative relationships were found between the carbamazepine sorption coefficients and its concentrations in roots of radish, lamb's lettuce, and spinach.
- Keywords
- Compound’s translocation in plant, Metabolites, Pharmaceuticals, Plant-dependent compound’s transformation, Plants, Root uptake, Soils,
- MeSH
- Atenolol metabolism MeSH
- Carbamazepine analysis metabolism MeSH
- Soil Pollutants analysis metabolism MeSH
- Plant Leaves metabolism MeSH
- Soil MeSH
- Raphanus metabolism MeSH
- Plants metabolism MeSH
- Sulfamethoxazole metabolism MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Atenolol MeSH
- Carbamazepine MeSH
- Soil Pollutants MeSH
- Soil MeSH
- Sulfamethoxazole MeSH
Insecticides usually present in low concentrations in streams are known to impair behaviour and development of non-target freshwater invertebrates. Moreover, there is growing awareness that the presence of natural stressors, such as predation risk may magnify the negative effects of pesticides. This is because perception of predation risk can by itself lead to changes on behaviour and physiology of prey species. To evaluate the potential combined effects of both stressors on freshwater detritivores we studied the behavioural and developmental responses of Chironomus riparius to chlorantraniliprole (CAP) exposure under predation risk. Also, we tested whether the presence of a shredder species would alter collector responses under stress. Trials were conducted using a simplified trophic chain: Alnus glutinosa leaves as food resource, the shredder Sericostoma vittatum and the collector C. riparius. CAP toxicity was thus tested under two conditions, presence/absence of the dragonfly predator Cordulegaster boltonii. CAP exposure decreased leaf decomposition. Despite the lack of significance for interactive effects, predation risk marginally modified shredder effect on leaf decomposition, decreasing this ecosystem process. Shredders presence increased leaf decomposition, but impaired chironomids performance, suggesting interspecific competition rather than facilitation. C. riparius growth rate was decreased independently by CAP exposure, presence of predator and shredder species. A marginal interaction between CAP and predation risk was observed regarding chironomids development. To better understand the effects of chemical pollution to natural freshwater populations, natural stressors and species interactions must be taken into consideration, since both vertical and horizontal species interactions play their role on response to stress.
- Keywords
- Chlorantraniliprole, Detritivore invertebrates, Leaf decomposition, Predation risk,
- MeSH
- Chironomidae drug effects growth & development physiology MeSH
- Insecta drug effects growth & development physiology MeSH
- Insecticides toxicity MeSH
- Larva drug effects growth & development physiology MeSH
- Plant Leaves MeSH
- Nymph drug effects growth & development physiology MeSH
- Alnus MeSH
- ortho-Aminobenzoates toxicity MeSH
- Food Chain * MeSH
- Predatory Behavior * MeSH
- Feeding Behavior drug effects MeSH
- Odonata growth & development physiology MeSH
- Animals MeSH
- Check Tag
- Animals MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- chlorantranilipole MeSH Browser
- Insecticides MeSH
- ortho-Aminobenzoates MeSH