Multiphase Ozonolysis of Bisphenol A: Chemical Transformations on Surfaces in the Environment.

High global plastic production volumes have led to the widespread presence of bisphenol compounds in human living and working environments. The most common bisphenol, bisphenol A (BPA), despite being endocrine disruptive and estrogenic, is still not fully banned worldwide, leading to continued human exposure via particles in air, dust, and surfaces in both outdoor and indoor environments. While its abundance is well documented, few studies have addressed the chemical transformations of BPA, the properties of its reactive products, and their toxicity. Here, the first gas-surface multiphase ozonolysis experiment of BPA thin films, at a constant ozone mixing ratio of 100 ppb, was performed in a flow tube for periods up to 24 h. Three transformation products involving the addition of 1, 2, and 3 oxygen atoms to the molecule were identified by LC-ESI-HRMS analyses. Exposure of indoor air to thin BPA surface films and BPA-containing thermal paper over periods of days validated the flow tube experiments, demonstrating the rapid nature of this multiphase ozonolysis reaction at atmospherically relevant ozone levels. Multiple transformation pathways are proposed that are likely applicable to not only BPA but also emerging commercial bisphenol products.

Pesticides in Greenhouse Airborne Particulate Matter: Occurrence, Distribution, Transformation Products, and Potential Human Exposure Risks.

Pesticides are frequently sprayed in greenhouses to ensure crop yields, where airborne particulate matter (PM) may serve as a carrier in depositing and transporting pesticides. However, little is known about the occurrence and fate of PM-borne pesticides in greenhouses. Herein, we examined the distribution, dissipation, and transformation of six commonly used pesticides (imidacloprid, acetamiprid, prochloraz, triadimefon, hexaconazole, and tebuconazole) in greenhouse PM (PM1, PM2.5, and PM10) after application as well as the associated human exposure risks via inhalation. During 35 days of experiment, the six pesticides were detected in all PM samples, and exhibited size- and time-dependent distribution characteristics, with the majority of them (>64.6%) accumulated in PM1. About 1.0-16.4% of initially measured pesticides in PM remained after 35 days, and a total of 12 major transformation products were elucidated, with six of them newly identified. The inhalation of PM could be an important route of human exposure to pesticides in the greenhouse, where the estimated average daily human inhalation dose (ADDinh) of the six individual pesticides was 2.1-1.2 × 104 pg/kg day-1 after application (1-35 days). Our findings highlight the occurrence of pesticides/transformation products in greenhouse PM, and their potential inhalation risks should be further concerned.

Methylation and Demethylation of Emerging Contaminants in Plants.

Many contaminants of emerging concern (CECs) have reactive functional groups and may readily undergo biotransformations, such as methylation and demethylation. These transformations have been reported to occur during human metabolism and wastewater treatment, leading to the propagation of CECs. When treated wastewater and biosolids are used in agriculture, CECs and their transformation products (TPs) are introduced into soil-plant systems. However, little is known about whether transformation cycles, such as methylation and demethylation, take place in higher plants and hence affect the fate of CECs in terrestrial ecosystems. In this study, we explored the interconversion between four common CECs (acetaminophen, diazepam, methylparaben, and naproxen) and their methylated or demethylated TPs in Arabidopsis thaliana cells and whole wheat seedlings. The methylation-demethylation cycle occurred in both plant models with demethylation generally taking place at a greater degree than methylation. The transformation rate of demethylation or methylation was dependent on the bond strength of R-CH3, with demethylation of methylparaben or methylation of acetaminophen being more pronounced. Although not explored in this study, these interconversions may exert influences on the behavior and biological activity of CECs, particularly in terrestrial ecosystems. The study findings demonstrated the prevalence of transformation cycles between CECs and their methylated or demethylated TPs in higher plants, contributing to a more complete understanding of risks of CECs in the human-wastewater-soil-plant continuum.

Reactive Oxygen Species Generated in Situ During Carbamazepine Photodegradation at 222 nm Far-UVC: Unexpected Role of H2O Molecules.

When 222 nm far-UVC is used to drive AOPs, photolysis emerges as a critical pathway for the degradation of numerous organic micropollutants (OMPs). However, the photodegradation mechanisms of the asymmetrically polarized OMPs at 222 nm remain unclear, potentially posing a knowledge barrier to the applications of far-UVC. This study selected carbamazepine (CBZ), a prevalent aquatic antiepileptic drug that degrades negligibly at 254 nm, to investigate its photodegradation mechanisms at 222 nm. Accelerated CBZ treatment by 222 nm far-UVC was mainly attributed to in situ ROS generation via self-sensitized photodegradation of CBZ. By quenching experiments and EPR tests, •OH radicals were identified as the major contributor to the CBZ photodegradation, whereas O2•- played a minor role. By deoxygenation and solvent exchange experiments, the H2O molecules were demonstrated to play a crucial role in deactivating the excited singlet state of CBZ (1CBZ*) at 222 nm: generating •OH radicals via electron transfer interactions with 1CBZ*. In addition, 1CBZ* could also undergo a photoionization process. The transformation products and pathways of CBZ at 222 nm were proposed, and the toxicities of CBZ's products were predicted. These findings provide valuable insights into OMPs' photolysis with 222 nm far-UVC, revealing more mechanistic details for far-UVC-driven systems.

Contamination Status of Novel Organophosphate Esters Derived from Organophosphite Antioxidants in Soil and the Effects on Soil Bacterial Communities.

The contamination status of novel organophosphate esters (NOPEs) and their precursors organophosphite antioxidants (OPAs) and hydroxylated/diester transformation products (OH-OPEs/di-OPEs) in soils across a large-scale area in China were investigated. The total concentrations of the three test NOPEs in soil were 82.4-716 ng g-1, which were considerably higher than those of traditional OPEs (4.50-430 ng g-1), OPAs (n.d.-30.8 ng g-1), OH-OPEs (n.d.-0.49 ng g-1), and di-OPEs (0.57-21.1 ng g-1). One NOPE compound, i.e., tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O) contributed over 65% of the concentrations of the studied OPE-associated contaminants. A 30-day soil incubation experiment was performed to confirm the influence of AO168 = O on soil bacterial communities. Specific genera belonging to Proteobacteria, such as Lysobacter and Ensifer, were enriched in AO168 = O-contaminated soils. Moreover, the ecological function of methylotrophy was observed to be significantly enhanced (t-test, p < 0.01) in soil treated with AO168 = O, while nitrogen fixation was significantly inhibited (t-test, p < 0.01). These findings comprehensively revealed the contamination status of OPE-associated contaminants in the soil environment and provided the first evidence of the effects of NOPEs on soil microbial communities.

Sequential Anaerobic-Aerobic Treatment Enhances Sulfamethoxazole Removal: From Batch Cultures to Observations in a Large-Scale Wastewater Treatment Plant.

Sulfamethoxazole (SMX) passes through conventional wastewater treatment plants (WWTPs) mainly unaltered. Under anoxic conditions sulfate-reducing bacteria can transform SMX but the fate of the transformation products (TPs) and their prevalence in WWTPs remain unknown. Here, we report the anaerobic formation and aerobic degradation of SMX TPs. SMX biotransformation was observed in nitrate- and sulfate-reducing enrichment cultures. We identified 10 SMX TPs predominantly showing alterations in the heterocyclic and N4-arylamine moieties. Abiotic oxic incubation of sulfate-reducing culture filtrates led to further degradation of the major anaerobic SMX TPs. Upon reinoculation under oxic conditions, all anaerobically formed TPs, including the secondary TPs, were degraded. In samples collected at different stages of a full-scale municipal WWTP, anaerobically formed SMX TPs were detected at high concentrations in the primary clarifier and digested sludge units, where anoxic conditions were prevalent. Contrarily, their concentrations were lower in oxic zones like the biological treatment and final effluent. Our results suggest that anaerobically formed TPs were eliminated in the aerobic treatment stages, consistent with our observations in batch biotransformation experiments. More generally, our findings highlight the significance of varying redox states determining the fate of SMX and its TPs in engineered environments.

Tracking Dynamic Chemical Reactivity Networks with High-Resolution Mass Spectrometry: A Case of Microplastic-Derived Dissolved Organic Carbon.

Chemical degradation testing often involves monitoring the loss of a chemical or the evolution of a single diagnostic product through time. Here, we demonstrate a novel approach to tracing complex degradation networks using mass-spectrometry-based methods and open cheminformatics tools. Ester- and ether-based thermoplastic polyurethane (TPU_Ester and TPU_Ether) microplastics (350 µm) and microplastics-derived dissolved organic carbon (MP-DOC) were photoweathered in a simulated marine environment and subsequently analyzed by liquid chromatography coupled to high-resolution mass spectrometry. We formula-annotated 1342 and 2344 unique features in the MP-DOC of TPU_Ester and TPU_Ether, respectively. From these, we extracted 199 and 568 plausible parent-transformation product pairs via matching of features (a) with complementary increasing and decreasing trends (Spearman's correlation coefficient between normalized intensity and time), (b) spectral similarities of at least three accurate mass MS2 fragments, and (c) at least 3 ppm agreement between the theoretical and measured change in m/z between the parent-transformation product formula. Molecular network analysis revealed that both chain scission and cross-linking reactions occur dynamically rather than degradation proceeding in a monotonic progression to smaller or more oxygenated structures. Network nodes with the highest degree of centrality were tentatively identified using in silico fragmentation and can be prioritized for toxicity screening or other physicochemical properties of interest. This work has important implications for chemical transformation tracking in complex mixtures and may someday enable improved elucidation of environmental transformation rules (i.e., structure-reactivity relationships) and fate modeling.

In silico ecotoxicity assessment of pharmaceutical residues in wastewater following oxidative treatment.

Advanced oxidation processes such as thermal plasma activation and UV-C/H2O2 treatment are considered as applications for the degradation of pharmaceutical residues in wastewater complementary to conventional wastewater treatment. It is supposed that direct oxidative treatment can lower the toxicity of hospital sewage water (HSW). The aim of this study was to predict the ecotoxicity for three aquatic species before and after oxidative treatment of 10 quantified pharmaceuticals in hospital sewage water. With the application of oxidative chemistry, pharmaceuticals are degraded into transformation products before reaching complete mineralization. To estimate the potential ecotoxicity for fish, Daphnia and green algae ECOSAR quantitative structure-activity relationship software was used. Structure information from pristine pharmaceuticals and their oxidative transformation products were calculated separately and in a mixture computed to determine the risk quotient (RQ). Calculated mixture toxicities for 10 compounds found in untreated HSW resulted in moderate-high RQ predictions for all three aquatic species. Compared to untreated HSW, 30-min treatment with thermal plasma activation or UV-C/H2O2 resulted in lowered RQs. For the expected transformation products originating from fluoxetine, cyclophosphamide and acetaminophen increased RQs were predicted. Prolongation of thermal plasma oxidation up to 120 min predicted low-moderate toxicity in all target species. It is anticipated that further degradation of oxidative transformation products will end in less toxic aliphatic and carboxylic acid products. Predicted RQs after UV-C/H2O2 treatment turned out to be still moderate-high. In conclusion, in silico extrapolation of experimental findings can provide useful predicted estimates of mixture toxicity. However due to the complex composition of wastewater this in silico approach is a first step to screen for ecotoxicity. It is recommendable to confirm these predictions with ecotoxic bioassays.

Analysis of nitrogen-containing rocket fuel transformation products in loamy soil by thermal desorption gas chromatography-tandem mass spectrometry.

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.

Concurrent Analysis of Tiafenacil and Its Transformation Products in Soil by Using Newly Developed UHPLC-QTOF-MS/MS-Based Approaches.

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.

Oxidative treatment of micropollutants present in wastewater: A special emphasis on transformation products, their toxicity, detection, and field-scale investigations.

Micropollutants have become ubiquitous in aqueous environments due to the increased use of pharmaceuticals, personal care products, pesticides, and other compounds. In this review, the removal of micropollutants from aqueous matrices using various advanced oxidation processes (AOPs), such as photocatalysis, electrocatalysis, sulfate radical-based AOPs, ozonation, and Fenton-based processes has been comprehensively discussed. Most of the compounds were successfully degraded with an efficiency of more than 90%, resulting in the formation of transformation products (TPs). In this respect, degradation pathways with multiple mechanisms, including decarboxylation, hydroxylation, and halogenation, have been illustrated. Various techniques for the analysis of micropollutants and their TPs have been discussed. Additionally, the ecotoxicity posed by these TPs was determined using the toxicity estimation software tool (T.E.S.T.). Finally, the performance and cost-effectiveness of the AOPs at the pilot scale have been reviewed. The current review will help in understanding the treatment efficacy of different AOPs, degradation pathways, and ecotoxicity of TPs so formed.

Organophosphate Triesters and Their Transformation Products in Sediments of Mangrove Wetlands in the Beibu Gulf, South China Sea.

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.

Tire-Derived Transformation Product 6PPD-Quinone Induces Mortality and Transcriptionally Disrupts Vascular Permeability Pathways in Developing Coho Salmon.

Urban stormwater runoff frequently contains the car tire transformation product 6PPD-quinone, which is highly toxic to juvenile and adult coho salmon (Onchorychus kisutch). However, it is currently unclear if embryonic stages are impacted. We addressed this by exposing developing coho salmon embryos starting at the eyed stage to three concentrations of 6PPD-quinone twice weekly until hatch. Impacts on survival and growth were assessed. Further, whole-transcriptome sequencing was performed on recently hatched alevin to address the potential mechanism of 6PPD-quinone-induced toxicity. Acute mortality was not elicited in developing coho salmon embryos at environmentally measured concentrations lethal to juveniles and adults, however, growth was inhibited. Immediately after hatching, coho salmon were sensitive to 6PPD-quinone mortality, implicating a large window of juvenile vulnerability prior to smoltification. Molecularly, 6PPD-quinone induced dose-dependent effects that implicated broad dysregulation of genomic pathways governing cell-cell contacts and endothelial permeability. These pathways are consistent with previous observations of macromolecule accumulation in the brains of coho salmon exposed to 6PPD-quinone, implicating blood-brain barrier disruption as a potential pathway for toxicity. Overall, our data suggests that developing coho salmon exposed to 6PPD-quinone are at risk for adverse health events upon hatching while indicating potential mechanism(s) of action for this highly toxic chemical.

Identification and Coexposure of Neonicotinoid Insecticides and Their Transformation Products in Retail Cowpea (Vigna unguiculata).

There is growing evidence that the transformation products of emerging contaminants in foodstuffs may pose a health risk to humans. However, the exact identities, levels, and estimated dietary intake (EDI) of neonicotinoid transformation products in crops remain poorly understood. We established an extended suspect screening strategy to investigate neonicotinoid insecticides and their transformation products in retail cowpea from 11 cities in Hainan Province, China. Forty-nine transformation products were identified in retail cowpea, of which 22-36 were found in 98.6% of the samples. Notably, 31 new transformation products were derived from new processes or a combination of different transformation processes. The mean concentrations of neonicotinoids and nine of the transformation products (with authentic standards) were in the ranges of 0.0824-5.34 and 0.0636-1.50 ng/g, respectively. The cumulative EDIs of the quantified transformation products were lower than those of parent neonicotinoids with the exception of clothianidin desmethyl, which had a ratio of 1157%. However, the coexistence of the other 40 transformation products (without authentic standards) in cowpea suggested that the exposure risk from all of the transformation products might be higher. This study demonstrated that pesticide transformation products should be considered in food chain risk assessments and included in future regulatory management.

Reactive Oxygen Species and Chromophoric Dissolved Organic Matter Drive the Aquatic Photochemical Pathways and Photoproducts of 6PPD-quinone under Simulated High-Latitude Conditions.

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).

Methylation and Demethylation of Emerging Contaminants Changed Bioaccumulation and Acute Toxicity in Daphnia magna.

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.

Suspect and Nontarget Screening Reveal the Underestimated Risks of Antibiotic Transformation Products in Wastewater Treatment Plant Effluents.

Antibiotics are anthropogenic contaminants with a global presence and of deep concern in aquatic environments, while less is known about the occurrence and risks of their transformation products (TPs). Herein, we developed a comprehensive suspect and nontarget screening workflow based on high-resolution mass spectrometry to identify unknown antibiotic TPs in wastewater treatment plant effluents. We identified 211 compounds (35 parent antibiotics and 176 TPs) at confidence levels of ≥3 and 107 TPs originated from macrolides. TPs were quantified by 17 TPs standards and semiquantified by the predicted response factors and accounted for 55.6-95.1% (76.7% on average) of the total concentrations of parents and TPs. 22.2%, 63.1%, and 18.8% of the identified TPs were estimated to be more persistent, mobile, and toxic than their parent antibiotics, respectively. Further ecological risk assessment based on concentrations and toxicity to aquatic organisms revealed that the cumulative risks of TPs were generally higher than those of parents. Despite the newly formed N-oxide TPs, the tertiary treatment process (mainly ozonation) could decrease the averaged 20.3% of concentrations and 36.2% of the risks of antibiotic-related compounds. This study highlights the necessity to include antibiotic TPs in environmental scrutiny and risk assessment of antibiotics in different aquatic environments.

Multi-Omic Profiling of a Newly Isolated Oxy-PAH Degrading Specialist from PAH-Contaminated Soil Reveals Bacterial Mechanisms to Mitigate the Risk Posed by Polar Transformation Products.

Polar biotransformation products have been identified as causative agents for the eventual increase in genotoxicity observed after the bioremediation of PAH-contaminated soils. Their further biodegradation has been described under certain biostimulation conditions; however, the underlying microorganisms and mechanisms remain to be elucidated. 9,10-Anthraquinone (ANTQ), a transformation product from anthracene (ANT), is the most commonly detected oxygenated PAH (oxy-PAH) in contaminated soils. Sand-in-liquid microcosms inoculated with creosote-contaminated soil revealed the existence of a specialized ANTQ degrading community, and Sphingobium sp. AntQ-1 was isolated for its ability to grow on this oxy-PAH. Combining the metabolomic, genomic, and transcriptomic analyses of strain AntQ-1, we comprehensively reconstructed the ANTQ biodegradation pathway. Novel mechanisms for polyaromatic compound degradation were revealed, involving the cleavage of the central ring catalyzed by Baeyer-Villiger monooxygenases (BVMO). Abundance of strain AntQ-1 16S rRNA and its BVMO genes in the sand-in-liquid microcosms correlated with maximum ANTQ biodegradation rates, supporting the environmental relevance of this mechanism. Our results demonstrate the existence of highly specialized microbial communities in contaminated soils responsible for processing oxy-PAHs accumulated by primary degraders. Also, they underscore the key role that BVMO may play as a detoxification mechanism to mitigate the risk posed by oxy-PAH formation during bioremediation of PAH-contaminated soils.

Toxicity Evaluation and Effect-Based Identification of Chlorine Disinfection Products of the Anti-COVID-19 Drug Chloroquine Phosphate.

Antiviral transformation products (TPs) generated during wastewater treatment are an environmental concern, as their discharge, in considerable amounts, into natural waters during a pandemic can pose possible risks to the aquatic environment. Identification of the hazardous TPs generated from antivirals during wastewater treatment is important. Herein, chloroquine phosphate (CQP), which was widely used during the coronavirus disease-19 (COVID-19) pandemic, was selected for research. We investigated the TPs generated from CQP during water chlorination. Zebrafish (Danio rerio) embryos were used to assess the developmental toxicity of CQP after water chlorination, and hazardous TPs were estimated using effect-directed analysis (EDA). Principal component analysis revealed that the developmental toxicity induced by chlorinated samples could be relevant to the formation of some halogenated TPs. Fractionation of the hazardous chlorinated sample, along with the bioassay and chemical analysis, identified halogenated TP387 as the main hazardous TP contributing to the developmental toxicity induced by chlorinated samples. TP387 could also be formed in real wastewater during chlorination in environmentally relevant conditions. This study provides a scientific basis for the further assessment of environmental risks of CQP after water chlorination and describes a method for identifying unknown hazardous TPs generated from pharmaceuticals during wastewater treatment.

Nontarget Discovery of Antimicrobial Transformation Products in Wastewater Based on Molecular Networks.

Antimicrobial transformation products (ATPs) in the environment have raised extensive concerns in recent years due to their potential health risks. However, only a few ATPs have been investigated, and most of the transformation pathways of antimicrobials have not been completely elucidated. In this study, we developed a nontarget screening strategy based on molecular networks to detect and identify ATPs in pharmaceutical wastewater. We identified 52 antimicrobials and 49 transformation products (TPs) with a confidence level of three or above. Thirty of the TPs had not been previously reported in the environment. We assessed whether TPs could be classified as persistent, mobile, and toxic (PMT) substances based on recent European criteria for industrial substances. Owing to poor experimental data, definitive PMT classifications could not be established for novel ATPs. PMT assessment based on structurally predictive physicochemical properties revealed that 47 TPs were potential PMT substances. These results provide evidence that novel ATPs should be the focus of future research.