Parent tetracyclines and their transformation products can be present in vegetables growth in soils amended with manure, treated sewage sludge, or irrigated with reclaimed urban wastewater. The presence of some tetracycline antibiotics and transformation products is already regulated in foodstuffs of animal origin but not yet in vegetables. In this paper, an analytical method is proposed for the determination of seven parent tetracycline antibiotics and six transformation products. Selected transformation products correspond to epimers and dehydration products, which have been reported to be the most toxic ones. The proposed method is based on miniaturized matrix solid-phase dispersion (& micro;-MSPD) method combined with online solid-phase extraction-liquid chromatography-tandem mass spectrometry (online SPE-LC-MS/MS) determination. The method has been validated in radish edible parts (leaves and bulb), to be used for food monitoring, and in roots, to be used in pollutant plant uptake and translocation studies. Proposed method provides MQLs lower than 5 ng g-1 dw, accuracy in the range 85-100%, and RSD% lower than 5.5%, for most of the compounds and matrices. Application of the method to radish samples revealed the presence of transformation products of tetracycline antibiotics even in samples where their respective parent compound was not detected. Greenness assessment, using ComplexGAPI and AGREEprep Green Analytical Chemistry metrics, revealed the highest greenness degree of the proposed method in comparison to other methods reported in literature for determination of tetracycline antibiotics in vegetables.

Chiral pharmaceuticals (CPs) have gained growing attention in environmental studies regarding the differential behavior of individual enantiomers in racemic mixtures. This study investigates the stereoselectivity and efficiency of montmorillonite (MMT), a natural and low-cost adsorbent, for the removal of a wide group chiral pharmaceuticals and metabolites (atenolol, propranolol, metoprolol, fluoxetine, venlafaxine, norfluoxetine, and O-desmethylvenlafaxine). The effects of adsorption conditions including initial CP concentration, contact time, adsorbent dose, solution pH, and humic acid content were evaluated. In most adsorption experiments, no significant stereoselective behavior was observed, except for the case where a low adsorbent dose was applied. Interestingly, as the solution humic acid content increased (up to 40 mg/L), the adsorption capacity was increased for most of the target CPs. Isotherm studies revealed that the Freundlich model described the experimental data well and the process was favorable. Adsorption mechanism was interpreted by material characterization before and after adsorption. High removal efficiencies (88.0 to 99.8%) and the non-enantioselective behavior of MMT indicate that it can be used effectively for the simultaneous removal of both enantiomeric forms of various chiral pharmaceuticals from aqueous matrices.

Background/Objectives: The application of organic soil amendments constitutes an important source of antibiotic residues in agricultural soils. However, studies have mainly focused on a few parent tetracyclines, whereas information on their transformation products (TPs) in organic amendments remains scarce. Therefore, this study assessed the occurrence and environmental risk of six tetracyclines and seven TPs in organic amendments. Methods: Processed livestock manures applied in the European Union (horse, poultry, and bovine manure), as well as fresh and treated sewage sludge, were analyzed using matrix solid-phase dispersion (MSPD) combined with online SPE-LC-MS/MS. Environmental risk was assessed using risk quotients (RQs) based on predicted environmental concentrations in soil (PECsoil) calculated from the maximum measured concentrations and predicted no-effect concentrations in soil (PNECsoil) obtained either directly from terrestrial ecotoxicity data or derived from aquatic ecotoxicity data using the equilibrium partitioning method and soil-water distribution coefficients. Results: Tetracyclines and their TPs were widely detected in both sample types, although concentrations varied according to matrix type and treatment. Overall, sludge showed higher detection frequencies and concentrations than manure. Doxycycline and tetracycline were the predominant parent compounds, reaching concentrations up to 2838 ng g−1 dry weight (dw) in manure and 2892 ng g−1 dw in sludge. Epimerized TPs were frequently detected and sometimes exceeded the concentrations of their parent compounds, especially epitetracycline and epioxytetracycline. Among the sludge types and treatment conditions investigated, anaerobically digested sludge showed the highest tetracycline concentrations, whereas the composted sludge sample presented the lowest concentrations. Individual RQs indicated insignificant to low ecotoxicological risk, whereas cumulative RQ (ΣRQ) values, used as conservative estimates of co-exposure to all evaluated tetracyclines and their TPs, fell within the medium-risk category for bovine manure and anaerobically digested sludge, with the composted sludge sample showing the lowest ΣRQ. Conclusions: These findings highlight the importance of including TPs in environmental monitoring and the differences in tetracycline occurrence and environmental risk to soil among the processed manure types and sludge treatment conditions investigated.

The contamination of water by cytostatic drugs poses a significant ecological risk. This study presents a novel TiO2/clay/Ag catalyst, synthesized through a simplified sol–gel method, and applied for the efficient removal of etoposide (ETP) from aqueous environments. A thorough characterization of the catalyst’s structural and morphological properties was carried out using various analytical techniques (XRD, FTIR, SEM, EDX, XPS). Several parameters, such as contact time, photocatalyst dosage, pH, and drug concentration, were studied. Under visible light irradiation, complete degradation (100

Sewage sludge tends to accumulate emerging contaminants during wastewater treatment, with many pollutants persisting even after undergoing sludge stabilization treatments, posing potential environmental risks. Antibiotic contamination is of particular concern due to their high persistence and ability to promote the development of resistance genes. However, limited information is available regarding the behavior of antibiotic metabolites. In this study, seventeen antibiotics and metabolites of five therapeutic groups of critically and highly important antibiotics were monitored in wastewater and sludges from fifteen wastewater treatment plants (WWTPs) with five different sludge stabilization treatments: anaerobic digestion, aerobic digestion, dehydration, composting, and lagooning. Results demonstrated that the distribution ratio of metabolites and parent compounds in influent wastewater was correlated with their excretion rates, reflecting pharmaceutical consumption as their primary source to WWTPs. Fluoroquinolone and sulfonamide antibiotics were predominant in influent wastewater, while macrolide antibiotics were more prevalent in primary sludge, likely due to their higher hydrophobicity, which results in greater retention in sludge. Parent compounds dominated over metabolites in sewage sludge, with composting plants showing the highest removal efficiency and highest metabolization among all sludge stabilization technologies studied. Tetracyclines were not detected in any of the sludge samples analyzed and macrolides resulted in the most persistent antibiotics in treated sludges. Results showed low environmental risks associated with the reuse of treated sludge as an organic amendment in agriculture.

Introduction:Poly- and perfluoroalkyl substances (PFASs) are a numerous group of synthetic organic compounds used in various industries. They pollute the natural environment and negatively affect humans and animals. The aim of the present investigation was to assess the exposure of sheep bred in the Kyrgyz Republic to six selected PFASs. Material and Methods:Six selected PFASs were assessed in 50 sheep (39 females and 11 males) of Kyrgyz and Arashan breeds ranging in age from 1 to 8 years (mean 2.1 ± 1.1), recruited equally from the Alamedin and Sokuluk regions. The substances were five perfluoroalkyl carboxylic acids (perfluorobutanoic acid - PFBuA, perfluoropentanoic acid - PFPeA, perfluorohexanoic acid - PFHxA, perfluoroheptanoic acid - PFHpA and perfluorooctanoic acid - PFOA) and perfluorooctane sulphonic acid (PFOS), and were determined through the liquid chromatography-tandem mass spectrometry of hair samples. Results:All the listed PFASs were found in the studied hair samples. The highest concentrations were noted for PFPeA and PFBuA. The concentration of PFPeA ranged from 0.99 ng/g to 27.90 ng/g (mean 5.55 ± 4.54 ng/g) and that of PFBuA from 0.95ng/g to 14.18 ng/g (mean 2.24 ± 2.34 ng/g). The mean concentration levels of other PFASs were as follows: 1.06 ± 0.78 ng/g for PFHxA, 1.02 ± 0.76 ng/g for PFHpA, 0.87 ± 0.68 ng/g for PFOA and below the method quantification limit for PFOS. Clear differences in PFASs levels were noted between the two regions. Conclusion:Sheep are exposed to various PFASs, and sheep wool and items made of it may be the source of human exposure to these compounds. Hair samples may be used for biomonitoring of sheep exposure to PFASs.

In 2000, the European Commission issued a draft document to regulate the application of sludges from wastewater treatment plants to soil, proposing concentration limits for certain organic compounds, including Linear Alkylbenzene Sulfonates (LAS). A concentration limit of 2600 mg/kg dry matter (dm) for LAS was set, although requirements vary across EU Member States. The aim of this work was to assess the influence of different types of treated sludge (anaerobically-digested, aerobically-digested, dehydrated, lagoon, and compost) on LAS degradation after soil application and to conduct an environmental risk assessment, considering the provisions of EU Directive 86/278/EEC. Laboratory experiments showed LAS concentrations in treated sludges ranged from 236 mg/kg dm in compost to 11,302 mg/kg dm in lagoon sludge. After soil amendment, LAS concentrations in soil ranged from less than 1.5 mg/kg to 66 mg/kg dm, and after three weeks, they ranged from 0.7 to 19 mg/kg dm. LAS degraded rapidly, with half-lives (DT50) from 2 days (dehydrated sludge) to 13 days (anaerobically-digested sludge and compost). Degradation followed a double-exponential decay model, with faster degradation in the solution phase compared to the sorbed phase. DT50 values for LAS increased with chain length for anaerobically- and aerobically-digested sludges but decreased for dehydrated sludge. The type of sludge influenced LAS degradation due to microbial populations and LAS sorption. LAS posed no ecological risk when applied via treated sludge, except for lagoon sludge, which posed a risk for up to seven days. Composting was the most recommended treatment for sludge prior to land application.

Linear alkylbenzene sulfonates (LAS) are one of the organic pollutants of most concern in sewage sludge due to their widespread occurrence in domestic sewage. In this work, the occurrence of LAS was assessed in 15 wastewater treatment plants (WWTPs), with different sludge stabilization treatments, from September 2023 to March 2024. Samples were analyzed by ultrasound-assisted extraction and LC-MS/MS. In primary sludge, LAS homologues displayed the typical fingerprint of laundry detergents, suggesting these products are a primary source in influent wastewater. There was no clear correlation between the population served and the LAS concentrations in the studied WWTPs. The highest concentrations of LAS (sum of the homologues C10–C13) were found in anaerobic lagoons, followed by aerobically (6438 mg/kg) and anaerobically digested (5521 mg/kg) sludge. The lower levels were observed in composted sludge (215 mg/kg). 100% of the composted samples showed concentrations lower than 2600 mg/kg (concentration limit currently proposed by the EU for LAS), while these percentages were reduced to 25 and 13% in the case of aerobically and anaerobically digested sludges. These results showed that composting could be an effective method for ensuring compliance with a future EU Directive on sludge application to the soil.

Este trabajo examina el uso de la extracción en fase sólida en línea (SPE en línea) como una técnica automatizada e innovadora para el análisis enantioselectivo de contaminantes emergentes quirales. Para ello, se destacan dos estudios de caso: el primero enfocado en el análisis de antibióticos fluoroquinolonas quirales en aguas residuales y superficiales y, el segundo, en la determinación de fármacos antidepresivos y β-bloqueantes quirales en aguas residuales, ambos mediante cromatografía de líquidos acoplada a espectrometría de masas en tándem con ionización por electrospray (LC-ESI-MS/MS). Los resultados demuestran que la SPE en línea ofrece alta eficiencia en la preconcentración de analitos, simplificando y automatizando el tratamiento de muestras. Comparada con métodos convencionales, mantiene una excelente enantioresolución, sensibilidad y reproducibilidad. Además, su simplicidad y compatibilidad con técnicas cromatográficas acopladas a sistemas de detección avanzados confirman su potencial como una alternativa automática y eficaz para el análisis enantioselectivo medioambiental.

Background/Objectives: The persistence of tetracycline residues in aquatic environments poses substantial risks to ecosystems and public health, emphasizing the need for effective removal strategies. This study examines the use of purified stevensite (ST), a natural clay mineral, as an efficient and cost-effective adsorbent for removing tetracycline antibiotics from contaminated water. Methods: Batch experiments were conducted to assess the adsorption kinetics, isotherms, and influence of environmental factors. Material characterization studies were performed before and after tetracycline adsorption. Results: ST demonstrated optimal removal efficiency at an acidic pH, achieving over 99% elimination of both tetracyclines and their metabolites at an adsorbent dose of 2 g L−1 and antibiotic concentration of 5 mg L−1. Equilibrium was reached within 30 min. Regeneration experiments confirmed that ST retained over 90% of its adsorption capacity after five adsorption–desorption cycles. Surface characterization revealed that ST’s large surface area, high cation exchange capacity, and potential for hydrogen bonding may explain its high adsorption capabilities. The material was tested on real samples of tap water, surface water, and wastewater, demonstrating an effective removal rate over 99%. Conclusions: With its high efficiency, low cost and favourable reusability, purified ST is a promising option for large-scale wastewater treatment, contributing to safer water resources and improved environmental protection.

BACKGROUND:Pharmacologically active compounds are emerging pollutants of greatest concern because of their continuous release to the aquatic media and potential effects on non-target organisms. Nevertheless, in spite that many pharmaceuticals are chiral compounds which enantiomers may have different environmental behaviour and effects, their enantiomeric determination has been scarcely evaluated. This fact can be explained by the great challenge to overcome when developing an analytical method for the individual determination of compounds with the same physical-chemical properties, as it is the case of enantiomers. RESULTS:In this work, an automatised method based on online solid phase extraction (SPE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) was optimised and validated for the enantiomeric determination of highly prescribed (β-blockers (atenolol, metoprolol and propranolol), antidepressants (citalopram, fluoxetine, sertraline, duloxetine and venlafaxine) and two of their metabolites in influent and effluent wastewater. Three of them (metoprolol, citalopram and venlafaxine) have been recently included in the European Union Directive 2024/3019 as substances that should be measured in wastewater. Method quantification limits in the range from 0.1 to 50 ng L-1 for most compounds. Accuracy ranged from 60.8 to 114 % and precision, expressed as relative standard deviation, was lower than 12.5 % for all the compounds. Method application to wastewater samples revealed the presence of the target compounds at concentrations between 1.06 and 1213 ng L-1 and a preferential degradation of some enantiomers: S-(-)-atenolol, metoprolol-E1, venlafaxine-E1 and O-desmethylvenlafaxine-E1. SIGNIFICANCE AND NOVELTY:This method is the first one for online SPE-chiral-LC-MS/MS determination of two therapeutic groups of chiral pharmaceuticals in wastewater. The method allows their automatised enantiomeric determination, including sample treatment, SPE column wash and conditioning, and LC-MS/MS determination, in 40 min with enantioresolution from 0.51 to 1.24. The online SPE method developed provides a fast way to obtain information about chiral compounds in wastewater reducing labour intensity, exposure to organic solvents, analyte loss and plastic waste.

Endocrine-disrupting chemicals (EDCs) pollute the environment and food, adversely affecting living organisms. It is known that exposure to EDCs increases the risk of various diseases in humans, but in veterinary medicine, the pathogenic impact of these substances is usually marginalised. Therefore, the aim of the present study was to determine whether exposure to EDCs is associated with a higher risk of chronic degenerative valve disease (CDVD) in dogs. The study included hair samples collected from 60 male and female dogs of various breeds and ages ranging from 9 months to 15 years. Hair samples collected from healthy dogs and dogs with CDVD were analysed for the presence of 15 EDCs (including bisphenol A, parabens, benzophenones and polyfluoroalkyl substances) using liquid chromatography and tandem mass spectrometry (LC-MS/MS) technique. Concentration levels of methylparaben, ethylparaben, propylparaben, perfluoroheptanoic acid and perfluorooctanoic acid in samples collected from dogs with CDVD were statistically significantly higher than those noted in healthy dogs. Differences in concentrations of other EDCs studied between ill and healthy dogs were not statistically significant. The results may suggest that greater exposure of dogs to certain EDCs (such as methylparaben, ethylparaben, propylparaben, perfluoroheptanoic acid, and perfluorooctanoic acid) may increase the risk of CDVD, but further comprehensive clinical and toxicological research is necessary to fully clarify this issue.

Introduction Surfactants are substances that are commonly used in the industry, and they pollute the environment and negatively affect living organisms. In this article, we describe, for the first time, the exposure of wild bats to selected surfactants: nonylphenol (NP) and linear alkylbenzene sulfonates (LASs), including LAS C10, LAS C11, LAS C12, and LAS C13 (where "C" with a number indicates the length of the alkyl carbon chain).Methods The levels of the abovementioned compounds were evaluated in guano samples collected from various colonies of the greater mouse-eared bat (Myotis myotis) using liquid chromatography coupled with mass spectrometry (LC-MS/MS). Results: All surfactants studied were found in the guano samples. Mean levels of LASs (+/- SD) ranged from 87 +/- 28.5 ng/g (median 75.1 ng/g) in the case of LAS C10 to 662 +/- 227.2 ng/g (median 560.5 ng/g) in the case of LAS C12. The mean concentration of NP was 65.2 +/- 74.9 ng/g (median 23.5 ng/g). Moreover, significant differences in surfactant levels were noted between particular bat colonies.Methods The levels of the abovementioned compounds were evaluated in guano samples collected from various colonies of the greater mouse-eared bat (Myotis myotis) using liquid chromatography coupled with mass spectrometry (LC-MS/MS). Results: All surfactants studied were found in the guano samples. Mean levels of LASs (+/- SD) ranged from 87 +/- 28.5 ng/g (median 75.1 ng/g) in the case of LAS C10 to 662 +/- 227.2 ng/g (median 560.5 ng/g) in the case of LAS C12. The mean concentration of NP was 65.2 +/- 74.9 ng/g (median 23.5 ng/g). Moreover, significant differences in surfactant levels were noted between particular bat colonies.Discussion The results showed that wild bats are highly exposed to LASs and NP, and the degree of this exposure shows clear intraregional differences. Moreover, the study demonstrated that guano samples serve as a valuable tool to assess bat exposure to these surfactants.

BACKGROUND:Tetracyclines are frequently detected in the environment due to their persistence and extensive use as antibiotics in human and veterinary medicine. They can accumulate in sludge and in agricultural soils fertilised with treated sludge or manure. This behaviour may lead to ecological risk, propagation of antibiotic resistance and can affect crops and human health through the consumption of vegetables and fruits. Analytical methods for the determination of tetracyclines and their transformation products (TPs) in sludge and agricultural soils are scarce, include a small number of tetracyclines, do not include their TPs and are not specifically developed for their determination. RESULTS:A matrix solid-phase dispersion (MSPD) method has been optimised for the simultaneous determination of six tetracyclines and six of their main TPs in the types of sludge applied as soil fertiliser (digested sludge and composted sludge) and in agricultural soil. Analytical determination by online SPE-LC-MS/MS has also been optimised. The method was validated for each of the above-mentioned matrices, with good linearity (R2 ≥ 0.98), precision (RSD ≤12.3 %), accuracy (64-117 %) and method quantification limits (below 10 ng g-1 dry weight (dw) for most compounds). Application of the method to digested sludge, composted sludge and agricultural soils revealed high concentrations not only of the parent compounds (tetracycline and doxycycline, up to 353 ng g-1 dw and 1069 ng g-1 dw, respectively, in digested sludge) but also of their TPs (epitetracycline, anhydrotetracycline and 4-epioxytetracycline up to 327 ng g-1 dw, 117 ng g-1 dw and 10.2 ng g-1 dw, respectively, in digested sludge). SIGNIFICANCE AND NOVELTY:This method allows the specific simultaneous determination of six tetracyclines and six of their TPs in sludge and soils. The proposed method constitutes a starting point to extend the use of MSPD, that is being applied mainly to biota and food, as a low-cost and easy-to-perform technique that allows simultaneous extraction and clean-up. Application of the method revealed the significance of the determination of TPs of tetracyclines for a proper environmental risk assessment.

Microplastics (MP) and antibiotics coexist in the environment and their combined exposure represents a source of increasing concern. MP may act as carriers of antibiotics because of their sorption capacity. Knowledge of the interactions between them may help improve understanding of their migration and transformation. In this work, the adsorption behaviour of a group of sulfonamides and their acetylated metabolites on different sizes of polyamide (PA) and polystyrene (PS) MP were investigated and compared. Sulfonamides were adsorbed on both MP (qmax up to 0.699 and 0.184 mg/g, for PA and PS, respectively) fitting to a linear isotherm model (R2 > 0.835). A low particle size and an acidic and salinity medium significantly enhances the adsorption capacity of sulfonamides (i.e. removal of sulfamethoxazole increased from 8% onto 3 mm PA pellets to 80% onto 50 mm of PA pellets). According to characterization results, adsorption mechanism is explained by pore filling and hydrogen bonds (for PA) and hydrophobic interactions (for PS). After adsorption, surface area was increased in both MP as result of a potential ageing of the particles and the intensity of XRD peaks was higher denoting a MP structure more amorphized. Metabolites were adsorbed more efficiently than their parent compounds on PS while the opposite effect was observed on PA explained by the acetylation of the amine group and, subsequently the reduction of hydrogen bond interactions. Although the dissolved organic matter inhibits sulfonamides adsorption, removal up to 65.2% in effluent wastewater and up to 72.1% in surface water were observed in experiments using real matrices denoting the role of MP as vectors of sulfonamide antibiotics in aquatic media.

The irrigation of soils with reclaimed contaminated wastewater or its amendment with sewage sludge contributes to the uptake of pharmaceuticals by vegetables growing in the soil. A multiresidue method has been devised to determine five pharmaceuticals and nine of their main metabolites in leafy and root vegetables. The method employs ultrasound-assisted extraction, clean-up via dispersive solid-phase extraction, and analysis through liquid chromatography-tandem mass spectrometry. Box-Behnken design was used to refine variables such as extraction solvent volume, time of extraction, number of extraction cycles, and the type and amount of d-SPE sorbent. The method achieved linearity (R2) greater than 0.994, precision (relative standard deviation) under 16% for most compounds, and detection limits ranging from 0.007 to 2.25 ng g-1 dry weight. This method was applied to a leafy vegetable (lettuce) and to a root vegetable (carrot) sourced from a local market. Parent compounds were detected at higher concentrations than their metabolites, with the exception of carbamazepine-10,11-epoxide.

Introduction Benzophenones (BPs) are used in various branches of industry as ultraviolet radiation filters, but they pollute the natural environment, penetrate living organisms, and disrupt endocrine balance. Knowledge of the exposure of domestic animals to these substances is extremely scant. The aim of the study was to investigate long-term exposure of companion dogs to BPs and relate this to environmental factors. Material and Methods Hair samples taken from 50 dogs and 50 bitches from under 2 to over 10 years old were analysed for BP content with liquid chromatography-tandem mass spectrometry. Results The results revealed that dogs are most often exposed to 2-hydroxy-4-methoxybenzophenone (BP-3) and 4-dihydroxybenzophenone (BP-1). Concentration levels of BP-3 above the method quantification limit (MQL) were noted in 100% of the samples and fluctuated from 4.75 ng/g to 1,765 ng/g. In turn, concentration levels of BP-1 above the MQL were noted in 37% of the samples and ranged from <0.50 ng/g to 666 ng/g. Various factors (such as the use of hygiene and care products and the dog's diet) were found to affect BP concentration levels. Higher levels of BP-3 were observed in castrated/spayed animals and in animals that required veterinary intervention more often. Conclusion The results obtained show that the analysis of hair samples may be a useful matrix for biomonitoring BPs in dogs, and that these substances may be toxic to them.