STAT3 Pathways Contribute to ß-HCH Interference with Anticancer Tyrosine Kinase Inhibitors.

Organochlorine pesticides (OCPs) are a class of environmentally persistent and bioaccumulative pollutants. Among these, ß-hexachlorocyclohexane (ß-HCH) is a byproduct of lindane synthesis, one of the most worldwide widespread pesticides. ß-HCH cellular mechanisms inducing chemical carcinogenesis correspond to many of those inducing chemoresistance, in particular, by the activation of signal transducer and activator of transcription 3 (STAT3) signaling pathways. For this purpose, four cell lines, representative of breast, lung, prostate, and hepatocellular cancers, were treated with ß-HCH, specific tyrosine kinase inhibitors (TKIs), and a STAT3 inhibitor. All cell samples were analyzed by a viability assay, immunoblotting analysis, a wound-healing assay, and a colony formation assay. The results show that ß-HCH reduces the efficacy of TKIs. The STAT3 protein, in this context, plays a central role. In fact, by inhibiting its activity, the efficacy of the anticancer drug is restored. Furthermore, this manuscript aimed to draw the attention of the scientific and socio-healthcare community to the issue of prolonged exposure to contaminants and their impact on drug efficacy.

Wetland technology for the treatment of HCH-contaminated water - Case study at Hajek site.

Hexachlorocyclohexanes (HCH) isomers and their transformation products, such as chlorobenzenes (ClB), generate severe and persistent environmental problems at many sites worldwide. The Wetland technology employing oxidation-reduction, biosorption, biodegradation and phytoremediation methods can sufficiently treat HCH-contaminated water. The treatment process is inherently natural and requires no supplementary chemicals or energy. The prototype with a capacity of 3 L/s was installed at Hajek quarry spoil heap (CZ), to optimize the technology on a full scale. The system is fed by drainage water with an average concentration of HCH 129 µg/L, ClB 640 µg/L and chlorophenols (ClPh) of 16 µg/L. The system was tested in two years of operation, regularly monitored for HCH, ClB and ClPh, and maintained to improve its efficiency. The assessment was not only for environmental effects but also for socio and economic indicators. During the operation, the removal efficiency of HCH ranged from 53.5 % to 96.9 % (83.9 % on average) depending on the flow rate. Removal efficiency was not uniform for individual HCH isomers but exhibited the trend: α = Î³ = Î´ > ß = Îµ. The improved water quality was reflected in a biodiversity increase expressed by a number of phytobenthos (diatoms) species, a common biomarker of aquatic environment quality. The Wetland outranked the conventional WWTP in 10 out of the 15 general categories, and it is the most relevant scenario from the socio, environmental, and economic aspects.

Organochlorine pesticides and risk of papillary thyroid cancer in U.S. military personnel: a nested case-control study.

BACKGROUND: The effects of organochlorine pesticide (OCP) exposure on the development of human papillary thyroid cancer (PTC) are not well understood. A nested case-control study was conducted with data from the U.S. Department of Defense Serum Repository (DoDSR) cohort between 2000 and 2013 to assess associations of individual OCPs serum concentrations with PTC risk. METHODS: This study included 742 histologically confirmed PTC cases (341 females, 401 males) and 742 individually-matched controls with pre-diagnostic serum samples selected from the DoDSR. Associations between categories of lipid-corrected serum concentrations of seven OCPs and PTC risk were evaluated for classical PTC and follicular PTC using conditional logistic regression, adjusted for body mass index category and military branch to compute odds ratios (OR) and 95% confidence intervals (CIs). Effect modification by sex, birth cohort, and race was examined. RESULTS: There was no evidence of associations between most of the OCPs and PTC, overall or stratified by histological subtype. Overall, there was no evidence of an association between hexachlorobenzene (HCB) and PTC, but stratified by histological subtype HCB was associated with significantly increased risk of classical PTC (third tertile above the limit of detection (LOD) vs.

Persistent ß-Hexachlorocyclohexane Exposure Impacts Cellular Metabolism with a Specific Signature in Normal Human Melanocytes.

BACKGROUND: Cutaneous melanoma arises from skin melanocytes and has a high risk of metastatic spread. Despite better prevention, earlier detection, and the development of innovative therapies, melanoma incidence and mortality increase annually. Major clinical risk factors for melanoma include fair skin, an increased number of nevi, the presence of dysplastic nevi, and a family history of melanoma. However, several external inducers seem to be associated with melanoma susceptibility such as environmental exposure, primarily unprotected sun experience, alcohol consumption, and heavy metals. In recent years, epidemiological studies have highlighted a potential risk of ß-hexachlorocyclohexane (ß-HCH), the most studied organochlorine pesticide, causing cancer induction including melanoma. METHODS: We evaluated in vitro the impact of this pollutant on epidermal and dermal cells, attempting to describe mechanisms that could render cutaneous cells more prone to oncogenic transformation. RESULTS: We demonstrated that ß-HCH impacts melanocyte biology with a highly cell-type specific signature that involves perturbation of AKT/mTOR and Wnt/ß-catenin signaling, and AMPK activation, resulting in lowering energy reserve, cell proliferation, and pigment production. CONCLUSIONS: In conclusion, long-term exposure to persistent organic pollutants damages melanocyte metabolism in its function of melanin production with a consequent reduction of melanogenesis indicating a potential augmented skin cancer risk.

Tracking the transformation of persistent organic pollutants in food webs using multi element isotope and enantiomer fractionation.

In order to track the transformation of persistent organic pollutants (POPs) in food webs, field experiments were conducted at two sites using stable isotope and enantiomer fractionation concepts. The enantiomers of α-hexachlorocyclohexane (α-HCH) were selected as representative compounds for POPs. Isotope and enantiomer fractionation allowed the characterization of α-HCH enantiomer biotransformation processes along trophic levels of the food web - from soil and plants to animal livers, fat tissues and milk. The enrichment of heavy isotopes in soils, plants and sediments as well as the changes of enantiomer fractionation indicate that the biotransformation of α-HCH occurred in these compartments. Moreover, the increase of carbon and chlorine isotopic compositions as well as the changes of enantiomer fractionation of liver, fat tissues and milk demonstrated that the overall HCH exposure was much higher than estimates based on concentration levels, while the isotope and enantiomer fractionation revealed the enantiomer specific enantiomer uptake across the blood-brain barriers. Dual element isotope analysis suggested that complex transformation processes have occurred along the potential food web from the HCH sources over different environmental compartments to animal livers, fat tissues and milk. The results imply that the analyses of stable isotope compositions and concentrations has potential to reconstruct the exposure of higher organisms to POPs.

Chemical analysis of wetland plants to evaluate the bioaccumulation and metabolism of hexachlorocyclohexane (HCH).

Hexachlorocyclohexanes (HCH) belong to the banned pesticides with short-time production and use during the last century. However, the consequences of this short period are still present as persistent environmental contamination. This study represents the large lab-scale experiment focused on the HCH accumulation and metabolism in selected wetland plants (Juncus effuses, Typha latifolia, Phragmites australis) and trees (Alnus glutinosa) after the exposure to the technical mix of HCH isomers (t-HCH) or δ-HCH at three different concentration. During the three-month exposure, morphological (biomass, height, relative chlorophyll content) and physiological (photosynthetic measurements - photosynthetic rate, stomatal conductance, transpiration and dark transpiration) parameters were measured to assess the HCH effect on plant's growth. The results showed that all selected plant species supported HCH removal from the soil. The total removal efficiency was lower for the t-HCH than for δ-HCH exposure, and the best results were provided by Alnus glutinosa tree. Also, no isomer preference was observed in plants exposed to t-HCH. Most HCH remained accumulated in the root biomass, and mainly α-HCH and δ-HCH were transported to the above-ground parts due to their physicochemical properties. Simultaneously, HCH uptake and metabolization to chlorobenzenes (CB) and chlorophenols (CP) occur. Non-targeted analysis showed that CP could be conjugated to glucose and malonyl in plant tissue, and secondary plant metabolism is affected positively and negatively after exposure to t-HCH depending on plant species and chemical concentration. Luteolin, quercetin and quercetin-3-O-glucoside found common to all species showed quantitative changes due to HCH. Nevertheless, most morphological and physiological parameters were adversely affected without statistical significance. This large-scale study provides information on the fate of HCH in the soil-plant system, the suitability of selected plants and their adaptation to chemical stress for use in the phytoremediation process.

Associations of chronic exposure to a mixture of pesticides and type 2 diabetes mellitus in a Chinese elderly population.

Epidemiological studies have related exposure to pesticides to increased risk of diabetes. However, few studies have evaluated the health effects of mixed pesticides exposure, especially in an elderly population. Here, we utilized gas chromatography-tandem mass spectrometry to quantify the levels of 39 pesticides in 4 categories in a Chinese elderly population. Then we used general linear models to explore the association between individual pesticide exposure and type 2 diabetes mellitus (T2DM). Restricted cubic spline (RCS) models were fitted to identify potential non-linearities between those associations. Furthermore, stratified analysis by gender was conducted to explore the gender-specific associations. Finally, we used weighted quantile sum (WQS) regression, quantile-based g computation (qgcomp), and Bayesian kernel machine regression (BKMR) to evaluate the effects of mixed exposure to 39 pesticides. The results showed that exposure to pesticides was associated with high risk of T2DM, with ß-Hexachlorocyclohexane (ß-BHC) and oxadiazon being the most significant independent contributors, which was pronounced among elderly women. Moreover, the association of ß-BHC and oxadiazon with T2DM was linear. These indicated that it is an urgent need to take practical measures to control these harmful pesticides.

Solar-assisted oxidation of organochlorine pesticides in groundwater using persulfate and ferrioxalate.

The oxidation of hexachlorocyclohexane isomers in the aqueous phase (Milli-Q and groundwater) was studied using persulfate activated by ferrioxalate and solar light at circumneutral pH. The experiments were conducted in a solar simulator reactor with local radiation fluxes qw= 1.12·10-7 E cm-2s-1 and in compound parabolic collectors with solar light (qw≈10-7 E cm-2s-1) for 390 min. The effect of activator dosage (18-125 µM ferrioxalate) and persulfate concentration (520-2600 µM) on hexachlorocyclohexane conversion and oxalate and oxidant consumption was analyzed. Conversion of about 95% of ß isomer was achieved at 390 min using 1300 µM of initial persulfate and 63 µM of Fe3+ concentration despite this ß isomer being the most recalcitrant to oxidation (XHexachlorocyclohexanes=0.98). Dechlorination above 80% was achieved under these conditions, analyzing the chlorides released into the water. The influence of chloride and bicarbonate on hexachlorocyclohexanes degradation was analyzed in milli-Q water and in groundwater. Hexachlorocyclohexane conversion at 390 min decreases from 98% to 83, 75 and 65% in the presence of chloride, bicarbonate or groundwater, respectively. Results obtained with compound parabolic collectors and solar light using 2600 µM Na2S2O8 and 63 µM Fe for removing hexachlorocyclohexanes agreed with those from the solar simulator reactor, supporting using solar light to activate persulfate for sustainable abatement of persistent organic pollutants in aqueous matrixes.

Draft genome sequence of Cupriavidus sp. strain TKC, isolated from a γ-hexachlorocyclohexane-degrading community.

Cupriavidus sp. strain TKC was isolated from a microbial community enriched with γ-hexachlorocyclohexane (γ-HCH). This strain did not show γ-HCH-degrading activity but was one of the major members of the community. Here, we present the draft genome sequence of the strain TKC with a size of 7 Mb.

Association between persistent organic pollutants in human milk and the infant growth and development throughout the first year postpartum in a cohort from Rio de Janeiro, Brazil.

Persistent organic pollutants (POPs) are compounds that are recalcitrant and ubiquitous that bioaccumulate in human milk (HM) and can impact infant growth and development. We explore the association between POP concentration in HM at 2-50 days postpartum and infant growth and development trajectory throughout the first year of life. A cohort of 68 healthy adult Brazilian women and their infants were followed from 28 to 35 gestational weeks to 12 months postpartum. HM samples were collected between 2 and 50 days postpartum, and POP concentrations were analyzed using gas chromatography with mass spectrometry. Concentrations of POPs >limit of quantification (LOQ) were defined as presence, and concentrations ≤LOQ as an absence. Growth z-scores were analyzed according to WHO growth charts and infant development scores according to Age & Stages Questionnaires at 1 (n = 66), 6 (n = 50), and 12 months (n = 45). Linear mixed effects (LME) models were used to investigate the association of POPs in HM with infant growth and development. Benjamini-Hochberg (BH) correction for multiple testing was performed to reduce the false discovery ratio. P < 0.1 was considered for models with the interaction between POPs and time/sex. After BH correction, adjusted LME models with time interaction showed (1) a positive association between the presence of ß hexachlorocyclohexane and an increase in head circumference-for-age z-score (ß = 0.003, P = 0.095); (2) negative associations between total POPs (ß = -0.000002, P = 0.10), total organochlorine pesticides (ß = -0.000002, P = 0.10), and dichlorodiphenyldichloroethylene concentrations in HM (ß = -0.000002, P = 0.10) and fine motor scores. No statistical difference between the sexes was observed. Postnatal exposure to organochlorine pesticides in HM shows a positive association with the trajectory of head circumference-for-age z-score and a negative association with the trajectories of fine motor skills scores. Future studies on POP variation in HM at different postpartum times and their effect on infant growth and development should be encouraged.

Targets for pollutants in rat and human pancreatic beta-cells: The effect of prolonged exposure to sub-lethal concentrations of hexachlorocyclohexane isomers on the expression of function- and survival-related proteins.

Decades after most countries banned hexachlorocyclohexane, HCH isomers still pollute the environment. Many studies described HCH as a pro-diabetic factor; nevertheless, the effect of HCH isomers on pancreatic beta-cells remains unexplored. This study investigated the effects of a one-month exposure to α-HCH, ß-HCH, and γ-HCH on protein expression in human (NES2Y) and rat (INS1E) pancreatic beta-cell lines. α-HCH and γ-HCH increased proinsulin and insulin levels in INS1E cells, while ß-HCH showed the opposite trend. α-HCH altered the expression of PKA, ATF3, and PLIN2. ß-HCH affected the expression of GLUT1, GLUT2, PKA, ATF3, p-eIF2α, ATP-CL, and PLIN2. γ-HCH altered the expression of PKA, ATF3, PLIN2, PLIN5, and IDH1. From the tested proteins, PKA, ATF3, and PLIN-2 were the most sensitive to HCH exposure and have the potential to be used as biomarkers.

Hexachlorocyclohexane impairs human sperm motility by affecting lysine glutarylation and mitochondrial functions.

Decreased sperm motility is a leading cause of male infertility and persistent organic pollutants are known to contribute significantly to the development of this disease. The effects of organochlorine pesticides such as hexachlorocyclohexane (HCH) on human sperm function and their mechanisms of action have received much attention, but are still not fully understood. Herein, we discovered that HCH has a concentration- and time-dependent inhibitory effect on human sperm motility in vitro. Moreover, HCH could reduce the levels of lysine glutarylation (Kglu) and glucose-6-phosphate dehydrogenase activity in sperm. Meanwhile, HCH could increase reactive oxygen species and thereby lead to mitochondrial depolarization and the down-regulation of adenosine triphosphate levels. In particular, we observed that sodium glutarate (Na-glu), the precursor of glutaryl-CoA, could alleviate the inhibitory effect of HCH on sperm Kglu levels, whereas the ROS scavenger N-acetyl-L-cysteine (NAC) had no effect. Intriguingly, both Na-glu and NAC were able to partially inhibit the HCH-induced increase in sperm ROS levels and impaired sperm motility. In conclusion, we propose that HCH inhibits sperm Kglu, leading to the disruption of mitochondrial energy metabolism, which in turn adversely affects sperm motility.

Simultaneous regulation of biocathodic γ-HCH dechlorination and CH4 production by tailoring the structure and function of biofilms based on quorum sensing.

Dechlorination of chlorinated organic pollutants and methanogenesis are attractive biocathode reductions in microbial electrolysis cells (MECs). Quorum sensing (QS) is applied to regulate microbial communications. However, how acyl-homoserine lactones (AHLs)-dependent QS organize the assembly of the biocathode microbial community, and then regulate multiple biocathode reductions remains unclear. By applying N-butanoyl homoserine lactone (C4-HSL), N-hexanoyl homoserine lactone (C6-HSL) and 3-oxo-hexanoyl homoserine lactone (3OC6-HSL) in γ-hexachlorocyclohexane (γ-HCH) contaminated MECs, this study investigated the changes of biofilm microbial structure and function and the mechanisms of AHLs-QS on γ-HCH dechlorination and CH4 production. Exogenous C4-HSL and 3OC6-HSL increased cytochrome c production and enriched dechlorinators, electroactive bacteria but not methanogens to accelerate γ-HCH dechlorination and inhibit CH4 production. C6-HSL facilitated dechlorination and CH4 production by enhancing biofilm electroactivity and increasing membrane transportation. Besides, exogenous C6-HSL restored the electron transfer capacity that was damaged by the concurrent addition of acylase, an endogenous AHL quencher. From the perspective of microbial assembly, this study sheds insights into and provides an efficient strategy to selectively accelerate dechlorination and CH4 production by harnessing microbial structure based on QS systems to meet various environmental demands.

Deciphering the kinetics and pathway of lindane biodegradation by novel soil ascomycete fungi for its implication in bioremediation.

Lindane, an organochlorine pesticide, negatively affects living beings and the ecosystem. In this study, the potential of 9 Ascomycetes fungi, isolated from an hexachlorocyclohexane dumpsite soil, was tested for biodegradation of lindane. The strain Pleurostoma richardsiae (FN5) showed lindane biodegradation rate constant (K value) of 0.144 d-1 and a half-life of 4.8d. The formation of intermediate metabolites upon lindane degradation including γ-pentachlorocyclohexene, 2,4-dichlorophenol, phenol, benzene, 1,3- cyclohexadiene, and benzoic acid detected by GC-MS and the potential pathway adopted by the novel fungal strain FN5 for lindane biodegradation has been elucidated. The study of gene profiles with reference to linA and linB in strain FN5 confirmed the same protein family with the reported heterologs from other fungal strains in the NCBI database. This study for the first time provides a thorough understanding of lindane biodegradation by a novel soil-borne Ascomycota fungal strain for its possible application in field-scale bioremediation.

Mechanochemical remediation of lindane-contaminated soils assisted by CaO: Performance, mechanism and overall assessment.

Soil contamination caused by persistent organic pollutants (POPs) has been a worldwide concern for decades. With lindane-contaminated soil as the target, a mechanochemical method assisted by CaO was comprehensively evaluated in terms of its remediation performance, degradation mechanism and overall assessment. The mechanochemical degradation performance of lindane in cinnamon soil or kaolin was determined under different additives, lindane concentrations and milling conditions. 2,2-Diphenyl-1-(2,4,6-trinitrophenyl) hydrazinyl free radical (DPPH•) and electron spin resonance (ESR) tests evidenced that the degradation of lindane in soil was caused mainly by the mechanical activation of CaO to produce free electrons (e-) and the alkalinity of the generated Ca(OH)2. Dehydrochlorination or dechlorination by elimination, alkaline hydrolysis, hydrogenolysis and the subsequent carbonization were the main degradation pathways of lindane in soil. The main final products included monochlorobenzene, carbon substances and methane. The mechanochemical method with CaO was proved to also efficiently degrade lindane in three other soils and other hexachlorocyclohexane isomers and POPs in soil. The soil properties and soil toxicity after remediation were assessed. This work presents a relatively clear discussion of various aspects of the mechanochemical remediation of lindane-contaminated soil assisted by CaO.

Revelation of bioremediation approaches for hexachlorocyclohexane degradation in soil.

This review elucidates different bioremediation approaches used for degradation of HCH from contaminated sites. It highlights the significance of degradative pathways, microbial diversity and impact of different environmental factors for developing viable bioremediation strategies. The application of innovative biotechnological approaches and a thorough understanding of HCH biodegradation pathways show great promise for the creation of long-term solutions to HCH pollution and the restoration of polluted soil ecosystems. Bioremediation technologies viz. biostimulation, bioaugmentation, phytoremediation have been considered till date for treating HCH-contaminated sites. Different bacterial and fungal strains have been reported for degradation of HCH residues. However, these methods are limited to γ-HCH degradation, at laboratory scale and achieving lower success rate for large scale demonstration trials. This review presents a theoretical background for degradation of different HCH isomers in soil through plants, microbes and through their cooperative interactions. This work briefly overviews the substantial contamination of the environment by HCH residues, along with spontaneous evolution of degradation pathways through various HCH degrading microbes. Bioremediation mechanism and pathways of HCH degradation through plants and microbes have been discussed thoroughly. Through molecular and genetic investigations, the complex metabolic pathways used by these microbes, including reductive dechlorination, hydrolysis, and ring cleavage, has been clarified. This study seeks to give a thorough summary of recent discoveries and developments in bioremediation methods for soil HCH degradation. Numerous microbial consortia, including fungi, plants, and bacteria have been recognised as important participants in the transformation of HCH.

Effects of irrigation with HCH-contaminated water on crop performance and HCH accumulation in plant and soil.

Lindane production is very ineffective since, for each ton of lindane obtained, between 6 and 10 tons of hexachlorocyclohexane (HCH) isomers and other toxic compounds are produced. Due to the disposal of these residues, contaminated zones still exist, and many dumpsites are close to rivers and water reservoirs. The current study examines the consequences of irrigating pea, maize, and alfalfa, with water containing different HCH concentrations on the accumulation of HCH in plant material and soils. The experiments were conducted on pots under controlled conditions using drinking water (as reference) and water with several HCH concentrations: 0.5 µg L-1 (the maximum threshold allowed for human consumption), 2.5 µg L-1, 5 µg L-1, and 20 µg L-1. Results showed that both surface and overhead irrigation with these HCH concentrations did not cause any toxicity effects on the considered crops. However, under overhead irrigation with HCH concentrations higher than 5 µgL-1 HCH is absorbed by maize leaves and its concentration in plant biomass surpassed the EU maximum residue level of 10 µg kg-1. In the case of fodder maize, an HCH concentration of 0.84 µg L-1 in irrigation water produced an HCH concentration in plant above 20 µg kg-1 dry matter, the upper threshold established in the Spanish legislation, that limits the use for animal feeding. In the case of alfalfa, HCH was detected in treatments with the highest HCH concentration (13 µg L-1) under surface irrigation, but concentration was below the EU maximum residue level. In conclusion, in overhead irrigated systems, water with HCH concentrations below 5 µg L-1 does not produce HCH accumulation in pea and maize grain above the maximum residue levels; however, for fodder maize, the HCH concentration in irrigation water should be controlled to avoid HCH accumulation in plants above the limit for animal feeding.

Exposure to environmental chemicals and cancer risk: epidemiological evidence from Japanese studies.

Exposure to certain chemicals in the environment may contribute to the risk of developing cancer. Although cancer risk from environmental chemical exposure among general populations is considered low compared to that in occupational settings, many people may nevertheless be chronically exposed to relatively low levels of environmental chemicals which vary by such various factors as residential area, lifestyle, and dietary habits. It is therefore necessary to assess population-specific exposure levels and examine their association with cancer risk. Here, we reviewed epidemiological evidence on cancer risk and exposure to dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), polychlorinated biphenyls (PCBs), per- and polyfluoroalkyl substances (PFASs), cadmium, arsenic, and acrylamide. Japanese are widely exposed to these chemicals, mainly through the diet, and an association with increased cancer risk is suspected. Epidemiological evidence from Japanese studies to date does not support a positive association between blood concentrations of DDT, HCH, PCBs, and PFASs and risk of breast or prostate cancer. We established assessment methods for dietary intake of cadmium, arsenic, and acrylamide using a food frequency questionnaire. Overall, dietary intakes of cadmium, arsenic, and acrylamide were not significantly associated with increased risk of total cancer and major cancer sites in the Japan Public Health Center-based Prospective Study. However, statistically significant positive associations were observed between dietary cadmium intake and risk of estrogen receptor-positive breast cancer among postmenopausal women, and dietary arsenic intake and risk of lung cancer among male smokers. In addition, studies using biomarkers as exposure assessment revealed statistically significant positive associations between urinary cadmium concentration and risk of breast cancer, and between ratio of hemoglobin adducts of acrylamide and glycidamide and risk of breast cancer. Epidemiological studies of general populations in Japan are limited and further evidence is required. In particular, studies of the association of organochlorine and organofluorine compounds with risk of cancer sites other than breast and prostate cancer are warranted, as are large prospective studies of the association between biomarkers of exposure and risk of cancer.

Conductive Materials on Biocathodes Altered the Electron-Transfer Paths and Modulated γ-HCH Dechlorination and CH4 Production in Microbial Electrochemical Systems.

Adding conductive materials to the cathode of a microbial electrochemical system (MES) can alter the route of interspecies electron transfer and the kinetics of reduction reactions. We tested reductive dechlorination of γ-hexachlorocyclohexane (γ-HCH), along with CH4 production, in MES systems whose cathodes were coated with conductive magnetite nanoparticles (NaFe), biochar (BC), magnetic biochar (FeBC), or anti-conductive silica biochar (SiBC). Coating with NaFe enriched electroactive microorganisms, boosted electro-bioreduction, and accelerated γ-HCH dechlorination and CH4 production. In contrast, BC only accelerated dechlorination, while FeBC only accelerated methanogenesis, because of their assemblies of functional taxa that selectively transferred electrons to those electron sinks. SiBC, which decreased electro-bioreduction, yielded the highest CH4 production and increased methanogens and the mcrA gene. This study provides a strategy to selectively control the distribution of electrons between reductive dechlorination and methanogenesis by adding conductive or anti-conductive materials to the MES's cathode. If the goal is to maximize dechlorination and minimize methane generation, then BC is the optimal conductive material. If the goal is to accelerate electro-bioreduction, then the best addition is NaFe. If the goal is to increase the rate of methanogenesis, adding anti-conductive SiBC is the best.

Modeling historical budget for ß-Hexachlorocyclohexane (HCH) in the Arctic Ocean: A contrast to α-HCH.

The historical annual loading to, removal from, and cumulative burden in the Arctic Ocean for ß-hexachlorocyclohexane (ß-HCH), an isomer comprising 5-12% of technical HCH, is investigated using a mass balance box model from 1945 to 2020. Over the 76 years, loading occurred predominantly through ocean currents and river inflow (83%) and only a small portion via atmospheric transport (16%). ß-HCH started to accumulate in the Arctic Ocean in the late 1940s, reached a peak of 810 t in 1986, and decreased to 87 t in 2020, when its concentrations in the Arctic water and air were ∼30 ng m-3 and ∼0.02 pg m-3, respectively. Even though ß-HCH and α-HCH (60-70% of technical HCH) are both the isomers of HCHs with almost identical temporal and spatial emission patterns, these two chemicals have shown different major pathways entering the Arctic. Different from α-HCH with the long-range atmospheric transport (LRAT) as its major transport pathway, ß-HCH reached the Arctic mainly through long-range oceanic transport (LROT). The much higher tendency of ß-HCH to partition into the water, mainly due to its much lower Henry's Law Constant than α-HCH, produced an exceptionally strong pathway divergence with ß-HCH favoring slow transport in water and α-HCH favoring rapid transport in air. The concentration and burden of ß-HCH in the Arctic Ocean are also predicted for the year 2050 when only 4.4-5.3 t will remain in the Arctic Ocean under the influence of climate change.