Compound-specific isotope analysis (CSIA) is an established tool to track the in situ transformation of organic chemicals at contaminated sites. In this work, we evaluated the potential of multi-element CSIA to assess biodegradation of 2,3-dichloroaniline (2,3-DCA), which is a major industrial feedstock. Using controlled laboratory experiments, we determined, for the first time, negligible carbon (<0.5‰) and hydrogen (<10‰) isotope fractionation and a significant inverse nitrogen isotope fractionation (>10‰) during aerobic 2,3-DCA biodegradation by a mixed enrichment culture. The tentative identification of a glutamate conjugate of 2,3-DCA as a reaction intermediate indicates that the initial multistep enzymatic reaction may be rate-limiting. The formation of the glutamate adduct would increase the bond energy at the N atom, thus likely explaining the observed inverse N isotope fractionation. The corresponding nitrogen enrichment factor was +6.8 ± 0.6‰. This value was applied to investigate the in situ 2,3-DCA biodegradation at a contaminated site where the carbon and nitrogen isotope signatures from field samples suggested similar aerobic processes by native microorganisms. Under the assumption of the applicability of the Rayleigh model in a pilot wetland treating contaminated groundwater, the extent of biodegradation was estimated to be up to 80-90%. This study proposes multi-element CSIA as a novel application to study 2,3-DCA fate in groundwater and surface water and provides insights into biodegradation pathways.

This study enhanced our understanding of antibiotic mixtures\' occurrence, transformation, toxicity, and ecological risks. The role of acid-modified biochar (BC) in treating antibiotic residues was explored, shedding light on how BC influences the fate, mobility, and environmental impact of antibiotics and transformation products (TPs) in an activated sludge (AS) microbiome. A mixture of oxytetracycline and sulfamethoxazole was found to synergistically (or additively) inhibit cell growth of AS and disrupt the microbiome structure, species richness/diversity, and function. The formation of TPs with potentially higher toxicity and persistence than the original compounds was identified, explaining the microbiome disruption. Agricultural waste-derived BC was optimized for contaminant adsorption, leading to a reduction in toxicity when added to AS by sequestering TPs on its surface. This work highlighted adsorbents as a practical engineering strategy for mitigating liquid-phase contaminants\' toxicological consequences, proactively controlling the fate and effects of antibiotics and TPs.

Anaerobic digestion (AD) has long been studied as an effective environmental and economic strategy for treating matrices contaminated with recalcitrant pollutants. In the present work, we investigated the bioremediation potential of AD on organic waste contaminated with chlordecone (CLD), an organochlorine pesticide extensively used in the French West Indies and classified among the most persistent organic pollutants. Digestates from animal and plant origins were supplemented with CLD and incubated under methanogenic conditions for over 40 days. The redox potential and pH monitoring showed that methanogenic conditions were preserved during the entire incubation period despite the presence of CLD. In addition, the comparison of the total biogas generated from digestates with and without CLD demonstrated no adverse effects of CLD on biogas production. For the first time, a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method, followed by GC-MS and LC-HRMS analyses, was developed to quantify CLD and its main known transformation products (TPs) in AD experiments. A decrease in CLD concentrations was evident to a greater extent under thermophilic conditions (55 °C) compared to mesophilic conditions (37.5 °C) (CLD removal of 85 % and 42 %, respectively, after 40 days of incubation). CLD degradation was confirmed by the detection and quantification of several TPs: 10-monohydroCLD (A1), two dihydroCLDs different from 2,8-dihydroCLD (A3), pentachloroindene (B1), tetrachloroindenes (B2, B3/B4), tetra- and tri-chloroindenecarboxylic acids (C1/C2, C3/C4). Determining TPs concentrations using the QuEChERS method provided an overview of CLD fate in AD. Overall, these results reveal that AD processes can efficiently degrade CLD into several TPs from A, B, and C families while maintaining satisfactory biogas production. They pave the way to developing a scaled-up AD process capable of treating CLD-contaminated organic wastes produced by farming, thus stopping any further transfer of CLD.

Nonylphenols (NPs) are crucial fine chemicals widely employed in producing industrial and consumer surfactants that ultimately enter the environment through various pathways, leading to environmental pollution. NPs are suspected endocrine-disrupting chemicals that may accumulate in the body over time, resulting in unusual reproductive function. Due to limitations in analytical methods, NPs have typically been quantified as a whole in some studies. However, NPs are a mixture of multibranched structures, and different NP isomers exhibit distinct environmental behaviors and toxic effects. Therefore, it is critical to analyze environmental and human biological samples at the isomer-specific level to elucidate the contamination characteristics, human exposure load, and toxic effects of NPs. Accurately analyzing NP samples with various isomers, metabolites, and transformation products presents a significant challenge. This review summarizes recent advances in analytical research on NPs in technical products, environmental, and human biological samples, particularly emphasizing the synthesis and separation of standards and the transformation of NP homolog isomers in samples. Finally, the review highlights the research gaps and future research directions in this domain.

OBJECTIVE: To investigate the production and physical stability of coamorphous materials (CAM) of naringenin (NAR) and coformers-caffeine, theophylline or theobromine (CAF/THY/THE, respectively). We independently assessed the impact of moisture and temperature on the physical stability of CAMs, and transformation products after destabilization were examined.
METHODS: Neat grinding, liquid assisted grinding and water slurry were selected to prepare multi-component materials with NAR and CAF, THY or THE. The physical stability of CAMs was investigated at 65°C/<10%RH, 21°C/85% RH and 21°C/<10% RH. Differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) were employed to monitor for recrystallization during the stability studies. Glass forming ability of amorphous NAR was assessed to understand CAM formation and physical stability.
RESULTS: NAR:THY and NAR:THE CAMs showed physical stability for approximately nine months, under 21°C/<10% RH while NAR:CAF CAMs destabilized in 2.5 weeks. All CAMs recrystallized within a week at 65°C/<10%RH, and the physical stability at 21°C/85% RH was in the order of - NAR:THY > NAR:THE > NAR:CAF. NAR:THY produced 1:1 cocrystal under all storage conditions, while NAR:CAF destabilized to a 1:1 cocrystal at high RH but a physical mixture at high temperature. NAR:THE was found to recrystallize as a physical mixture in all conditions. NAR was found to be strong glass, with moderate kinetic fragility and good glass forming ability.
CONCLUSIONS: Five naringenin-based multi-component solids were generated in this study: 3 new CAMs, 1 new cocrystal, and 1 previously reported cocrystal. Destabilization of CAMs was found to be exposure specific and coformer dependent.

Due to their prevalence in urban contaminated water, the driving factors of organophosphate esters (OPEs) need to be well examined, and their related ecological impacts should include that of their transformation products (TPs). Additionally, a robust framework needs to be developed to integrate multiple variables related to ecological impacts for improving the ecological health assessment. Therefore, OPEs and TPs in urban stormwater and wastewater in Hong Kong were analyzed to fill these gaps. The results revealed that the total concentrations of OPEs in stormwater were positively correlated with the area of transportation land. Individual TP concentrations and the mass ratios of individual TPs/OPEs were somewhat higher in sewage effluents than that in stormwater. OPEs generally showed relatively higher risk quotients than TPs; however, the total risk quotients increased by approximately 38% when TPs were factored in. Moreover, the molecular docking results suggested that the investigated TPs might cause similar endocrine disruption in marine organisms as their parent OPEs. This study employed the Toxicological-Priority-Index scheme to successfully integrate the ecological risks and endocrine-disrupting effects to refine the ecological health assessment of the exposure to OPEs and their TPs, which can better inform the authority on the prioritization for regulating these contaminants of emerging concern in urban built environments.

Halogenated estrogens are formed during chlorine-based wastewater disinfection and have been detected in wastewater treatment plant effluent; however, very little is known about their susceptibility to biodegradation in natural waters. To better understand the biodegradation of free and halogenated estrogens in a large river under environmentally relevant conditions, we measured estrogen kinetics in aerobic microcosms containing water and sediment from the Willamette River (OR, USA) at two concentrations (50 and 1250 ng L-1). Control microcosms were used to characterize losses due to sorption and other abiotic processes, and microbial dynamics were monitored using 16S rRNA gene sequencing and ATP. We found that estrogen biodegradation occurred on timescales of hours to days and that in river water spiked at 50 ng L-1 half-lives were significantly shorter for 17β-estradiol (t1/2,bio = 42 ± 3 h) compared to its monobromo (t1/2,bio = 49 ± 5 h), dibromo (t1/2,bio = 88 ± 12 h), and dichloro (t1/2,bio = 98 ± 16 h) forms. Biodegradation was also faster in microcosms with high initial estrogen concentrations as well as those containing sediment. Free and halogenated estrone were important transformation products in both abiotic and biotic microcosms. Taken together, our findings suggest that biodegradation is a key process for removing free estrogens from surface waters but likely plays a much smaller role for the more highly photolabile halogenated forms.

Organochlorine pesticides show biological toxicity and their degradation typically takes many years. Previous studies of agrochemical-contaminated areas have mainly focused on limited target compounds, and emerging pollutants in soil have been overlooked. In this study, we collected soil samples from an abandoned agrochemical-contaminated area. Target analysis and non-target suspect screening by gas chromatography coupled with time-of-flight mass spectrometry were combined for qualitative and quantitative analysis of organochlorine pollutants. Target analysis showed that dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethylene (DDE), and dichlorodiphenyldichloroethane (DDD) were the main pollutants. With concentrations between 3.96 × 106 and 1.38 × 107 ng/g, these compounds posed significant health risks at the contaminated site. Non-target suspect screening identified 126 organochlorine compounds, most of which were chlorinated hydrocarbons and 90% of the compounds contained a benzene ring structure. The possible transformation pathways of DDT were inferred from proven pathways and the compounds identified by non-target suspect screening that had similar structures to DDT. This study will be useful for studies of the degradation mechanism of DDT. Semi-quantitative and hierarchical cluster analysis of compounds in soil showed that the distribution of contaminants in soil was influenced by the types of pollution sources and distance to them. Twenty-two contaminants were found in the soil at relatively high concentrations. The toxicities of 17 of these compounds are currently not known. These results improve our understanding of the environmental behavior of organochlorine contaminants in soil and are useful for further risk assessments of agrochemical-contaminated areas.

The efficiency of an advanced oxidation process (AOP) using direct and indirect ozonation for the removal of pharmaceutical residues from deliberately spiked deionized water was examined. Both direct and indirect ozonation demonstrated 34% to 100% removal of the parent compounds. However, based on the products\' chemical structure and toxicity, we suggest that despite using accepted and affordable ozone and radical concentrations, the six parent compounds were not fully degraded, but merely transformed into 25 new intermediate products. The transformation products (TPs) differed slightly in structure but were mostly similar to their parent compounds in their persistence, stability and toxicity; a few of the TPs were found to be even more toxic than their parent compounds. Therefore, an additional treatment is required to improve and upgrade the traditional AOP toward degradation and removal of both parent compounds and their TPs for safer release into the environment.

Broflanilide, as a novel meta-diamide insecticide, presents high bioactivity against agricultural pests. However, there was limited report regarding the photolysis fate of broflanilide. In this study, the photodegradation kinetics and influence factors of broflanilide, including different solvents, pH, iron, S2O82- and SO32- were investigated under UV condition, and the reaction mechanism and transformation pathway were explored. The reaction rates (k) showed solvent-specificity in ultrapure water (0.015 min-1), ethyl acetate (0.051 min-1), methanol (0.084 min-1) and acetonitrile (0.193 min-1), correspondingly. The photolysis of broflanilide was slowest in the acid condition (pH = 4.0) compared with that in the neutral (pH = 7.0) and alkaline (pH = 9.0) conditions. The iron (Fe2+ and Fe3+) presented significant inhibition on the photodegradation due to the light shielding effect. Additionally, the UV/peroxydisulfate (S2O82-) and UV/sulfite (SO32-) technologies could effectively accelerate the photodegradation of broflanilide, which has the potential for rapid treatment of pesticides in the aqueous environment. Six transformation products (TPs) were detected in water, peroxydisulfate and sulfite solutions, and the possible transformation pathways, including dehalogenation, cyclization, N-dealkylation, oxidation, reduction and hydrolysis, were proposed. Importantly, the reaction mechanism was explained through the analysis of molecular electrostatic potential and molecular orbitals. The predicted toxicity of the TPs indicated that several highly toxic TPs need to pay more attention in future risk assessments. This study provides a new perspective for evaluating the ecological fate and risks of pesticides.