Persistent Organic Pollutants Research Articles

The catalytic hydro-dechlorination of 2, 4, 4’ trichlorobiphenyl at mild temperatures and atmospheric pressure

ABSTRACT Polychlorinated biphenyls (PCBs), including all 209 congeners, are designated as persistent organic pollutants (POPs) due to their high toxicity and bioaccumulation in human bodies and the ecosystem. The need for PCB remediation still remains long after their production ban. In this study, a catalytic hydro-dechlorination (HDC) method was employed to dechlorinate 2,4,4’-trichlorobiphenyl (PCB 28), a congener found ubiquitously in multiple environmental media. The HDC of PCB 28 was experimentally studied at mild temperatures viz. ~20, 50, and ~ 77°C and atmospheric pressure. Et3N (triethylamine) was added as a co-catalyst. The dechlorination rates increased with temperature as well as Et3N dosage, and the HDC pathway was hypothesized based on the product and intermediates observed. The less chlorinated intermediates suggested that the position of the chlorine strongly impacted HDC rates, and the preference of HDC at para positions can be orders of magnitudes higher than the ortho. The activation energy, was estimated in the range of 12.4-13.9 kJ/mole, indicating a diffusion-controlled HDC system. Implication Statement The remediation need for polychlorinated biphenyls (PCBs) still remains long after their production ban around the world. The development of low cost methods is highly desirable, especially for developing countries, in response to the Stockholm Convention. In this study, the dechorination of a ubiquitously present PCB congener was studied using a catalytic hydro-dechlorination (HDC) method in low temperatures up to ~ 77°C and was able to achieve near 100% dechlorination in six hours. Results indicated that the HDC process can be performed under mild temperatures and atmospheric conditions and can be a potential solution to real world PCB contamination issues.

Environmental transformation and hazards of decachlorobiphenyl on suspended particles under sunlight irradiation.

Decachlorobiphenyl (PCB-209) can be widely detected in suspended particles and sediments due to its large hydrophobicity, and some of its transformation products may potentially threaten organisms through the food chain. Here we investigate the photochemical transformation of PCB-209 on suspended particles from the Yellow River. It was found that the suspended particles had an obvious shielding effect to largely inhibit the photodegradation of PCB-209. Meanwhile, the presence of inorganic ions (e.g. Mg2+ and NO3-) and organic matters (e.g. humic acid, HA) in the Yellow River water inhibited the reaction. The main transformation products of PCB-209 were lower-chlorinated and hydroxylated polychlorinated biphenyls (OH-PCBs), and small amounts of pentachlorophenol (PCP) and polychlorinated dibenzofurans (PCDFs) were also observed. The mechanisms of PCP formation by double •OH attacking carbon bridge and PCDFs formation by elimination reaction of ionic state OH-PCBs were proposed using theoretical calculations, which provided some new insights into the inter-transformations between persistent organic pollutants. In combination with VEGA and EPI Suite software, some intermediates such as PCDFs were more toxic to organisms than PCB-209. This study deepens the understanding of the transformation behavior of PCB-209 on suspended particles under sunlight.

Revealing the Enhanced Visible-light-driven Photocatalytic Activity of In2S3/CeO2 Heterojunction: Bandgap Structure Analysis and Active Radicals Determination

Background: The widespread presence of persistent organic pollutants, such as dyes in effluent from printing and textile industries, poses a significant threat to aquatic life and human health. Photocatalytic degradation is widely recognized as a promising technology to address this pollution crisis. The efficiency of photocatalysis is intricately tied to both the active radicals and the band structure of the catalyst. These factors play a crucial role in governing the photodegradation of dye molecules. Methods: In2S3/CeO2 heterojunctions were synthesized using an in-situ precipitation method and subsequently analyzed through SEM, XRD, and XPS techniques. Notably, the bandgap structure of the heterojunctions was examined through UV-Vis DRS. The photocatalytic performance of the synthesized samples was assessed by studying the degradation of methyl orange. To further validate the photocatalytic process, EPR spectroscopy was employed to confirm the presence of radicals generated within the heterojunction. Results: The heterojunction displayed a characteristic type-II structure, enhancing light absorption and facilitating the separation of photoinduced carriers. Among the In2S3/CeO2 composites, the one with a 15 wt% CeO2 content exhibited the highest photocatalytic activity, achieving an 88% degradation of methyl orange after 90 min of exposure to visible light irradiation. Additionally, •O2 − is identified as the primary active species responsible for degradation. Conclusion: UV-Vis DRS illustrated the improved transfer and separation of photogenerated electrons attributed to the optimized band structure of the heterojunction. EPR spectroscopy yielded valuable information on active radicals, thereby proposing the photocatalytic degradation mechanism.

Accommodating detection limits of multiple exposures in environmental mixture analyses: an overview of statistical approaches

BackgroundIdentifying the impact of environmental mixtures on human health is an important topic. However, such studies face challenges when exposure measurements lie below limit of detection (LOD). While various approaches for accommodating a single exposure subject to LOD have been used, their impact on mixture analysis has not been thoroughly investigated. Our study aims to understand the impact of five popular LOD accommodation approaches on mixture analysis results with multiple exposures subject to LOD, including omitting subjects with any exposures below LOD (complete case analysis); single imputations by LOD/2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sqrt{2}$$\\end{document}, and by estimates from a censored accelerated failure time (AFT) model; and multiple imputation (MI) with or without truncation based on LOD.MethodsIn extensive simulation studies with high-dimensional and highly correlated exposures and a continuous health outcome, we examined the performance of each LOD approach on three mixture analysis methods: elastic net regression, weighted quantile sum regression (WQS) and Bayesian kernel machine regression (BKMR). We further analyzed data from the National Health and Nutrition Examination Survey (NHANES) on how persistent organic pollutants (POPs) influenced leukocyte telomere length (LTL).ResultsComplete case analysis was inefficient and could result in severe bias for some mixture methods. Imputation by LOD/2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sqrt{2}$$\\end{document} showed unstable performance across mixture methods. Conventional MI was associated with consistent mild biases, which can be reduced by using a truncated distribution for imputation. Estimating censored values by AFT models had a minimal impact on the results. In the NHANES analysis, imputation by LOD/2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sqrt{2}$$\\end{document}, truncated MI and censored AFT models performed similarly, with a positive overall effect of POPs on LTL while PCB126, PCB169 and furan 2,3,4,7,8-pncdf being the most important exposures.ConclusionsOur study favored using truncated MI and censored AFT models to accommodate values below LOD for the stability of downstream mixture analysis.

Epoxiconazole degradation in water samples: a comparative study of Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis processes.

Epoxiconazole (EPO) is classified as a persistent organic pollutant due to its ability to persist in the environment for prolonged periods. Its degradation is pivotal in mitigating its environmental impact. This investigation focuses on assessing the degradation of EPO using various methodologies, namely Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis, conducted in both Milli-Q water and groundwater. These experiments encompassed evaluations at both the standard pH typically used in photo-Fenton reactions and the natural pH levels inherent to the respective aqueous environments. Additionally, EPO degradation products were analyzed after a 60-min reaction. Notably, in systems utilizing groundwater, the inclusion of additional iron was unnecessary, as the naturally occurring iron content in the groundwater facilitated the intended processes. Specifically, in Milli-Q water, solar photo-Fenton demonstrated an EPO degradation efficiency of 97%. Furthermore, the substitution of Milli-Q water with groundwater in Fenton-like processes did not significantly affect the efficacy of EPO degradation. These findings underscore the potential of solar photo-Fenton as an economically viable and environmentally sustainable strategy for EPO degradation.

Advances in the Removal of Organic Pollutants from Water by Photocatalytic Activation of Persulfate: Photocatalyst Modification Strategy and Reaction Mechanism.

Environmental pollution caused by persistent organic pollutants has imposed big threats to the health of human and ecological systems. The development of efficient methods to effectively degrade and remove these persistent organic pollutants is therefore of paramount importance. Photocatalytic persulfate-based advanced oxidation technologies (PS-AOTs), which depend on the highly reactive SO4·- radicals generated by the activation of PS to degrade persistent organic pollutants, have shown great promise. This work discusses the application and modification strategies of common photocatalysts in photocatalytic PS-AOTs, and compares the degradation performance of different catalysts for pollutants. Furthermore, essential elements impacting photocatalytic PS-AOTs are discussed, including the water matrix, reaction process mechanism, pollutant degradation pathway, singlet oxygen generation, and potential PS hazards. Finally, the existing issues and future challenges of photocatalytic PS-AOTs are summarized and prospected to encourage their practical application. In particular, by providing new insights into the PS-AOTs, this review sheds light on the opportunities and challenges for the development of photocatalysts with advanced features for the PS-AOTs, which will be of great interests to promote better fundamental understanding of the PS-AOTs and their practical applications.

Optimization of excitation and emission wavelengths for the UHPLC fluorescence detector for priority polycyclic aromatic hydrocarbons (PAHs)

AbstractPolycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) that are widely distributed in the environment and cause significant environmental damage. Furthermore, they endanger human health by polluting food from the natural environment and food processing. Therefore, it is necessary to accurately detect PAHs in various sample matrices, which requires precise, practical, and rapid detection methods. The purpose of this research is to develop a high sensitivity analysis method by analyzing the optimum excitation and emission wavelengths of EPA's 15 priority polyaromatic hydrocarbons in the UHPLC fluorescence detector (Acenaphthene, Anthracene, Benzo[a]anthracene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[ghi]perylene, Benzo[a]pyrene, Chrysene, Dibenzo[a,h]anthracene, Fluoranthene, Fluorene, Indeno[1,2,3-cd]pyrene, Naphthalene, Phenanthrene, and Pyrene). An average of 17–25 analyses were performed for each polyaromatic hydrocarbon, and optimized excitation and emission wavelengths were obtained. LOD levels between 2 and 90 ppt were obtained with the method created in this direction. It is worth mentioning that the limits achieved for some PAH parameters are lower than those reported in the literature after pre-concentration steps.

A Review About the Occurrence and Effectiveness of Conventional and Advanced Treatment Technologies of Persistent Organic Pollutants in Surface Water

A Review About the Occurrence and Effectiveness of Conventional and Advanced Treatment Technologies of Persistent Organic Pollutants in Surface Water

Boosting highly effective photocatalytic activity through g-C3N4 coupled Al doped zinc ferrite nanoparticles: Maximizing dye degradation kinetics

Photocatalysts have gotten much attention because of the growing need to protect the environment, and metal-doped zinc ferrite heterojunctions are an exciting system to look into. The current study involves synthesizing aluminum-doped zinc ferrite (Al@ZF) nanoparticles (NPs) and nanocomposites of Al@ZF with S@g-C3N4 via a hydrothermal method and then evaluating their photocatalytic activity. Al@ZF NPs were prepared by varying the percentage of aluminum (0.5, 1, 3, 5, 7 and 9 wt %). Photocatalytic measurements were carried out employing methylene blue (MB) as the model dye. The Al@ZF NPs with 1 % concentration showed the best photocatalytic capability among all of them. Correspondingly, the S@g-C3N4/Al@ZF nanocomposites (NCs) were made by varying the percentage of S@g-C3N4 (10, 30, 50 and 70 wt %) with the 1 % Al@ZF NPs. Then, photocatalytic working measurements of the S@g-C3N4/Al@ZF NCs proved that the 50 % S@g-C3N4/Al@ZF NC showed the highest photocatalytic activity and completely degraded MB within 150 min of light irradiation. To verify the morphological structure of these artificial nanoparticles and nanocomposites, several analytical techniques including XRD, SEM, TEM, BET, FTIR, and XPS were used. The produced photocatalyst's quick degradation kinetics and simplicity in separation may provide new opportunities for the oxidation of persistent organic pollutants. To our best knowledge, no prior report has been made on the synthesized nanocomposite. The proposed modification of Al@ZF using 50 % S@g-C3N4 is effective, less expensive, non-toxic, and highly efficient for scalable wastewater treatment applications.

Highly efficient degradation and detoxification of antibiotics over C–Dots/siderite heteroaggregates in photo-Fenton systems: The crucial role of C–Dots

The substantial presence of antibiotics in aquatic environments remains as a critical environmental issue that needs to be urgently addressed. In this study, mimetics of C–Dots/siderite heteroaggregates (CSI) were studied in a visible-light-responsive Fenton system as a platform for the degradation of antibiotics in contaminated water. By virtue of the excellent electron transfer of C–Dots, the sustained conversion cycles of Fe(II) → Fe(III) → Fe(II) in CSI were greatly accelerated, and meanwhile the H2O2 utilization was enhanced. The optimized CSI–3 nanocomposite displayed a prominent degradation efficiency towards a series of tetracycline analogs at ppb levels. Density functional theory (DFT) calculations indicated the excellent photo-Fenton catalytic performance of CSI originated from the increased d-band center and electron density, which considerably improves the utilization of H2O2. Both experimental and theoretical studies revealed that the correlated toxicity of degradation intermediates was significantly decreased. Additionally, a continuous flow device integrating the CSI photo-Fenton system maintained a high degradation efficiency after long-term treatment of simulated chlortetracycline wastewater. The presented work thereby confirms a spontaneous remediation process for the decontamination and detoxification of persistent organic pollutants under the action of heteroaggregates formed by engineered nanoparticles and natural minerals.

Multiple-component covalent organic frameworks for simultaneous extraction and determination of multitarget pollutants in sea foods

Persistent organic pollutants (POPs), such as perfluoroalkyl and polyfluoroalkyl substances (PFASs), polychlorinated biphenyls (PCBs), and bisphenols (BPs), have been raising global concerns due to their toxic effects on environment and human health. The monitoring of residues of POPs in seafood is crucial for assessing the accumulation of these contaminants in the study area and mitigating potential risks to human health. However, the diversity and complexity of POPs in seafood present significant challenges for their simultaneous detection. Here, a novel multi-component fluoro-functionalized covalent organic framework (OH-F-COF) was designed as SPE adsorbent for simultaneous extraction POPs. On this basis, the recognition and adsorption mechanisms were investigated by molecular simulation. Due to multiple interactions and large specific surface area, OH-F-COF displayed satisfactory coextraction performance for PFASs, PCBs, and BPs. Under optimized conditions, the OH-F-COF sorbent was employed in a strategy of simultaneous extraction and stepwise elution (SESE), in combination with HPLC−MS/MS and GC−MS method, to effectively determined POPs in seafood collected from coastal areas of China. The method obtained low detection limits for BPs (0.0037 −0.0089 ng/g), PFASs (0.0038 −0.0207 ng/g), and PCBs (0.2308 −0.2499 ng/g), respectively. This approach provided new research ideas for analyzing and controlling multitarget POPs in seafood. Environmental implicationsPersistent organic pollutants (POPs), such as perfluoroalkyl and polyfluoroalkyl substances (PFASs), polychlorinated biphenyls (PCBs), and bisphenols (BPs), have caused serious hazards to human health and ecosystems. Hence, there is a need to develop a quantitative method that can rapidly detect POPs in environmental and food samples. Herein, a novel multi-component fluorine-functionalized covalent organic skeletons (OH-F-COF) were prepared at room temperature, and served as adsorbent for POPs. The SESE-SPE strategy combined with chromatographic techniques was used to achieve a rapid detection of POPs in sea foods from the coastal provinces of China. This method provides a valuable tool for analyzing POPs in environmental and food samples.

Interactions of Brominated Flame Retardants with Membrane Models of Dehalogenating Bacteria: Langmuir Monolayer and Grazing Incidence X-ray Diffraction Studies.

Brominated flame retardants (BFRs) are small organic molecules containing several bromine substituents added to plastics to limit their flammability. BFRs can constitute up to 30% of the weight of some plastics, which is why they are produced in large quantities. Along with plastic waste and microplastic particles, BFRs end up in the soil and can easily leach causing contamination. As polyhalogenated molecules, multiple BFRs were classified as persistent organic pollutants (POPs), meaning that their biodegradation in the soils is especially challenging. However, some anaerobic bacteria as Dehaloccocoides can dehalogenate BFRs, which is important in the bioremediation of contaminated soils. BFRs are hydrophobic, can accumulate in plasma membranes, and disturb their function. On the other hand, limited membrane accumulation is necessary for BFR dehalogenation. To study the BFR-membrane interaction, we created membrane models of soil dehalogenating bacteria and tested their interactions with seven legacy and novel BFRs most common in soils. Phospholipid Langmuir monolayers with appropriate composition were used as membrane models. These membranes were doped in the selected BFRs, and the incorporation of BFR molecules into the phospholipid matrix and also the effects of BFR presence on membrane physical properties and morphology were studied. It turned out that the seven BFRs differed significantly in their membrane affinity. For some, the incorporation was very limited, and others incorporated effectively and could affect membrane properties, while one of the tested molecules induced the formation of bilayer domains in the membranes. Thus, Langmuir monolayers can be effectively used for pretesting BFR membrane activity.

Effects of PFAS on human liver transporters: implications for health outcomes.

Per- and polyfluoroalkyl substances (PFAS) have become internationally recognized over the past three decades as persistent organic pollutants used in the production of various consumer and industrial goods. Research efforts continue to gauge the risk that historically used, and newly produced, PFAS may cause to human health. Numerous studies report toxic effects of PFAS on the human liver as well as increased serum cholesterol levels in adults. A major concern with PFAS, also dubbed "forever chemicals", is that they accumulate in liver and kidney and persist in serum. The mechanisms responsible for their disposition and excretion in humans are poorly understood. A better understanding of the interaction of PFAS with liver transporters, as it pertains to the disposition of PFAS and other xenobiotics, could provide mechanistic insight into human health effects and guide efforts toward risk assessment of compounds in development. This review summarizes the current state of the literature on the emerging relationships (e.g., substrates, inhibitors, modulators of gene expression) between PFAS and specific hepatic transporters. The adaptive and toxicological responses of hepatocytes to PFAS that reveal linkages to pathologies and epidemiological findings are highlighted. The evidence suggests that our understanding of the molecular landscape of PFAS must improve to determine their impact on the expression and function of hepatocyte transporters that play a key role in PFAS or other xenobiotic disposition. From here, we can assess what role these changes may have in documented human health outcomes.

Accumulation of typical persistent organic pollutants and heavy metals in bioretention facilities: Distribution, risk assessment, and microbial community impact

Bioretention facilities have proven highly effective in removing pollutants from runoff. However, there is a concerning paucity of research on the contamination characteristics and associated risks posed by refractory pollutants in these facilities following long-term operation. This research focuses on the distribution, sources, microbial community impact, and human health risks of pollutants in eight bioretention facilities that have been operational for 5–11 years. The results showed that the distribution of Cu, Zn, and Cd was closely related to anti-seepage measures. PAHs, PCBs, and OCPs primarily accumulated in the surface, with concentrations ranging from 7.42 to 20.34 mg/kg, 31.8–77.3 μg/kg, and 60.5–163.6 μg/kg, respectively. Their concentrations inversely correlate with the depth of the media. Although the majority of contaminants remained below their respective risk thresholds, their concentrations typically exceeded those of background soil values, indicating an enrichment phenomenon. Source analysis revealed that PAHs primarily originate from oil combustion, PCBs were linked to their related industrial products, DDTs had their main sources in technical DDx and residues from the use of dicofol, while HCHs were traced back to historical residues from agricultural activities. Microbial α-diversity (Chao 1 and Shannon) decreased by 8.3–23.4% and 0.8–4.4%, respectively, in different facilities after long-term operation. The most dominant microbial phylum in the facilities was Proteobacteria (all relative abundances >48%). The total relative abundance of dominant genera was 6.7–34.3% higher than the control site, and Pseudomonas, a typical POPs-heavy metal degrading bacterium, had the highest relative abundance (>1.2%). Cu, Zn, and Cd present no non-carcinogenic risks and have low potential ecological risks. However, the lifetime cancer risk for PAHs is 10−6 ∼10−4 in most facilities and is of concern. The cancer risk for PCBs is acceptable, while OCPs pose a low cancer risk only for children.

Assessing the effect of COVID 19 lockdowns on the composition of organic compounds and potential source of PM2.5 in Hanoi, Vietnam.

The ambient air quality during COVID-19 lockdowns has been improved in many cities in the world. This study is to assess the changes in persistent organic pollutants in PM2.5 during the COVID-19 lockdown in Hanoi. Individual organic species in PM2.5 ((e.g., polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), and organochlorine pesticides (OCPs)) were measured in an urban residential area in Hanoi from before the March 10th to April 22nd, 2020, including before the partial lockdown (BL) and the partial lockdown (PL) phases. During the PL phase, the concentration of Σ14PAHs and Σ28PCBs was reduced by 38 and 52% compared with the BL period, respectively. The diagnostic ratio method implied that the sources of PAHs within the PL phase had a less effect on traffic and industrial activities than in the BL phase. The characteristic ratio method indicated that PCBs were mixed by commercial product and combustion process in both the BL and the PL periods, however, the source of PCBs in the BL phase was influenced by municipal waste incineration more than those in the PL phase. The decreasing concentration of Σ20OCPs during the partial lockdown was attributed to the restriction of human activities during the quarantine period. The results suggested that the source of OCPs was probably derived from the usage of pesticides in current and, historical degradation or the transportation of pesticides from the soil to the atmosphere.

Simultaneous Cu(II)-EDTA decomplexation and Cu(II) recovery using integrated contact-electro-catalysis and capacitive deionization from electroplating wastewater

The complex of heavy metals and organic acids leads to high difficulty in heavy metals separation by traditional technologies. Meanwhile, alkaline precipitation commonly used in industry causes the great consumption of resources and extra pollution. Herein, the effective decomplexation of Cu(Ⅱ)-EDTA and synchronous recycling of Cu2+ were realized by contact-electro-catalysis (CEC) coupled with capacitive deionization (CDI) innovatively. In particular, fluorinated ethylene propylene (FEP) as dielectric powders could generate reactive oxygen species under ultrasonic stimulation, realizing continuous deaminization and decarboxylation of Cu(Ⅱ)-EDTA and accelerating the totally breakage of Cu-O and Cu-N bonds. Additionally, the degradation pathway and intermediates evolution of Cu(Ⅱ)-EDTA were investigated using various characterization methods. It was confirmed that decarboxylation predominantly governed the degradation process of Cu(Ⅱ)-EDTA in CEC. During the course of treatment, the degradation ratio of Cu(Ⅱ)-EDTA reached 86.4 % within 150 min. Impressively, this strategy had satisfactory applicability to other metal combinations and excellent cycle stability. Subsequently, the released Cu ions were captured by CuSe cathode electrode through CDI. This research elucidated the degradation mechanism of persistent organic pollutant during CEC, and provided a novel approach for efficiently treating industrial wastewater containing metal complexes and advancing the exploitation and utilization of new technologies for metal recovery.

Thyroid Cancer and Endocrine Disruptive Chemicals: A Case-Control Study on Persistent Organic Pollutants (POPs)

Thyroid Cancer and Endocrine Disruptive Chemicals: A Case-Control Study on Persistent Organic Pollutants (POPs)

Gradual effects of gradient concentrations of perfluorooctane sulfonate on the antioxidant ability and gut microbiota of red claw crayfish (Cherax quadricarinatus)

Perfluorooctane sulfonate (PFOS) is a typical persistent organic pollutant that is characterized by environmental persistence, bioaccumulation, and toxicity. In this study, we investigated the gut microbial response of the red claw crayfish Cherax quadricarinatus after 28 days of exposure to 0 ng/L, 1 ng/L, 10 μg/L, or 10 mg/L of PFOS as a stressor. We measured oxidative stress-related enzyme activities and expression of molecules related to detoxification mechanisms to evaluate the toxic effects of PFOS. We found that PFOS disturbed microbial homeostasis in the gut of C. quadricarinatus, resulting in increased abundance of the pathogen Shewanella and decreased abundance of the beneficial bacterium Lactobacillus. The latter especially disturbed amino acid transport and carbohydrate transport. We also found that the activities of glutathione S-transferase and glutathione peroxidase were positively correlated with the expression levels of cytochrome P450 genes (GST1-1, GSTP, GSTK1, HPGDS, UGT5), which are products of PFOS-induced oxidative stress and play an antioxidant role in the body. The results of this study provided valuable ecotoxicological data to better understand the biological fate and effects of PFOS in C. quadricarinatus.

Identification of UDP-glucuronosyltransferase (UGT) isoforms involved in the metabolism of Chlorophenols (CPs)

Chlorophenols (CPs) are a group of pollutants that pose a great threat to the environment, they are widely used in industrial and agricultural wastes, pesticides, herbicides, textiles, pharmaceuticals and plastics. Among CPs, pentachlorophenol was listed as one of the persistent organic pollutants (POPs) by the Stockholm convention. This study aims to identify the UDP-glucosyltransferase (UGT) isoforms involved in the metabolic elimination of CPs. CPs’ mono-glucuronide was detected in the human liver microsomes (HLMs) incubation mixture with co-factor uridine-diphosphate glucuronic acid (UDPGA). HLMs-catalyzed glucuronidation metabolism reaction equations followed Michaelis-Menten or substrate inhibition type. Recombinant enzymes and chemical reagents inhibition experiments were utilized to phenotype the main UGT isoforms involved in the glucuronidation of CPs. UGT1A6 might be the major enzyme in the glucuronidation of mono-chlorophenol isomer. UGT1A1, UGT1A6, UGT1A9, UGT2B4 and UGT2B7 were the most important five UGT isoforms for metabolizing the di-chlorophenol and tri-chlorophenol isomers. UGT1A1 and UGT1A3 were the most important UGT isoforms in the catalysis of tetra-chlorophenol and pentachlorophenol isomers. Species differences were investigated using rat liver microsomes (RLMs), pig liver microsomes (PLMs), dog liver microsomes (DLMs), and monkey liver microsomes (MyLMs). All these results were helpful for elucidating the metabolic elimination and toxicity of CPs.

Urchin-like Ni-Fe-Mo sulfide: An effective electrochemical calcium sulfite activator for tetracycline degradation

Sulfite is deemed as a promising precursor to produce highly reactive species for contaminants remediation. Herein, the urchin-like Ni-Fe-Mo sulfide (NiFeMoSx) was anchored in-situ on nickel foam as a cathode to activate CaSO3 for efficient degradation of tetracycline (TC) under natural condition. The degradation efficiency reached 92.7% within 60 min, which was about 1.81 times higher than that of the electro-Fenton process based on NiFeMoSx. The beneficial performance came from the synergistic activation of CaSO3 by simultaneous rapid redox cycles of Fe(II)/Fe(III) and Ni(II)/Ni(III) on the NiFeMoSx cathode. Specifically, the primary intermediates Fe(II)-HSO3- and Ni(II)-SO32- triggered a series of radical chain reactions, accompanied the reduction of Ni(III)/Fe(III) by electrochemistry and electron donor of Mo(IV) and S2- on the surface of the catalyst. The regeneration of the Fe(II)/Ni(II) was quickly realized and subsequently triggered the chain reactions, which would accelerate the formation rate of reactive species, such as SO4∙−, ·OH, O2∙− and 1O2, of which 1O2 and O2•- played important roles on degradation TC. This work provides a promising application for the efficient removal of persistent organic pollutants by metal sulfide activated sulfite.