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Introduction: Soil bacteria offer a promising approach to bioremediate pesticide contamination in agricultural ecosystems. This study investigated the potential of bacteria isolated from rice paddy soil for bioremediating fipronil and thiobencarb, common agricultural pesticides. Methods: Bacterial isolates capable of degrading fipronil and thiobencarb were enriched in a mineral salt medium. A response surface methodology with a Box-Behnken design was utilized to optimize pesticide degradation with the isolated bacteria. Bioaugmentation tests were performed in paddy soils with varying conditions. Results and discussion: Six strains, including single isolates and their mixture, efficiently degraded these pesticides at high concentrations (up to 800 µg/mL). Enterobacter sp., Brucella sp. (alone and combined), and a mixture of Stenotrophomonas sp., Bordetella sp., and Citrobacter sp. effectively degraded fipronil and thiobencarb, respectively. Notably, a single Pseudomonas sp. strain degraded a mixture of both pesticides. Optimal degradation conditions were identified as a slightly acidic pH (6-7), moderate pesticide concentrations (20-50 µg/mL), and a specific inoculum size. Bioaugmentation assays in real-world paddy soils (sterile/non-sterile, varying moisture) demonstrated that these bacteria significantly increased degradation rates (up to 14.15-fold for fipronil and 5.13-fold for thiobencarb). The study identifies these novel bacterial strains as promising tools for bioremediation and bioaugmentation strategies to tackle fipronil and thiobencarb contamination in paddy ecosystems. [ABSTRACT FROM AUTHOR]

Most antibiotics contain ionizable groups that undergo acid-base dissociation giving rise to diverse dissociated forms in aquatic systems depending on the pH of the system. In sunlit surface waters, photochemical transformation plays a crucial role in determining the fate of antibiotics. This study presents a comprehensive examination of the photo-transformation degradation kinetics, pathways and photoinduced toxicity of three widely detected tetracyclines (TCs): tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC). Under simulated sunlight (λ > 290 nm), their apparent photolysis followed pseudo-first-order kinetics, with rate constants significantly increasing from H2TCs0 to TCs2−. Through competition kinetic experiments and matrix calculations, it was found that the anions HTCs− or TCs2− (pH ∼ 8–10) were more reactive toward hydroxyl radicals (•OH), while TCs2− (pH ∼ 10) reacted the fastest with singlet oxygen (1O2). Considering the dissociated species, the total environmental photo-transformation half-lives of TCs were determined, revealing a strong dependence on the water pH and seasonal variation in sunlight. Generally, apparent photolysis was the dominant photochemical process, followed by 1O2 and •OH oxidation. Different transformation pathways for the three reactions were determined based on the key photoproducts identified using HPLC-MS/MS. Toxicity tests and ECOSAR software calculations confirmed that the intermediates produced by the •OH and 1O2 photo-oxidation processes were more toxic than the parent compounds. These findings significantly enhance our understanding of the complex photochemical fate and associated risks of TCs in aqueous environments. [ABSTRACT FROM AUTHOR]

Cardiovascular drugs have been a burning topic in the field of environmental analytical chemistry in the last few decades. Growing modern healthcare has led to the widespread use of pharmaceuticals. Among these, antihypertensives (sartans, angiotensin-converting enzyme inhibitors) and lipid-regulating drugs (fibrates and statins) are the most frequently consumed and, thus, excreted into wastewater. Their chemical fate during conventional and advanced wastewater treatment, such as ozonation, remains unclear. Analytical chemistry, providing sample pretreatment followed by instrumental analysis, has a tremendous role in water treatment evaluation, mostly from the perspective of parent contaminants' removals and also assessment of transformation pathways. Ultrasensitive liquid chromatography–mass spectrometry (LC-MS) systems provide many opportunities. By carefully using planned workflows for chromatographic and mass-spectrometric data processing, i.e., suspect and non-target screening approaches, LC-MS allows for the identification and structural elucidation of unknown, predicted, suspected or selected transformation products. Accordingly, some examples and case studies on selected cardiovascular drugs in this review are presented to show the applicability of the used analytical approaches and workflows. [ABSTRACT FROM AUTHOR]

The photochemical degradation pathways of 6PPD-quinone (6PPDQ, 6PPD-Q), a toxic transformation product of the tire antiozonant 6PPD, were determined under simulated sunlight conditions typical of high-latitude surface waters. Direct photochemical degradation resulted in 6PPDQ half-lives ranging from 17.5 h at 20 °C to no observable degradation over 48 h at 4 °C. Sensitization of excited triplet-state pathways using Cs+ and Ar purging demonstrated that 6PPDQ does not decompose significantly from a triplet state relative to a singlet state. However, assessment of processes involving reactive oxygen species (ROS) quenchers and sensitizers indicated that singlet oxygen and hydroxyl radical do significantly contribute to the degradation of 6PPDQ. Investigation of these processes in natural lake waters indicated no difference in attenuation rates for direct photochemical processes at 20 °C. This suggests that direct photochemical degradation will dominate in warm waters, while indirect photochemical pathways will dominate in cold waters, involving ROS mediated by chromophoric dissolved organic matter (CDOM). Overall, the aquatic photodegradation rate of 6PPDQ will be strongly influenced by the compounding effects of environmental factors such as light screening and temperature on both direct and indirect photochemical processes. Transformation products were identified via UHPLC-Orbitrap mass spectrometry, revealing four major processes: (1) oxidation and cleavage of the quinone ring in the presence of ROS, (2) dealkylation, (3) rearrangement, and (4) deamination. These data indicate that 6PPDQ can photodegrade in cool, sunlit waters under the appropriate conditions: t1/2 = 17.4 h tono observable decrease (direct); t1/2 = 5.2-11.2 h (indirect, CDOM).

Contaminants of emerging concern (CECs) in the environment undergo various transformations, leading to the formation of transformation products (TPs) with a modified ecological risk potential. Although the environmental significance of TPs is increasingly recognized, there has been relatively little research to understand the influences of such transformations on subsequent ecotoxicological safety. In this study, we used four pairs of CECs and their methylated or demethylated derivatives as examples to characterize changes in bioaccumulation and acute toxicity in Daphnia magna, as a result of methylation or demethylation. The experimental results were further compared to quantitative structure-activity relationship (QSAR) predictions. The methylated counterpart in each pair generally showed greater acute toxicity in D. magna, which was attributed to their increased hydrophobicity. For example, the LC50 values of methylparaben (34.4 ± 4.3 mg L-1) and its demethylated product (225.6 ± 17.3 mg L-1) differed about eightfold in D. magna. The methylated derivative generally exhibited greater bioaccumulation than the demethylated counterpart. For instance, the bioaccumulation of methylated acetaminophen was about 33-fold greater than that of acetaminophen. In silico predictions via QSARs aligned well with the experimental results and suggested an increased persistence of the methylated forms. The study findings underline the consequences of simple changes in chemical structures induced by transformations such as methylation and demethylation and highlight the need to consider TPs to achieve a more holistic understanding of the environmental fate and risks of CECs.

Abstract Semiconductor manufacturing employs per- and polyfluoroalkyl substances (PFAS) as fluoroasurfactants to enhance the quality of photolithography lines. Our research, employing a fragment-based approach to investigate nontarget PFAS, overcomes conventional homologous series limitations. In a mixture of PFAS standards used as a quality control sample, 92% (36 out of 39 compounds spanning 11 compound classes) were detectable through the fragment-based nontarget procedure. This indicates the effectiveness of this approach in identifying the hydrophobic and hydrophilic characteristics of various fluorosurfactants. Eighty-three PFAS were detected in wastewater and effluent samples from semiconductor industry, including 29 newly discovered compounds, categorized into three groups. First, besides detecting perfluorobutane sulfonamido ethanol (FBSE), various fluoroalkyl chain structures of FBSE derivatives were initially identified in wastewater. These include perfluorobutyl ether sulfonamido ethanol, unsaturated FBSE, and hydrogen-substituted FBSE. These derivatives were also detected in trace amounts in commercial authentic standards of FBSE. To quantify their presence, we analyzed the FBSE derivatives from the authentic standard, and the relative proportions of these derivatives contribute to approximately 0.5%. This suggests that the FBSE derivative series detected in wastewater may arise from byproducts of chemical formulations used in the manufacturing of semiconductors. Second, transformation products from FBSE during oxidation, including the first identified intermediate transformation compounds, perfluorobutane sulfonamido acetaldehyde and its hydrate, were discovered. Third, diverse reaction products are generated from the intricate processes of semiconductor manufacturing, which utilize strong acids, bases, and solvents under UV light or heated conditions. These processes include the formation of PFAS-related compounds through hydration, sulfonation, oxidation, and nitrification. This study revealed 25 isomeric PFAS, encompassing headgroup isomers and functional tail group isomers. These findings underscore the importance of comprehending diverse reactions and the overall emission compositions of PFAS in semiconductor wastewater, highlighting its complexity and presenting challenges for subsequent wastewater treatment.

Unsymmetrical dimethylhydrazine (UDMH) based rocket fuel, when released into the soil, undergoes oxidative transformations to form a variety of toxic nitrogen‐containing products (TPs). Loamy soils containing aluminosilicates (clay) are capable of strong binding and retention of UDMH TPs due to a combination of polar sorption and cation‐exchange properties, posing challenges for their extraction and quantification. To overcome this problem, the present study proposes direct thermal desorption (TD) of analytes from loam facilitated by the addition of modifiers competing with UDMH TPs for sorption centers and ensuring their conversion into molecular form. Among tested additives, the mixture of potassium chloride and hydroxide demonstrated the best performance and provided recoveries of the most UDMH TPs exceeding 70% under optimized TD conditions (200°C, 30 min). The online combination of TD with gas chromatography‐tandem mass spectrometry allowed for the development of a method for the determination of 15 UDMH TPs in loamy soils with limits of detection in the range of 0.2–15 µg/kg. The use of matrix‐matched calibration and deuterated internal standards ensured high accuracy (80%–100%) and precision (relative standard deviation < 18%) of the analysis. The developed method was validated and successfully tested in the analyses of real loamy soil samples polluted with rocket fuel. [ABSTRACT FROM AUTHOR]

Dexamethasone (DEX) degradation was investigated using three UV-based advanced oxidation processes combined with sodium persulphate, hydrogen peroxide, and free chlorine in aqueous solutions in a bench-scale reactor. The goal was to determine which process would be the best option in terms of DEX degradation without the subsequent generation of toxic compounds. The process performance for DEX degradation followed the UV/S2O82−> UV/H2O2> UV/HOCl order under equal conditions. In the UV/S2O82− process, sulphate radicals led to a 70.4% DEX degradation. The experimental mineral inhibitory factors showed that nitrite and bicarbonate further decrease the efficiency of the UV/S2O82− process. In the optimal conditions, the UV/S2O8−2 process removed DEX by 100% and had a 74.1% mineralisation. Furthermore, the intermediates were detected using LC-MS/MS, and the cytotoxicity of the UV/S2O8−2 process effluent was evaluated using human embryonic kidney cultured cells. The treatment of DEX solution by the UV/S2O8−2 process significantly decreased the toxicity of the effluent. Therefore, it can be concluded that the UV/S2O8−2 process can be a reliable process for DEX degradation and detoxification in aqueous solutions. [ABSTRACT FROM AUTHOR]

As new pesticides continue to emerge in agricultural systems, understanding their environmental behavior is crucial for effective risk assessment. Tiafenacil (TFA), a promising novel pyrimidinedione herbicide, was the focus of this study. We developed an efficient QuEChERS-UHPLC-QTOF-MS/MS method to measure TFA and its transformation products (TP1, TP2, TP3, TP4, and TP5) in soil. Our calibration curves exhibited strong linearity (R2 ≥ 0.9949) ranging from 0.015 to 2.0 mg/kg within a low limit of quantification (LOQ) of 2.0 µg/kg. Inter-day and intra-day recoveries (0.10 to 2.0 mg/kg, 80.59% to 110.05%, RSD from 0.28% to 12.93%) demonstrated high sensitivity and accuracy. Additionally, TFA dissipation under aerobic conditions followed first-order kinetics, mainly yielding TP1 and TP4. In contrast, TP1 and TP2 were mainly found under sterilized and anaerobic conditions, and TFA dissipation followed second-order kinetics. Moreover, we predicted the transformation pathways of TFA using density functional theory (DFT) and assessed the toxicity levels of TFA and its TPs to aquatic organisms using ECOSAR. Collectively, these findings hold significant implications for a better understanding of TFA fate in diversified soil, benefiting its risk assessment and rational utilization. [ABSTRACT FROM AUTHOR]

Semiconductor manufacturing employs per- and polyfluoroalkyl substances (PFAS) as fluoroasurfactants to enhance the quality of photolithography lines. Our research, employing a fragment-based approach to investigate nontarget PFAS, overcomes conventional homologous series limitations. In a mixture of PFAS standards used as a quality control sample, 92% (36 out of 39 compounds spanning 11 compound classes) were detectable through the fragment-based nontarget procedure. This indicates the effectiveness of this approach in identifying the hydrophobic and hydrophilic characteristics of various fluorosurfactants. Eighty-three PFAS were detected in wastewater and effluent samples from semiconductor industry, including 29 newly discovered compounds, categorized into three groups. First, besides detecting perfluorobutane sulfonamido ethanol (FBSE), various fluoroalkyl chain structures of FBSE derivatives were initially identified in wastewater. These include perfluorobutyl ether sulfonamido ethanol, unsaturated FBSE, and hydrogen-substituted FBSE. These derivatives were also detected in trace amounts in commercial authentic standards of FBSE. To quantify their presence, we analyzed the FBSE derivatives from the authentic standard, and the relative proportions of these derivatives contribute to approximately 0.5%. This suggests that the FBSE derivative series detected in wastewater may arise from byproducts of chemical formulations used in the manufacturing of semiconductors. Second, transformation products from FBSE during oxidation, including the first identified intermediate transformation compounds, perfluorobutane sulfonamido acetaldehyde and its hydrate, were discovered. Third, diverse reaction products are generated from the intricate processes of semiconductor manufacturing, which utilize strong acids, bases, and solvents under UV light or heated conditions. These processes include the formation of PFAS-related compounds through hydration, sulfonation, oxidation, and nitrification. This study revealed 25 isomeric PFAS, encompassing headgroup isomers and functional tail group isomers. These findings underscore the importance of comprehending diverse reactions and the overall emission compositions of PFAS in semiconductor wastewater, highlighting its complexity and presenting challenges for subsequent wastewater treatment. [ABSTRACT FROM AUTHOR]

The occurrence of pharmaceuticals in water bodies is of growing concern as they pose potential toxicity to wildlife and humans. Since the removal of these compounds via conventional wastewater treatment plants is typically not efficient, advanced processes such as oxidation and adsorption are considered alternatives. In this review study, ozonation combined with adsorption filtration systems is evaluated for the removal of pharmaceuticals and their transformation products from municipal wastewater effluents. Ozonation has a large capacity for the removal of pharmaceuticals from municipal wastewater; however, potential toxic transformation products can be created which require a post-treatment step to mitigate the adverse effects in recipient waters. Various sorption methods have been investigated as post-treatment, with activated carbon being addressed as the most common one. Other sorption technologies such as ion exchange, biochar, constructed wetlands, and biofiltration were also evaluated in this review article. Biochar was considered to have great potential as a promising alternative adsorbent which is known as a more sustainable material. The combination of ozonation with the adsorption method enables the limitations of each single treatment to be reduced and allows the treatment train to become more efficient. [ABSTRACT FROM AUTHOR]

Antibiotics in wastewater may inhibit the operation of biological treatment systems. Sulfapyridine (SPY) not only has antibacterial activity, but also chelates with other substances, and its antibacterial activity becomes stronger. An enhanced hydrolysis was applied to remove antibiotics as a promising pretreatment. An increase of 10°C accelerated the SPY hydrolysis rate by 1.98–2.40 fold, and the hydrolysis half‐life of SPY was shortened by 2.92 fold when pH was increased from 3 to 11 at 85°C. Herein, the contribution of hydrolysis to the SPY degradation increased as temperature, and the cleavage of bond is mainly way of SPY hydrolysis. The trend in the TP1 concentration indicate that NC cleavage may occur at the beginning of the reaction. According to result, the contribution of SPY to antibacterial activity decreased as the reaction progressed. The hydrolysis half‐life of SPY was shortened by condition optimization under normal pressure. The optimal conditions are pH = 10.8 and 60°C through response surface methodology (RSM) and EEO value with SPY concentration, antibacterial activity removal efficiency and low energy consumption as targets. Enhanced hydrolysis broken chemical bonds through hydrolysis and oxidation, shortening the hydrolysis half‐life of SPY at high temperature and alkaline. The energy consumption of SPY hydrolysis was calculated for the first time. Under the conditions of pH = 11 and 65°C, the energy consumption of per unit concentration SPY degradation was minimal. The results of this study demonstrated that enhanced hydrolysis is effective and energy conservation as a pretreatment technology for antibiotic. [ABSTRACT FROM AUTHOR]

Unplanned water reuse for crop irrigation may pose a global health risk due to the entry of contaminants into the food chain, undesirable effects on crop quality, and impact on soil health. In this study, we evaluate the impact derived from the co-occurrence of pharmaceuticals (Phs), trace metals (TMs), and one metalloid within the water–soil–plant continuum through bioassay experiments with Lactuca sativa L. Results indicate that the co-occurrence of Phs and TMs has synergistic or antagonistic effects, depending on target contaminants and environmental compartments. Complex formations between drugs and TMs may be responsible for enhanced sorption onto the soil of several Phs and TMs. Concerning plant uptake, the co-occurrence of Phs and TMs exerts antagonistic and synergistic effects on carbamazepine and diazepam, respectively. With the exception of Cd, drugs exert an antagonistic effect on TMs, negatively affecting their uptake and translocation. Drug contents in lettuce edible parts do not pose any threat to human health, but Cd levels exceed the maximum limits set for leafy vegetable foodstuffs. Under Ph-TM conditions, lettuce biomass decreases, and a nutrient imbalance is observed. Soil enzyme activity is stimulated under Ph-TM conditions (β-galactosidase) and Ph and Ph-TM conditions (urease and arylsulfatase), or it is not affected (phosphatase). [ABSTRACT FROM AUTHOR]

Photocatalysis is a prominent alternative wastewater treatment technique that has the potential to completely degrade pesticides as well as other persistent organic pollutants, leading to detoxification of wastewater and thus paving the way for its efficient reuse. In addition to the more conventional photocatalysts (e.g., TiO2, ZnO, etc.) that utilize only UV light for activation, the interest of the scientific community has recently focused on the development and application of visible light-activated photocatalysts like g-C3N4. However, some disadvantages of g-C3N4, such as the high recombination rate of photogenerated charges, limit its utility. In this light, the present study focuses on the synthesis of WO3 fibers/g-C3N4 Z-scheme heterojunctions to improve the efficiency of g-C3N4 towards the photocatalytic removal of the widely used insecticide clothianidin. The effect of two different g-C3N4 precursors (urea and thiourea) and of WO3 fiber content on the properties of the synthesized composite materials was also investigated. All aforementioned materials were characterized by a number of techniques (XRD, SEM-EDS, ATR-FTIR, Raman spectroscopy, DRS, etc.). According to the results, mixing 6.5% W/W WO3 fibers with either urea or thiourea derived g-C3N4 significantly increased the photocatalytic activity of the resulting composites compared to the precursor materials. In order to further elucidate the effect of the most efficient composite photocatalyst in the degradation of clothianidin, the generated transformation products were tentatively identified through UHPLC tandem high-resolution mass spectroscopy. Finally, the detoxification effect of the most efficient process was also assessed by combining the results of an in-vitro methodology and the predictions of two in-silico tools. [ABSTRACT FROM AUTHOR]

N-(1,3-Dimethyl butyl)-N′-phenyl-phenylenediamine-quinone (6PPD-Q) is a derivative of the widely used rubber tire antioxidant 6PPD, which was first found to be acutely toxic to coho salmon. Subsequent studies showed that 6PPD-Q had species-specific acute toxicity in fishes and potential hepatotoxicity in mice. In addition, 6PPD-Q has been reported in human urine, demonstrating the potential widespread exposure of humans to this chemical. However, whether 6PPD-Q poses a higher risk to humans than its parent compound, 6PPD, and could cause adverse effects in humans is still unclear. In this study, we utilized two human liver cell models (the human proto-hepatocyte model L02 and the human hepatocellular carcinoma cell line HepG2) to investigate the potentially differential effects of these two chemicals. Cell viability curve analysis showed that 6PPD-Q had lower IC50 values than 6PPD for both liver cell lines, suggesting higher toxicity of 6PPD-Q to human liver cells than 6PPD. In addition, L02 cells are more sensitive to 6PPD-Q exposure, which might be derived from its weaker metabolic transformation of 6PPD-Q, since significantly lower levels of phase I and phase II metabolites were detected in 6PPD-Q-exposed L02 cell culture medium. Furthermore, pathway analysis showed that 6PPD-Q exposure induced changes in phenylalanine, tyrosine, and tryptophan biosynthesis and tyrosine metabolism pathways in L02 cells, which might be the mechanism underlying its liver cell toxicity. Gene expression analysis revealed that exposure to 6PPD-Q induced excessive ROS production in L02 cells. Our results further supported the higher risk of 6PPD-Q than 6PPD and provided insights for understanding the effects of 6PPD-Q on human health. [ABSTRACT FROM AUTHOR]

IntroductionSoil bacteria offer a promising approach to bioremediate pesticide contamination in agricultural ecosystems. This study investigated the potential of bacteria isolated from rice paddy soil for bioremediating fipronil and thiobencarb, common agricultural pesticides.MethodsBacterial isolates capable of degrading fipronil and thiobencarb were enriched in a mineral salt medium. A response surface methodology with a Box-Behnken design was utilized to optimize pesticide degradation with the isolated bacteria. Bioaugmentation tests were performed in paddy soils with varying conditions.Results and discussionSix strains, including single isolates and their mixture, efficiently degraded these pesticides at high concentrations (up to 800 µg/mL). Enterobacter sp., Brucella sp. (alone and combined), and a mixture of Stenotrophomonas sp., Bordetella sp., and Citrobacter sp. effectively degraded fipronil and thiobencarb, respectively. Notably, a single Pseudomonas sp. strain degraded a mixture of both pesticides. Optimal degradation conditions were identified as a slightly acidic pH (6-7), moderate pesticide concentrations (20-50 µg/mL), and a specific inoculum size. Bioaugmentation assays in real-world paddy soils (sterile/non-sterile, varying moisture) demonstrated that these bacteria significantly increased degradation rates (up to 14.15-fold for fipronil and 5.13-fold for thiobencarb). The study identifies these novel bacterial strains as promising tools for bioremediation and bioaugmentation strategies to tackle fipronil and thiobencarb contamination in paddy ecosystems.

The widespread occurrence of N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-Q) in aquatic environments and its hazards to aquatic species underscore the necessity of comprehending its environmental fate. Here, we investigated the transformation from 6PPD to 6PPD-Q and the attenuation of 6PPD-Q in surface water under natural conditions. Contrary to prior findings, this work revealed that 6PPD-Q and its precursor 6PPD-OH/6PPD-(OH)2, were not detected through target analysis and suspect screening during 6PPD transformation in the surface water under the natural conditions. 6PPD-Q predominantly accumulated in TWPs in ambient atmosphere with 1.28 % mass yield from the 6PPD dissipation. Subsequently, 6PPD-Q was eluted from TWPs and released to the water environment. The investigation on the natural attenuation of 6PPD-Q in the surface water demonstrated that direct and indirect photolysis facilitated the rapid dissipation of 6PPD-Q with a half-life of 2.57 h. Utilizing the liquid chromatography high resolution mass spectrometry (LC-HRMS), including both time of flight (TOF) MS and Orbitrap MS, twelve novel transformation products (TPs) of 6PPD-Q were identified by using a comprehensive non-targeted screening strategy. The results from two dimensions gas chromatography (GC×GC) TOF-MS revealed additional two TPs. Based on the molecular structure of TPs, four major pathways of 6PPD-Q attenuation were proposed, including bond cleavage, hydroxylation, quinone cleavage and rearrangement. All TPs were predicted to exhibit lower toxicity, indicating the natural attenuation of 6PPD-Q reduced its toxicity and potential environmental risks. This study provides crucial insights into the environmental fate of 6PPD-Q, highlighting the significance of understanding both its formation from 6PPD and its subsequent attenuation processes under natural conditions.

Abstract Background Persistent, mobile and toxic (PMT), or very persistent and very mobile (vPvM) substances are a wide class of chemicals that are recalcitrant to degradation, easily transported, and potentially harmful to humans and the environment. Due to their persistence and mobility, these substances are often widespread in the environment once emitted, particularly in water resources, causing increased challenges during water treatment processes. Some PMT/vPvM substances such as GenX and perfluorobutane sulfonic acid have been identified as substances of very high concern (SVHCs) under the European Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) regulation. With hundreds to thousands of potential PMT/vPvM substances yet to be assessed and managed, effective and efficient approaches that avoid a case-by-case assessment and prevent regrettable substitution are necessary to achieve the European Union's zero-pollution goal for a non-toxic environment by 2050. Main Substance grouping has helped global regulation of some highly hazardous chemicals, e.g., through the Montreal Protocol and the Stockholm Convention. This article explores the potential of grouping strategies for identifying, assessing and managing PMT/vPvM substances. The aim is to facilitate early identification of lesser-known or new substances that potentially meet PMT/vPvM criteria, prompt additional testing, avoid regrettable use or substitution, and integrate into existing risk management strategies. Thus, this article provides an overview of PMT/vPvM substances and reviews the definition of PMT/vPvM criteria and various lists of PMT/vPvM substances available. It covers the current definition of groups, compares the use of substance grouping for hazard assessment and regulation, and discusses the advantages and disadvantages of grouping substances for regulation. The article then explores strategies for grouping PMT/vPvM substances, including read-across, structural similarity and commonly retained moieties, as well as the potential application of these strategies using cheminformatics to predict P, M and T properties for selected examples. Conclusions Effective substance grouping can accelerate the assessment and management of PMT/vPvM substances, especially for substances that lack information. Advances to read-across methods and cheminformatics tools are needed to support efficient and effective chemical management, preventing broad entry of hazardous chemicals into the global market and favouring safer and more sustainable alternatives.

Abstract Straw returning is an important strategy for effectively using straw resources to improve soil fertility and quality, but the effects of this process on reactive intermediates (RIs) formation in paddy water are not fully explored. In this study, we conducted a field experiment to explore the effects of straw returning on RIs formation including triplet chromophoric dissolved organic matter (3CDOM*), hydroxyl radicals (•OH), and singlet oxygen (1O2) in paddy water. It was found that straw returning considerably increased the steady-state concentration of RIs, and the application of rice straw with 25% and 75% organic replacement ratio increased RIs concentration by 2.52 and 2.25 times, respectively. The optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis and structural equation model showed that straw returning produces abundant humified and aromatic DOM containing fulvic acid, lignin and protein-like substances, which could induce more RIs under irradiation. In addition, straw returning significantly accelerated imidacloprid (IMD) degradation, yielding degradation products that were highly toxic to aquatic animals (i.e., fish and daphnia) but less toxic to aquatic plants (i.e., green algae). This study would offer an innovative viewpoint on the effects of straw returning on the photochemistry of paddy water and the naturally occurring abiotic degradation pathway of organic contaminants.

Contaminants of emerging concern (CECs) as well as their transformation products (TPs) are often found in treated wastewater and biosolids, raising concerns about their environmental risks. Small changes in chemical structure, such as the addition or loss of a methyl group, as the result of methylation or demethylation reaction, may significantly alter a chemicals physicochemical properties. In this study, we evaluated the difference in accumulation and translocation between four CECs and their respective methylated or demethylated derivatives in plant models. Suspended Arabidopsis thaliana cell culture and wheat seedlings were cultivated in nutrient solutions containing individual compounds at 1 mg/L. The methylated counterparts were generally more hydrophobic and showed comparative or greater accumulation in both plant models. For example, after 1 h incubation, methylparaben was found in A. thaliana cells at levels two orders of magnitude greater than demethylated methylparaben. In contrast, the demethylated counterparts, especially those with the addition of a hydroxyl group after demethylation, showed decreased plant uptake and limited translocation. For example, acetaminophen and demethylated naproxen were not detected in the shoots of wheat seedlings after hydroponic exposure. Results from this study suggest that common transformations such as methylation and demethylation may affect the environmental fate of CECs, and should be considered to obtain a more comprehensive understanding of risks of CECs in the environment.

Introduction: Fipronil (FIP) and thiobencarb (THIO) represent widely utilized pesticides in paddy fields, presenting environmental challenges that necessitate effective remediation approaches. Despite the recognized need, exploring bacterial consortia efficiently degrading FIP and THIO remains limited. Methods: This study isolated three unique bacterial consortia--FD, TD, and MD--demonstrating the capability to degrade FIP, THIO, and an FIP + THIO mixture within a 10-day timeframe. Furthermore, the bioaugmentation abilities of the selected consortia were evaluated in paddy soils under various conditions. Results: Sequencing results shed light on the consortia's composition, revealing a diverse bacterial population prominently featuring Azospirillum, Ochrobactrum, Sphingobium, and Sphingomonas genera. All consortia efficiently degraded pesticides at 800 µg/mL concentrations, primarily through oxidative and hydrolytic processes. This metabolic activity yields more hydrophilic metabolites, including 4-(Trifluoromethyl)-phenol and 1,4-Benzenediol, 2-methyl-, for FIP, and carbamothioic acid, diethyl-, S-ethyl ester, and Benzenecarbothioic acid, S-methyl ester for THIO. Soil bioaugmentation tests highlight the consortia's effectiveness, showcasing accelerated degradation of FIP and THIO--individually or in a mixture--by 1.3 to 13-fold. These assessments encompass diverse soil moisture levels (20 and 100% v/v), pesticide concentrations (15 and 150 µg/g), and sterile conditions (sterile and non-sterile soils). Discussion: This study offers an understanding of bacterial communities adept at degrading FIP and THIO, introducing FD, TD, and MD consortia as promising contenders for bioremediation endeavors. [ABSTRACT FROM AUTHOR]

Background: Persistent, mobile and toxic (PMT), or very persistent and very mobile (vPvM) substances are a wide class of chemicals that are recalcitrant to degradation, easily transported, and potentially harmful to humans and the environment. Due to their persistence and mobility, these substances are often widespread in the environment once emitted, particularly in water resources, causing increased challenges during water treatment processes. Some PMT/vPvM substances such as GenX and perfluorobutane sulfonic acid have been identified as substances of very high concern (SVHCs) under the European Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) regulation. With hundreds to thousands of potential PMT/vPvM substances yet to be assessed and managed, effective and efficient approaches that avoid a case-by-case assessment and prevent regrettable substitution are necessary to achieve the European Union's zero-pollution goal for a non-toxic environment by 2050. Main: Substance grouping has helped global regulation of some highly hazardous chemicals, e.g., through the Montreal Protocol and the Stockholm Convention. This article explores the potential of grouping strategies for identifying, assessing and managing PMT/vPvM substances. The aim is to facilitate early identification of lesser-known or new substances that potentially meet PMT/vPvM criteria, prompt additional testing, avoid regrettable use or substitution, and integrate into existing risk management strategies. Thus, this article provides an overview of PMT/vPvM substances and reviews the definition of PMT/vPvM criteria and various lists of PMT/vPvM substances available. It covers the current definition of groups, compares the use of substance grouping for hazard assessment and regulation, and discusses the advantages and disadvantages of grouping substances for regulation. The article then explores strategies for grouping PMT/vPvM substances, including read-across, structural similarity and commonly retained moieties, as well as the potential application of these strategies using cheminformatics to predict P, M and T properties for selected examples. Conclusions: Effective substance grouping can accelerate the assessment and management of PMT/vPvM substances, especially for substances that lack information. Advances to read-across methods and cheminformatics tools are needed to support efficient and effective chemical management, preventing broad entry of hazardous chemicals into the global market and favouring safer and more sustainable alternatives. [ABSTRACT FROM AUTHOR]

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Straw returning is an important strategy for effectively using straw resources to improve soil fertility and quality, but the effects of this process on reactive intermediates (RIs) formation in paddy water are not fully explored. In this study, we conducted a field experiment to explore the effects of straw returning on RIs formation including triplet chromophoric dissolved organic matter (3CDOM*), hydroxyl radicals (•OH), and singlet oxygen (1O2) in paddy water. It was found that straw returning considerably increased the steady-state concentration of RIs, and the application of rice straw with 25% and 75% organic replacement ratio increased RIs concentration by 2.52 and 2.25 times, respectively. The optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis and structural equation model showed that straw returning produces abundant humified and aromatic DOM containing fulvic acid, lignin and protein-like substances, which could induce more RIs under irradiation. In addition, straw returning significantly accelerated imidacloprid (IMD) degradation, yielding degradation products that were highly toxic to aquatic animals (i.e., fish and daphnia) but less toxic to aquatic plants (i.e., green algae). This study would offer an innovative viewpoint on the effects of straw returning on the photochemistry of paddy water and the naturally occurring abiotic degradation pathway of organic contaminants. Highlights: • Straw returning produces abundant humified and aromatic DOM as a key photosensitizer. • Straw returning increased the steady-state concentration of RIs in paddy water. • Straw returning significantly accelerated IMD degradation and 3DOM* was the dominant RI for IMD degradation in paddy water. [ABSTRACT FROM AUTHOR]

N-nitrosodimethylamine (NDMA) is a disinfection byproduct that forms at the presence of an organic nitrogen precursor. Doxylamine, an antihistaminic pharmaceutical, is a precursor of NDMA and has been shown to form NDMA in the presence of chloramine. In this study, the effect of Doxylamine as an NDMA precursor has been further studied during chloramination. The end product and byproducts during chloramination were investigated using a high-resolution mass spectrometer by taking samples at different time intervals. Results suggest that NDMA is not the only end product forming during chloramination of Doxylamine and several transformation products that do not end up as NDMA may form. A group of these transformation products have been selected based on their relative amounts during chloramination with time and notated as Focus Tentative Transformation Products (FTTPn). The identification of these byproducts will make it easier to study the conditions during chloramination that may favour these 'known' transformation products with the use of less sophisticated analytical instruments. Then, it might lead to the establishment of chloramination protocols that will minimise the formation of NDMA from its precursors. [ABSTRACT FROM AUTHOR]

As emerging pollutants, organophosphate esters (OPEs) have been reported in coastal environments worldwide. Nevertheless, information on the occurrence and ecological risks of OPEs, especially the related transformation products, in mangrove wetlands is scarce. For the first time, the coexistence and distribution of OP triesters and their transformation products in three mangrove wetlands in the Beibu Gulf were investigated using ultrasonication and solid-phase extraction, followed by UHPLC-MS/MS detection. The studied OPEs widely existed in all the sampling sites, with the total concentrations ranging from 6.43 ng/g dry weight (dw) to 39.96 ng/g dw and from 3.33 ng/g dw to 22.50 ng/g dw for the OP triesters and transformation products, respectively. Mangrove wetlands tend to retain more OPEs than the surrounding coastal environment. Pearson correlation analysis revealed that the TOC was not the sole factor in determining the OPEs' distribution, and degradation was not the main source of the transformation products in mangrove sediments in the Beibu Gulf. The ecological risks of selected OPEs for different organisms were also assessed, revealing a medium to high risk posed by OP diesters to organisms. The levels or coexistence of OPEs and their metabolites in mangroves need constant monitoring, and more toxicity data should be further studied to assess the effect on normal aquatic organisms. [ABSTRACT FROM AUTHOR]

In the present study, the photocatalytic oxidation and detoxification of aqueous matrices contaminated with boscalid using g-C3N4 catalyst and UV-A light was investigated. The UV-A/g-C3N4 process was found to achieve higher than 83% removal of boscalid in both matrices, with h+ and O 2 • − being the main species. UHPLC-HRMS analysis allowed the identification of five TPs, while the main degradation pathways involved hydroxylation, cyclization, and dechlorination. Scenedesmus rubescens microalgae species was exposed to boscalid solutions and lake water spiked with the fungicide before the photocatalytic treatment and inhibition in the growth rate was observed. An increase in the toxicity was also observed during the first stages of the treatment. The results from the in silico study correlate with the observed evolution of ecotoxicity during the application of the process, as some of the identified TPs were found to be toxic or very toxic for aquatic organisms. However, prolonged application of the process can lead to detoxification. It was also observed that the g-C3N4 catalyst can retain its photochemical stability and activity after at least three cycles. However, a slight decrease in the activity was observed when repeated another two times. This study demonstrated that the suggested photocatalytic process can both decrease the harmful effects of boscalid as well as effectively lower its concentration in water. [ABSTRACT FROM AUTHOR]

Purpose: Hexavalent chromium [Cr(VI)] and imidacloprid (IMI) are the typical inorganic contaminants and neonicotinoid insecticides, the transformation processes of which are poorly understood when they co-exist in soil. Materials and methods: Here, five soils with contrasting properties were spiked with Cr(VI) (250 mg kg−1) and IMI (10 mg kg−1) and incubated for 90 days to determine their interactions and transformation or degradation. Results and discussion: The aging process Cr(VI) was divided into three phases corresponding with day 1 and days 2–50/70 and 50/70–90. The Cr(VI) content decreased by 62.0–95.2% in soils spiked with 250 mg Cr(VI) kg−1, slightly lower than that in soils spiked with 250 mg Cr(VI) kg−1 and 10 mg IMI kg−1 together (75.1–98.0%). Addition of 250 mg Cr(VI) kg−1 significantly increased the half-life of IMI to 89.7–192 days compared with 54.2–159 days in soils spiked with 10 mg IMI kg−1 only. HPLC-QTOF-MS/MS analysis reveals the presence of four transformation products (TPs) of IMI after incubation for 90 days, namely TP209, TP211, TP226 and TP240, and the presence of 250 mg Cr(VI) kg−1 promoted the formation of TP240. Conclusions: The results indicate that the addition of IMI scarcely influenced the aging process of Cr(VI) while the latter had significant effects in the transformation process of the former. These findings shed new light on our understanding of the fate of co-occurring Cr(VI) and IMI contaminants in soils. [ABSTRACT FROM AUTHOR]

• Hydrolyzed urine notably inhibited pharmaceutical removal in the mFe-PS system. • Phosphate, (bi)carbonate and pH hinder pharmaceutical removal in the mFe-PS system. • Phosphate and carbonate radicals decreased pharmaceutical removal efficiencies. • Phosphate radicals preferentially attack the benzene ring of pharmaceuticals. • Carbonate radicals react with pharmaceuticals through hydroxylation preferentially. This study investigated the degradation of clofibric acid (CFA), bezafibrate (BZF), and sulfamethoxazole (SMX) in synthetic human urine using a novel mesoporous iron powder-activated persulfate system (mFe-PS system), and identified the factors limiting their degradation in synthetic human urine. A kinetic model was established to expose the radical production in various reaction conditions, and experiments were conducted to verify the modeling results. In the phosphate-containing mFe-PS system, the 120 min removal efficiency of CFA decreased from 95.1% to 76.6% as the phosphate concentration increased from 0.32 to 6.45 mmol/L, but recovered to 90.5% when phosphate concentration increased to 16.10 mmol/L. Meanwhile, the increased concentration of phosphate from 0.32 to 16.10 mmol/L reduced the BZF degradation efficacy from 91.5% to 79.0%, whereas SMX removal improved from 37.3% to 62.9%. The mFe-PS system containing (bi)carbonate, from 4.20 to 166.70 mmol/L, reduced CFA and BZF removal efficiencies from 100% to 76.8% and 80.4%, respectively, and SMX from 83.5% to 56.7% within a 120-min reaction time. In addition, alkaline conditions (pH ≥ 8.0) inhibited CFA and BZF degradations, while nonacidic pH (pH ≥ 7.0) remarkably inhibited SMX degradation. Results of the kinetic model indicated the formation of phosphate (H 2 PO 4 ·/HPO 4 ·−) and/or carbonate radicals (CO 3 ·−) could limit pharmaceutical removal. The transformation products (TPs) of the pharmaceuticals revealed more incompletely oxidized TPs occurred in the phosphate- and (bi)carbonate-containing mFe-PS systems, and indicated that H 2 PO 4 ·/HPO 4 ·− mainly degraded pharmaceuticals via a benzene ring-opening reaction while CO 3 ·− preferentially oxidized pharmaceuticals via a hydroxylation reaction. [Display omitted] [ABSTRACT FROM AUTHOR]

Pesticides are emerging contaminants that pose various risks to human health and aquatic ecosystems. In this work, diuron was considered as a contaminant model to investigate the influence of the back-side illumination mode (BSI) on the photocatalytic activity of TiO2 coatings grown on Pyrex plates by metal–organic chemical vapour deposition (MOCVD). A photoreactor working in recirculation mode was irradiated at 365 nm with ultraviolet A (UVA) light-emitting diodes in BSI. The degradation of diuron and its transformation products was analysed by high-performance liquid chromatography, ion chromatography, and total organic carbon analysis. The coatings were characterised by X-ray diffraction analysis and scanning electron microscopy. Five coatings containing 3, 7, 10, 12 and 27 mg of TiO2 exhibited different morphology, crystallinity, thickness and photocatalytic activities. The morphology and crystallinity of the coatings had no significant influence on their photocatalytic activity, unlike their mass and thickness. TiO2 contents less than 10 mg limit the photocatalytic activity, whereas those greater than 15 mg are inefficient in the BSI because of their thickness. The maximum efficiency was achieved for coatings of thickness 1.8 and 2 µm with TiO2 contents of 10 and 12 mg, revealing that the photocatalyst thickness controls the photocatalytic efficiency in the BSI. [ABSTRACT FROM AUTHOR]

In this study, the aqueous photolytic degradation of the neonicotinoid pesticide clothianidin was studied in suspensions and aqueous extracts of hydrochar produced from olive kernels. A slight and nonsignificant decrease in the photodegradation rate of clothianidin in aqueous extracts of hydrochar (HCw) with an initial concentration of hydrochar ranged from 50 to 400 mg L−1 (rate constants ranged between k = 0.0034 and 0.0039 min−1) was observed in comparison to the respective rate in the bi-distilled water (k = 0.0040 min−1). On the contrary, in the presence of hydrochar suspensions (HCp), a significant decrease was observed for 50 mg L−1 hydrochar particle concentration (k = 0.020 min−1), while for higher concentrations (100 to 400 mg L−1), rate constants increased but with nonsignificant differences compared with the kinetics followed in the absence of them. Generally, the photodegradation rate of clothianidin, in the presence of HCw and HCp, is reduced compared to the photodegradation rate in bi-distilled aqueous solutions, except in the case of the aqueous suspension with an HCp concentration of 200 mg L−1. The transformation products (TPs) of clothianidin formed in the photolytic degradation processes were identified using ultrahigh-performance liquid chromatography coupled with accurate high-resolution mass spectrometry technique (UHPLC-LTQ-ORBITRAP). The formation profiles of TPs varied according to the matrix showing different degrees of participation of direct and indirect (photosensitized) phototransformation pathways. Photolytic degradation of clothianidin takes place mainly through denitration, hydroxylation and dechlorination pathways. Finally, the toxicity of the identified TPs was studied using the Vibrio fischeri bioassay. Toxicity was slightly reduced after 300 min of irradiation while maximum value was observed after 180–240 min of irradiation showing the formation of more toxic TPs along the photochemical degradation. [ABSTRACT FROM AUTHOR]

IntroductionFipronil (FIP) and thiobencarb (THIO) represent widely utilized pesticides in paddy fields, presenting environmental challenges that necessitate effective remediation approaches. Despite the recognized need, exploring bacterial consortia efficiently degrading FIP and THIO remains limited.MethodsThis study isolated three unique bacterial consortia—FD, TD, and MD—demonstrating the capability to degrade FIP, THIO, and an FIP + THIO mixture within a 10-day timeframe. Furthermore, the bioaugmentation abilities of the selected consortia were evaluated in paddy soils under various conditions.ResultsSequencing results shed light on the consortia’s composition, revealing a diverse bacterial population prominently featuring Azospirillum, Ochrobactrum, Sphingobium, and Sphingomonas genera. All consortia efficiently degraded pesticides at 800 µg/mL concentrations, primarily through oxidative and hydrolytic processes. This metabolic activity yields more hydrophilic metabolites, including 4-(Trifluoromethyl)-phenol and 1,4-Benzenediol, 2-methyl-, for FIP, and carbamothioic acid, diethyl-, S-ethyl ester, and Benzenecarbothioic acid, S-methyl ester for THIO. Soil bioaugmentation tests highlight the consortia’s effectiveness, showcasing accelerated degradation of FIP and THIO—individually or in a mixture—by 1.3 to 13-fold. These assessments encompass diverse soil moisture levels (20 and 100% v/v), pesticide concentrations (15 and 150 µg/g), and sterile conditions (sterile and non-sterile soils).DiscussionThis study offers an understanding of bacterial communities adept at degrading FIP and THIO, introducing FD, TD, and MD consortia as promising contenders for bioremediation endeavors.

Synthetic antioxidants (AOs) are commonly used in everyday items and industrial products to inhibit oxidative deterioration. However, the presence of AOs in food packaging and packaged foods has not been thoroughly documented. Moreover, studies on human exposure to AOs through skin contact with packaging or ingesting packaged foods are limited. In this study, we analyzed twenty-three AOs—including synthetic phenolic antioxidants (SPAs) and organophosphite antioxidants (OPAs)—along with six transformation products in various food samples and their packaging materials. We found AOs in food products at concentrations ranging from 1.30 × 103 to 1.77 × 105 ng/g, which exceeded the levels in both outer packaging (6.05 × 102–3.07 × 104 ng/g) and inner packaging (2.27 × 102–1.09 × 105 ng/g). The most common AOs detected in foodstuffs were tris(2,4-di-tert-butylphenyl) phosphate (AO168O), butylated hydroxytoluene (BHT), and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO1076), together constituting 95.7 % of the total AOs found. Our preliminary exposure assessment revealed that dietary exposure—estimated at a median of 2.55 × 104 ng/kg body weight/day for children and 1.24 × 104 ng/kg body weight/day for adults—is a more significant exposure route than dermal contact with packaging. Notably, four AOs were identified in food for the first time, with BHT making up 76.8 % and 67.6 % of the total BHT intake for children and adults, respectively. These findings suggest that food consumption is a significant source of BHT exposure. The estimated daily intakes of AOs via consumption of foodstuffs were compared with the recommended acceptable daily intake to assess the risks. This systematic investigation into AOs contributes to understanding potential exposure and health risks associated with AOs in packaged foods. It emphasizes the need for further evaluation of human exposure to these substances.

In this study, the aqueous photolytic degradation of the neonicotinoid pesticide clothianidin was studied in suspensions and aqueous extracts of hydrochar produced from olive kernels. A slight and nonsignificant decrease in the photodegradation rate of clothianidin in aqueous extracts of hydrochar (HCw) with an initial concentration of hydrochar ranged from 50 to 400 mg L−1 (rate constants ranged between k = 0.0034 and 0.0039 min−1) was observed in comparison to the respective rate in the bi-distilled water (k = 0.0040 min−1). On the contrary, in the presence of hydrochar suspensions (HCp), a significant decrease was observed for 50 mg L−1 hydrochar particle concentration (k = 0.020 min−1), while for higher concentrations (100 to 400 mg L−1), rate constants increased but with nonsignificant differences compared with the kinetics followed in the absence of them. Generally, the photodegradation rate of clothianidin, in the presence of HCw and HCp, is reduced compared to the photodegradation rate in bi-distilled aqueous solutions, except in the case of the aqueous suspension with an HCp concentration of 200 mg L−1. The transformation products (TPs) of clothianidin formed in the photolytic degradation processes were identified using ultrahigh-performance liquid chromatography coupled with accurate high-resolution mass spectrometry technique (UHPLC-LTQ-ORBITRAP). The formation profiles of TPs varied according to the matrix showing different degrees of participation of direct and indirect (photosensitized) phototransformation pathways. Photolytic degradation of clothianidin takes place mainly through denitration, hydroxylation and dechlorination pathways. Finally, the toxicity of the identified TPs was studied using the Vibrio fischeri bioassay. Toxicity was slightly reduced after 300 min of irradiation while maximum value was observed after 180–240 min of irradiation showing the formation of more toxic TPs along the photochemical degradation.

Contaminants of emerging concern (CECs) and their respective transformation products (TPs) formed following photodegradation pose considerable threats to the environment and our health. The formation of TPs during UV-LED-based degradation of three target pollutants in the EU Watch List of CECs was accessed by LC-MS-Orbitrap, and their reaction pathways were elucidated. The influence of different matrices and treatments of choice on TP formation was investigated. Results showed that matrix changes did not produce different reaction pathways during UV-A photocatalysis, although plots of TP peak areas vs. time were different for each case. A new TP was found for the antidepressant venlafaxine, (1-[2-(dimethylnitroryl)-1-(4-methoxyphenyl)ethyl]cyclohexanol. When comparing UV-A photocatalysis with UV-C photolysis, dissimilar pathways were observed due to the distinct reaction mechanisms of each process, since photocatalysis, unlike photolysis, relies on radical-based reaction routes. Different levels of confidence were obtained for each TP depending on the availability of MS2 data in the literature and of standards for comparison. All the found TPs had similar molecular masses in comparison to their respective parent compounds. Most of the TPs remained in the effluent after 6 hours of photodegradation, which highlights the importance of their control, close-monitoring, and further toxicity assessments. HIGHLIGHTS Detection of transformation products of contaminants of emerging concern in water.; Elucidation of reaction pathways for photolysis and photocatalysis.; A new transformation product found for venlafaxine.; No difference in detected compounds for tap and ultrapure water.;

As new pesticides continue to emerge in agricultural systems, understanding their environmental behavior is crucial for effective risk assessment. Tiafenacil (TFA), a promising novel pyrimidinedione herbicide, was the focus of this study. We developed an efficient QuEChERS-UHPLC-QTOF-MS/MS method to measure TFA and its transformation products (TP1, TP2, TP3, TP4, and TP5) in soil. Our calibration curves exhibited strong linearity (R2 ≥ 0.9949) ranging from 0.015 to 2.0 mg/kg within a low limit of quantification (LOQ) of 2.0 µg/kg. Inter-day and intra-day recoveries (0.10 to 2.0 mg/kg, 80.59% to 110.05%, RSD from 0.28% to 12.93%) demonstrated high sensitivity and accuracy. Additionally, TFA dissipation under aerobic conditions followed first-order kinetics, mainly yielding TP1 and TP4. In contrast, TP1 and TP2 were mainly found under sterilized and anaerobic conditions, and TFA dissipation followed second-order kinetics. Moreover, we predicted the transformation pathways of TFA using density functional theory (DFT) and assessed the toxicity levels of TFA and its TPs to aquatic organisms using ECOSAR. Collectively, these findings hold significant implications for a better understanding of TFA fate in diversified soil, benefiting its risk assessment and rational utilization.

Unplanned water reuse for crop irrigation may pose a global health risk due to the entry of contaminants into the food chain, undesirable effects on crop quality, and impact on soil health. In this study, we evaluate the impact derived from the co-occurrence of pharmaceuticals (Phs), trace metals (TMs), and one metalloid within the water–soil–plant continuum through bioassay experiments with Lactuca sativa L. Results indicate that the co-occurrence of Phs and TMs has synergistic or antagonistic effects, depending on target contaminants and environmental compartments. Complex formations between drugs and TMs may be responsible for enhanced sorption onto the soil of several Phs and TMs. Concerning plant uptake, the co-occurrence of Phs and TMs exerts antagonistic and synergistic effects on carbamazepine and diazepam, respectively. With the exception of Cd, drugs exert an antagonistic effect on TMs, negatively affecting their uptake and translocation. Drug contents in lettuce edible parts do not pose any threat to human health, but Cd levels exceed the maximum limits set for leafy vegetable foodstuffs. Under Ph-TM conditions, lettuce biomass decreases, and a nutrient imbalance is observed. Soil enzyme activity is stimulated under Ph-TM conditions (β-galactosidase) and Ph and Ph-TM conditions (urease and arylsulfatase), or it is not affected (phosphatase).

Photocatalysis is a prominent alternative wastewater treatment technique that has the potential to completely degrade pesticides as well as other persistent organic pollutants, leading to detoxification of wastewater and thus paving the way for its efficient reuse. In addition to the more conventional photocatalysts (e.g., TiO2, ZnO, etc.) that utilize only UV light for activation, the interest of the scientific community has recently focused on the development and application of visible light-activated photocatalysts like g-C3N4. However, some disadvantages of g-C3N4, such as the high recombination rate of photogenerated charges, limit its utility. In this light, the present study focuses on the synthesis of WO3 fibers/g-C3N4 Z-scheme heterojunctions to improve the efficiency of g-C3N4 towards the photocatalytic removal of the widely used insecticide clothianidin. The effect of two different g-C3N4 precursors (urea and thiourea) and of WO3 fiber content on the properties of the synthesized composite materials was also investigated. All aforementioned materials were characterized by a number of techniques (XRD, SEM-EDS, ATR-FTIR, Raman spectroscopy, DRS, etc.). According to the results, mixing 6.5% W/W WO3 fibers with either urea or thiourea derived g-C3N4 significantly increased the photocatalytic activity of the resulting composites compared to the precursor materials. In order to further elucidate the effect of the most efficient composite photocatalyst in the degradation of clothianidin, the generated transformation products were tentatively identified through UHPLC tandem high-resolution mass spectroscopy. Finally, the detoxification effect of the most efficient process was also assessed by combining the results of an in-vitro methodology and the predictions of two in-silico tools.

In this study, the nutritional components of Hongjundouzha inoculated with Neurospora crassa at different fermentation times were analyzed. RNA sequencing (RNA-seq), quantitative real-time polymerase chain reaction (real-time PCR) and ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)-based non-target metabolomics were used to find out the main differentially expressed genes (DEGs), key metabolites and metabolic pathways affecting the fermentation of this strain, and the transcription and expression of cellulase, an important gene, was explored. The results showed that the second day of fermentation was the key period for the transformation of nutrients in Hongjundouzha and the most active period of gene expression, where cellulase expression was the highest. Carbohydrates in okara were metabolized through the starch and sucrose metabolism and carbon metabolism pathways to produce D-arabinose, sorbitol, D-xylose, L-fucose, linoleic acid, gamma-linolenic acid and arachidonic acid. On the third day, amino acid metabolism occurred. Proteins in okara were metabolized into glutamate, alanine, valine and other amino acids through the amino acid biosynthesis pathway. On the fourth day, secondary metabolites were produced. Daidzein, genistein and genistin in okara were transformed into neohesperidin, strychnine, squamolone and other substances with special physiological activities through the secondary metabolite biosynthesis pathway. The mycelia began to age, lysophosphatidyl choline (LPC) 18:4/18:1 and 18:1, lipids indicating food spoilage, appeared. In general, the second day of fermentation was the most active period of nutrient transformation in Hongjundouzha. The product matured on the third day of fermentation, and began to age and rot on the fourth day.

Integrative passive samplers such as the Chemcatcher are often proposed as alternatives for conventional grab sampling of surface waters. So far, their routine application for regulatory monitoring is hampered (among others) by the fact that TWA concentrations may depend significantly on the design and specifics of the samplers employed. The presented study addresses this issue, focusing on the uptake of polar organic pollutants in three different Chemcatcher configurations and polydimethylsiloxane (PDMS) sheets in the field. Covering waste water treatment plant effluents, creeks, and rivers, samplers were deployed for periods of 14–21 days in eight trials over the course of one year. 33 organic pesticides, 14 transformation products and 31 pharmaceuticals could be detected at least once in TWA concentrations ranging from 0.03 ng/L to 16.5 μg/L. We show that through employing generic, i.e. sampler specific, rather than compound specific sampling rates, the variation among results from three integrative passive sampler designs yields linear correlations with an offset of less than 0.1 and correlation coefficients r2 > 0.8. In this way, TWA concentrations enable the identification of low-concentration xenobiotics of concern, which may support regulatory monitoring correspondingly.

Sulfonamides circulating in the environment lead to disturbances in food chains and local ecosystems, but most importantly contribute to development of resistance genes, which generate problems with multidrug-resistant bacterial infections treatment. In urban areas, sources of sulfonamide distribution in soils have received comparatively less attention in contrast to rural regions, where animal-derived manure, used as a natural fertilizer, is considered the main source. The aim of this study was to determine eight sulfonamides (sulfadiazine, sulfamerazine, sulfamethazine, sulfamethizole, sulfamethoxazole, sulfapyridine, sulfathiazole, and sulfisoxazole) in environmental soil samples collected from urbanized regions in Silesian Voivodeship with increased animal activity. These soils were grouped according to the organic carbon content. It was necessary to develop versatile and efficient extraction and determination method to analyze selected sulfonamides in various soil types. The developed LC–MS/MS method for sulfonamides analyzing was validated. The obtained recoveries exceeded 45% for soil with medium organic carbon content and 88% for sample with a very low organic carbon content (arenaceous quartz). The obtained results show the high impact of organic matter on analytes adsorption in soil, which influences recovery. All eight sulfa drugs were determined in environmental samples in the concentration range 1.5–10.5 ng g-1. The transformation products of the analytes were also identified, and 29 transformation products were detected in 24 out of 27 extracts from soil samples. [ABSTRACT FROM AUTHOR]

Anaerobic bioreactors are an efficient technology for the biodegradation of emerging contaminants in environmental matrices. In this work, a horizontal-flow anaerobic immobilized biomass (HAIB) bioreactor was used to remove caffeine (CAF), which is frequently found in various aqueous matrices. The acrylic bench top bioreactor, with dimensions of 100 × 5.00 cm, was operated with a hydraulic retention time (HRT) of 12 h, during 45 weeks, under mesophilic conditions. The operation was performed in 4 phases: without CAF addition (phase I); CAF spiked at 300 μg L−1 (phase II); CAF at 600 μg L−1 (phase III); and CAF at 900 μg L−1 (phase IV). Samples of bioreactor influent and effluent were analyzed by liquid chromatography/tandem mass spectrometry (LC–MS/MS). The bioreactor removed organic matter (OM) and CAF with efficiencies of 88 and 93%, respectively. The first-order apparent removal constant (Kapp) values for OM and CAF were 0.419 and 0.304 h−1, respectively. Five transformation products (TPs) were identified, with m/z 243, 227, 211, and 181 (two products). The HAIB bioreactor is a suitable system for the removal of CAF present in wastewater, even at a concentration level of µg L−1. [ABSTRACT FROM AUTHOR]

The Covid-19 pandemic has affected the global population since 2019. The rapid development and approval of vaccines has brought relief. Yet, effective cures are still being researched. Even if the pandemic situation may end, SARS-CoV-2 will remain and, thus, continued application of the drugs will lead to emissions of the active ingredients into the aquatic environment, as with other anthropogenic micropollutants. However, a general method for trace analysis of antiviral drugs is still missing. To this purpose, favipiravir, remdesivir, its active metabolite GS-441524, molnupiravir and its active metabolite EIDD-1931 were selected as representative analytes. A method was developed based on solid phase extraction and high-performance liquid chromatography combined with electrospray ionization quadrupole time-of-flight high-resolution mass spectrometry. Optimization comprised the choice of chromatographic columns, elution gradient, mass spectrometry and tandem mass spectrometry parameters. Solid phase extraction proved suitable for increase in limits of detection and quantitation. amelioration of the limits of detection and quantitation. Matrix effects were investigated applying the optimized method to a wastewater sample with added virustatics. All five compounds could be separated with reversed phase chromatography, whereas EIDD-1931 profited from hydrophilic interaction liquid chromatography. The optimized method yielded limits of detection and quantification of 2.1·10-1, 6.9·10-1 µg·L-1 for favipiravir, 1.8·10-3, 5.5·10-3 µg·L-1 for remdesivir, 1.9·10-3, 7.6·10-3 µg·L-1 for GS-441524, 2.9·10-3, 8.7·10-3 µg·L-1 for molnupiravir, and 1.3·10-1, 3.8·10-1 µg·L-1 for EIDD 1931. The method was first applied to compound stability testing at pH 2.8 and 9.7. At pH 2.8, remdesivir, GS-441524 and molnupiravir proved stable, whereas about 14% of EIDD-1931 and favipiravir were degraded. All five antiviral compounds were almost completely decomposed at pH 9.7. The application of the method was further demonstrated for potential transformation product detection on favipiravir ozonation monitoring. [ABSTRACT FROM AUTHOR]

Objective: To reveal the oxidation mechanisms and transformation products of HOCl reacting with unsaturated fatty acids. Methods: Gaussian 16 software package was used, in which density functional method M06-2X (D3) in conjunction with 6-31+G (d) basis set along with implicit SMD solvent model were selected. Results: In the oxidation reaction of HOCl with oleic acid, a monounsaturated fatty acid, chloronium ion intermediate was initially generated, and then it reacted with water molecule to yield chlorohydrin. Conclusion: The initial chloronium ion intermediate formation was the rate-limiting step with the activation free energy of ~8 kcal/mol. Epoxide and truncated aldehyde were two transformation products. The former was produced from dehydrochlorination of chlorohydrins, while the latter was yielded from epoxide and chlorohydrin through a series of reactions with hypochlorite. Their activation free energies of the rate-limiting steps were ~23 and 24 kcal/mol, respectively. Ethylene substituted with two ethyl groups was selected as the oleic acid model, and its activation free energy in reacting with HOCl was higher than that of oleic acid by only 1 kcal/mol. The activation free energies of HOCl reacting with linoleic acid, cis-9, trans-11 LCA, catalpic acid, and arachidonic acid models to generate chlorohydrin were ~10, 13, 16, and 14 kcal/mol, respectively. The chloronium ion intermediate formation is the main mechanism in the oxidation reaction of HOCl and unsaturated fat acid and the activation free energy is generally lower than 15 kcal/mol, which indicates that this oxidation reaction is kinetically feasible to occur. The oxidation product chlorohydrin can transform into epoxide and truncated aldehyde, but the activation free energies are relatively high with the values of ~23 and 24 kcal/mol, respectively. The structure within 3 carbon atoms from the double bond in the unsaturated fat acid can be selected as the model, which can well reflect the reaction activity of unsaturated fat acid. [ABSTRACT FROM AUTHOR]

Urban stormwater contains various micropollutants, such as biocides, which are washed off from facades during wind-driven rain events. Biocides can reach the groundwater via stormwater infiltration systems (SIS), although the soil layer acts as a reactive barrier preventing the leaching of biocides but producing transformation products (TPs). Little is known about the occurrence and concentration of biocides in SIS soils, their distribution and temporal behavior. Here, we present a first systematic screening of three commonly used biocides (diuron, octylisothiazolinone (OIT), terbutryn) and four TPs of terbutryn in 46 French and German SIS. Overall, biocide occurrence in SIS topsoils was ubiquitous but low, while point source inputs to specific SIS were high but rare. Low concentrations (< 2ng g-1) of terbutryn were detected in 78% of the SIS. Maximum concentrations occurred in recently constructed SIS, suggesting that this is due to higher biocide loads entering the SIS. The frequent detection of terbutryn supports the idea that it is a non-point source marker, as it is relatively stable in soil (t1/2 > 90 days) and widely used in renders and paints. In contrast, high concentrations of diuron (168 ng g-1) and OIT (58 ng g-1) were observed in only one sample, suggesting an urban point source contamination, possibly from a freshly repainted facade. The distinction between source types provides a basis for targeted measures to prevent biocide entry to groundwater. Altogether, this study opens the door to a more systematic consideration of micropollutant dissipation and ecotoxicological effects in SIS design and monitoring. [ABSTRACT FROM AUTHOR]

With the development of urbanization and industrialization, more and more chemicals were produced in large quantities and widely used. As a result, they entered the water environment through sewage discharge and agricultural drainage. Currently, the analytical methods of contaminants in water include three main strategies, including target screening, suspect analysis and nontarget screening. The number of compounds identified using target screening methods has increased to hundreds, which is far from meeting the current demand for emerging contaminants (ECs) detection in water environment. To comprehensively screen potential emerging contaminants in the Yangtze River in Jiangsu Province, a nontarget screening strategy combined spectral library search with a molecular network was proposed in Jiangsu-Anhui provincial boundary cross section and 22 drinking water sources in Jiangsu section of Yangtze River. Under this strategy, through spectral library screening using a in-house library, a total of 118 emerging contaminants were identified by accurate mass, isotope distribution and MS/MS fragment ions. These contaminants involved pesticides, herbicides, fungicides, drugs, antibiotics, persistent organic pollutants, flame retardants, plasticizers, indicated active agents, chemical intermediates, and other categories. Since traditional targeted screening relies on commercial standards and screening lists, nontarget screening is a more favorable approach to study ECs and their transformation products in water. Therefore, unannotated chemical substances with similar structures to known contaminants were identified through molecular network technology based on the premise that structurally similar compounds have similar fragment ions. Through using the Global Natural Products Society molecular network (GNPS) to extract molecular families, another contaminant with similar toxicity to amantadine, N-methyl-1-adamantaneamine was found. Furthermore, twenty-three contaminants were confirmed through commercial standard, and 14 of them were detected at a rate of 100%. The quantitative analysis revealed the prevalence of perfluorinated compounds, pharmaceuticals, and personal care products in water bodies, and the total concentrations of the 23 contaminants in each sample ranged from 6.46×102 ng/L to 1.72×103 ng/L. Seven drugs and personal care products were detected. Amantadine was detected at the highest concentration among all locations, and perfluorooctanoic acid (PFOA), amantadine and 2,4-dinitrophenol were detected with the highest mean concentration levels in each location. The nontarget screening strategy using spectral library search and molecular network enabled high-throughput identification of contaminants in water without prior information and standards, in which the structures of unannotated characteristic peaks were inferred from annotated substances with spectral libraries. This strategy will accelerate the systematic discovery of emerging and unknown contaminants in the aqueous environment.

N-(1,3-Dimethyl butyl)-N′-phenyl-phenylenediamine-quinone (6PPD-Q) is a derivative of the widely used rubber tire antioxidant 6PPD, which was first found to be acutely toxic to coho salmon. Subsequent studies showed that 6PPD-Q had species-specific acute toxicity in fishes and potential hepatotoxicity in mice. In addition, 6PPD-Q has been reported in human urine, demonstrating the potential widespread exposure of humans to this chemical. However, whether 6PPD-Q poses a higher risk to humans than its parent compound, 6PPD, and could cause adverse effects in humans is still unclear. In this study, we utilized two human liver cell models (the human proto-hepatocyte model L02 and the human hepatocellular carcinoma cell line HepG2) to investigate the potentially differential effects of these two chemicals. Cell viability curve analysis showed that 6PPD-Q had lower IC50 values than 6PPD for both liver cell lines, suggesting higher toxicity of 6PPD-Q to human liver cells than 6PPD. In addition, L02 cells are more sensitive to 6PPD-Q exposure, which might be derived from its weaker metabolic transformation of 6PPD-Q, since significantly lower levels of phase I and phase II metabolites were detected in 6PPD-Q-exposed L02 cell culture medium. Furthermore, pathway analysis showed that 6PPD-Q exposure induced changes in phenylalanine, tyrosine, and tryptophan biosynthesis and tyrosine metabolism pathways in L02 cells, which might be the mechanism underlying its liver cell toxicity. Gene expression analysis revealed that exposure to 6PPD-Q induced excessive ROS production in L02 cells. Our results further supported the higher risk of 6PPD-Q than 6PPD and provided insights for understanding the effects of 6PPD-Q on human health.

The use of agrochemical and pharmaceutical active ingredients is essential in our modern society. Given the increased concern and awareness of the potential risks of some chemicals, there is a growing need to align with ‘green chemistry’ and ‘safe and sustainable by design’ principles and thus to evaluate the hazards of agrochemical and pharmaceutical active ingredients in early stages of R&D. We give an overview of the current challenges and opportunities to assess the principle of biodegradability in the environment. Development of new medium/high-throughput methodologies, combining predictive tools and wet-lab experimentation are essential to design biodegradable chemicals early in the active ingredient discovery and selection process.

The photocatalytic degradation of the antidepressant drug bupropion (BUP) has been studied using TiO2 as catalyst. Complete removal of the target compound is achieved within 90 min of treatment and the effect of various operational parameters like the catalyst dose, the initial concentration of the drug or the pH of the treated solution, have been evaluated. The influence of various inorganic or organic constituents usually present in natural waters like chloride or nitrate ions and humic acids respectively, was also investigated revealing a negative impact on the photocatalytic degradation process. Accordingly, the degradation of BUP was also evaluated in different water matrices like wastewater effluents or leachate exhibiting slower degradation kinetics. Finally, employing high-resolution mass spectrometry, 38 transformation products (TPs) have been identified 24 out of which have been presented for the first time herein.