Generation of zero-valent sulfur from dissimilatory sulfate reduction in sulfate-reducing microorganisms.

Dissimilatory sulfate reduction (DSR) mediated by sulfate-reducing microorganisms (SRMs) plays a pivotal role in global sulfur, carbon, oxygen, and iron cycles since at least 3.5 billion y ago. The canonical DSR pathway is believed to be sulfate reduction to sulfide. Herein, we report a DSR pathway in phylogenetically diverse SRMs through which zero-valent sulfur (ZVS) is directly generated. We identified that approximately 9% of sulfate reduction was directed toward ZVS with S8 as a predominant product, and the ratio of sulfate-to-ZVS could be changed with SRMs' growth conditions, particularly the medium salinity. Further coculturing experiments and metadata analyses revealed that DSR-derived ZVS supported the growth of various ZVS-metabolizing microorganisms, highlighting this pathway as an essential component of the sulfur biogeochemical cycle.

In Situ Photodeposition of Gold Nanoparticles with Exposed High-Activity Crystal Facets under Different Sacrificial Agents.

In situ photodeposition presents a powerful approach for integrating noble metal co-catalysts onto semiconductor surfaces. However, achieving precise control over the microstructure of the deposited co-catalyst remains a major challenge. Au nanoparticles (NPs) are deposited onto H-KCNO using HAuCl4 in the presence of various sacrificial agents in this study. Notably, the choice of sacrificial agent decisively influences the exposed crystal facets, loaded content, and particle size of the deposited Au NPs. Importantly, in situ photodeposition under an ethanol solution facilitates the exposure of the highly active (111) and (220) crystal facets of Au. The introduction of Au NPs significantly enhances photocatalytic hydrogen evolution, achieving rates of 4.93, 57.88, and 15.44 µmol/h for H-KCNO/Au-(water, ethanol, and lactic acid), respectively. The observed photocatalytic activity for hydrogen evolution indicates that the exposure of the highly active planes emerges as critical for significant performance enhancement. Photoelectrochemical and photoluminescence measurements suggest that the highly active (111) and (220) crystal facets effectively segregate sites for redox reactions, thereby impeding the recombination of photogenerated electron-hole pairs.

Unlock the Visible-Light Photocatalytic OWS by Surface Disorder-Engineered Bi-Based Composite Oxides through Phosphorization.

It has been proven that the introduction of disorder in the surface layers can narrow the energy band gap of semiconductors. Disordering the surface's atomic arrangement is primarily achieved through hydrogenation reduction. In this work, we propose a new approach to achieve visible-light absorption through surface phosphorization, simultaneously raising the energy band structure. In particular, the surface phosphorization of BixY1-xVO4 was successfully prepared by annealing them with a small amount of NaH2PO2 under a N2 atmosphere. After this treatment, the obtained BixY1-xVO4 showed distinct absorption in visible light. The surface phosphorization treatment not only improves the photocatalytic activity of BixY1-xVO4 but also enables visible-light photocatalytic overall water splitting. Furthermore, we demonstrate that this surface phosphorization method is universal for Bi-based composite oxides.

Improve Niche Colonization and Microbial Interactions for Organohalide-Respiring-Bacteria-Mediated Remediation of Chloroethene-Contaminated Sites.

Organohalide-respiring bacteria (OHRB)-mediated reductive dehalogenation is promising in in situ bioremediation of chloroethene-contaminated sites. The bioremediation efficiency of this approach is largely determined by the successful colonization of fastidious OHRB, which is highly dependent on the presence of proper growth niches and microbial interactions. In this study, based on two ecological principles (i.e., Priority Effects and Coexistence Theory), three strategies were developed to enhance niche colonization of OHRB, which were tested both in laboratory experiments and field applications: (i) preinoculation of a niche-preparing culture (NPC, being mainly constituted of fermenting bacteria and methanogens); (ii) staggered fermentation; and (iii) increased inoculation of CE40 (a Dehalococcoides-containing tetrachloroethene-to-ethene dechlorinating enrichment culture). Batch experimental results show significantly higher dechlorination efficiencies, as well as lower concentrations of volatile fatty acids (VFAs) and methane, in experimental sets with staggered fermentation and niche-preconditioning with NPC for 4 days (CE40_NPC-4) relative to control sets. Accordingly, a comparatively higher abundance of Dehalococcoides as major OHRB, together with a lower abundance of fermenting bacteria and methanogens, was observed in CE40_NPC-4 with staggered fermentation, which indicated the balanced syntrophic and competitive interactions between OHRB and other populations for the efficient dechlorination. Further experiments with microbial source tracking analyses suggested enhanced colonization of OHRB by increasing the inoculation ratio of CE40. The optimized conditions for enhanced colonization of OHRB were successfully employed for field bioremediation of trichloroethene (TCE, 0.3-1.4 mM)- and vinyl chloride (VC, ∼0.04 mM)-contaminated sites, resulting in 96.6% TCE and 99.7% VC dechlorination to ethene within 5 and 3 months, respectively. This study provides ecological principles-guided strategies for efficient bioremediation of chloroethene-contaminated sites, which may be also employed for removal of other emerging organohalide pollutants.

Reciprocal Interactions of Abiotic and Biotic Dechlorination of Chloroethenes in Soil.

Chloroethenes (CEs) as common organic pollutants in soil could be attenuated via abiotic and biotic dechlorination. Nonetheless, information on the key catalyzing matter and their reciprocal interactions remains scarce. In this study, FeS was identified as a major catalyzing matter in soil for the abiotic dechlorination of CEs, and acetylene could be employed as an indicator of the FeS-mediated abiotic CE-dechlorination. Organohalide-respiring bacteria (OHRB)-mediated dechlorination enhanced abiotic CEs-to-acetylene potential by providing dichloroethenes (DCEs) and trichloroethene (TCE) since chlorination extent determined CEs-to-acetylene potential with an order of trans-DCE > cis-DCE > TCE > tetrachloroethene/PCE. In contrast, FeS was shown to inhibit OHRB-mediated dechlorination, inhibition of which could be alleviated by the addition of soil humic substances. Moreover, sulfate-reducing bacteria and fermenting microorganisms affected FeS-mediated abiotic dechlorination by re-generation of FeS and providing short chain fatty acids, respectively. A new scenario was proposed to elucidate major abiotic and biotic processes and their reciprocal interactions in determining the fate of CEs in soil. Our results may guide the sustainable management of CE-contaminated sites by providing insights into interactions of the abiotic and biotic dechlorination in soil.

BrainIAK tutorials: User-friendly learning materials for advanced fMRI analysis.

Advanced brain imaging analysis methods, including multivariate pattern analysis (MVPA), functional connectivity, and functional alignment, have become powerful tools in cognitive neuroscience over the past decade. These tools are implemented in custom code and separate packages, often requiring different software and language proficiencies. Although usable by expert researchers, novice users face a steep learning curve. These difficulties stem from the use of new programming languages (e.g., Python), learning how to apply machine-learning methods to high-dimensional fMRI data, and minimal documentation and training materials. Furthermore, most standard fMRI analysis packages (e.g., AFNI, FSL, SPM) focus on preprocessing and univariate analyses, leaving a gap in how to integrate with advanced tools. To address these needs, we developed BrainIAK (brainiak.org), an open-source Python software package that seamlessly integrates several cutting-edge, computationally efficient techniques with other Python packages (e.g., Nilearn, Scikit-learn) for file handling, visualization, and machine learning. To disseminate these powerful tools, we developed user-friendly tutorials (in Jupyter format; https://brainiak.org/tutorials/) for learning BrainIAK and advanced fMRI analysis in Python more generally. These materials cover techniques including: MVPA (pattern classification and representational similarity analysis); parallelized searchlight analysis; background connectivity; full correlation matrix analysis; inter-subject correlation; inter-subject functional connectivity; shared response modeling; event segmentation using hidden Markov models; and real-time fMRI. For long-running jobs or large memory needs we provide detailed guidance on high-performance computing clusters. These notebooks were successfully tested at multiple sites, including as problem sets for courses at Yale and Princeton universities and at various workshops and hackathons. These materials are freely shared, with the hope that they become part of a pool of open-source software and educational materials for large-scale, reproducible fMRI analysis and accelerated discovery.

Spatial Distribution, Bioconversion and Ecological Risk of PCBs and PBDEs in the Surface Sediment of Contaminated Urban Rivers: A Nationwide Study in China.

Surface sediments of polluted urban rivers can be a reservoir of hydrophobic persistent organic pollutants (POPs). In this study, we comprehensively assessed the contamination of two groups of POPs, that is, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), in 173 black-odorous urban rivers in China. Spatial distribution of PCBs and PBDEs showed similar patterns but very different contamination levels in surface sediments, that is, average concentrations of 10.73 and 401.16 ng/g dw for the ∑PCBs and ∑PBDEs, respectively. Tetra-/di-CBs and deca-BDE are major PCBs and PBDEs and accounted for 59.11 and 95.11 wt % of the ∑PCBs and ∑PBDEs, respectively. Compared with the persistence of PBDEs, the EF changes of chiral PCBs together with previous cultivation evidence indicated indigenous bioconversion of PCBs in black-odorous urban rivers, particularly the involvement of uncharacterized Dehalococcoidia in PCB dechlorination. Major PCB sources (and their relative contributions) included pigment/painting (25.36%), e-waste (22.92%), metallurgical industry (13.25%), and e-waste/biological degradation process (10.95%). A risk assessment indicated that exposure of resident organisms in urban river sediments to deca-/penta-BDEs could pose a high ecological risk. This study provides the first insight into the contamination, conversion and ecological risk of PCBs and PBDEs in nationwide polluted urban rivers in China.

Sludge digestibility and functionally active microorganisms in methanogenic sludge digesters revealed by E. coli-fed digestion and microbial source tracking.

Methanogenic sludge digestion plays a pivotal role in attenuating and hygienizing the massively-produced waste activated sludge (WAS), which is predominantly composed of microbial cells and extracellular polymeric substances (EPS). The efficient sludge digestion requires a variety of functionally active microorganisms working together closely to convert sludge organic matter into biogas. Nonetheless, the digestion efficiency (or digestibility quantified as carbon removal efficiency) of major sludge constituents (i.e., microbial cells and EPS) and associated functionally active microorganisms in sludge digesters remain elusive. In this study, we identified the digestibility of sludge microbial cells and the associated functionally active microorganisms by using Escherichia coli (E. coli)-fed digestion and microbial source tracking. The average carbon removals in four digesters fed with fresh WAS (WAS-AD), thermal pretreated WAS (Thermal-WAS-AD), E. coli cells (E.coli-AD) and thermal pretreated E. coli cells (Thermal-E.coli-AD) were 30.6 ± 3.4%, 45.8 ± 2.9%, 69.0 ± 3.4% and 68.9 ± 4.6%, respectively. Compared to WAS-AD and Thermal-WAS-AD, the significantly higher carbon removals in E. coli-AD and Thermal-E. coli-AD suggested the remarkably higher digestibility of microbial cells than EPS, and releasing organic matter from EPS might be a rate-limiting step in sludge digestion. Functionally active microorganisms for microbial cell digestion predominantly included fermenters (e.g., Petrimonas and Lentimicrobium), syntrophic acetogens (e.g., Synergistaceae) and methanogens (e.g., Methanosaeta and Methanosarcina). Microbial source tracking estimation showed that the microbial cell-digesting populations accounted for 35.6 ± 9.1% and 70.3 ± 10.1% of total microbial communities in the WAS-AD and Thermal-WAS-AD, respectively. Accordingly, the functionally active microorganisms for digestion of both microbial cells and EPS accounted for 64.5 ± 12.1% and 97.3 ± 2.0% of total digestion sludge microbiome in WAS-AD and Thermal-WAS-AD, respectively. By contrast, feeding WAS-derived microorganisms accounted for 23.2 ± 4.4% and 2.3 ± 1.2% of total microbial communities in the WAS-AD and Thermal-WAS-AD, respectively.

Coupling of biostimulation and bioaugmentation for enhanced bioremoval of chloroethylenes and BTEX from clayey soil.

The bioremoval potential of Pseudomonas plecoglossicida toward mixed contaminants was explored through the coupled biostimulation and bioaugmentation in soil microcosm. Response surface methodology was employed to optimize nutrients and innoculum size for the cometabolic removal of two representative chloroethylenes, trichloroethylene (TCE) and cis-1,2-dichloroethylene (cis-DCE), mixed with benzene, toluene, ethylbenzene, and xylenes (BTEX). The interactive effects of nutrients [nitrogen (N) and phosphorus (P)] and inoculum size toward the bioremoval of mixture of BTEX (600 mg kg-1), cis-DCE (10 mg kg-1), and TCE (10 mg kg-1) were estimated using principal component analysis and two-dimensional hierarchical cluster analysis. The optimal condition was confirmed with C:N:P ratio of 100:26.7:1.8-4.8 and higher inoculum size (≥25%), where 97.7% of benzene, 98.3% of toluene, 91.2% of ethylbenzene, 45.6% of m,p-xylene, 31.2% of o-xylene, 26.9% of cis-DCE, and 33.5% of TCE were bioremoved.

Solid-phase denitrification for water remediation: processes, limitations, and new aspects.

Nitrate pollution in water environments is a ubiquitous problem. Solid-phase denitrification (SPD) is a technology that has attracted in recent years increasing attention due to its significant advantage suitability over the aqueous-based denitrification for in situ water remediation. This paper provides a view of new aspects of the application of SPD for water remediation. The processes and mechanisms for nitrogen transformation in SPD, for example, direct denitrification, dissimilatory nitrate reduction to ammonium, and anammox are presented. The main processes of the transformation of the carbon substrate in SPD are also discussed. The major limitations of SPD, including low carbon availability, NO2 - and N2O accumulation, dissolved organic carbon release, and NH4 + production, are summarized and the factors associated with such limitations are also discussed. In addition, some novel measures to mitigate these limitations, such as applying a biodegradable polymer substrate and heterotrophic-autotrophic denitrification (HAD) process, are described. Finally, simultaneous removal of nitrate and some typical concurrent contaminants for expanded application of SPD are discussed. This review attempts to advance our understanding of engineered denitrification processes for wastewater treatment or water remediation.

Effect of bandgap alignment on the photoreduction of CO2 into methane based on Cu2O-decorated CuO microspheres.

Semiconductors' band gap alignment is important for the photoreduction of CO2 to methane. In the paper, two kinds of Cu2O-decorated CuO microspheres composed with nanoflakes were prepared by using two different methods. Their electron behaviors were studied from the XPS spectra and photoelectrochemical measurements. Both samples are p-type CuO covered with an amount of Cu2O nanoparticles on their surface. Combined with their bandgaps and flat band potentials, CuO-Mic has a well-matched bandgap alignment between Cu2O and CuO, which is favorable for the separation of photogenerated electron-hole pairs. Those photogenerated carriers are beneficial for the conversion of CO2 to CH4, as an 8-electron process for the conversion of CO2 to CH4 will consume more photogenerated electrons for the chemical reactions than that of the 2-electron process for CO2 reduction to CO. Therefore, CuO-Mic has much better photocatalytic activity for CO2 reduction to CH4 with a CH4 yield ten times higher than that of CuO-Hyd under a visible light irradiation, the CO yields of the CO2 reduction are identical.

Organohalide-Respiring Bacteria in Polluted Urban Rivers Employ Novel Bifunctional Reductive Dehalogenases to Dechlorinate Polychlorinated Biphenyls and Tetrachloroethene.

Polluted urban river sediments could be a sink of persistent and toxic polychlorinated biphenyls (PCBs) in urban areas and provide desired growth niches for organohalide-respiring bacteria (OHRB). In this study, microcosms were set up with surface sediments of nationwide polluted urban rivers in China, of which 164 cultures could dechlorinate tetrachloroethene (PCE) to dichloroethenes (DCEs) and to vinyl chloride and/or ethene. Further in vivo tests showed extensive PCB dechlorination with different pathways in 135 PCE pregrown cultures. Taking reductive dechlorination of PCB180 (2345-245-CB) as an example, 121 and 14 cultures preferentially removed flanked para- and meta-chlorines, respectively. Strikingly, all in vitro assays with the 135 PCE pregrown cultures showed identical PCB dechlorination pathways with their living cultures, implying the involvement of bifunctional reductive dehalogenases (RDases) to dechlorinate both PCBs and PCE. Further 16S rRNA and RDase gene-based analyses, together with enantioselective dechlorination of chiral PCBs, suggested that Dehalococcoides and Dehalogenimonas in the 135 cultures largely employed distinctively different novel bifunctional RDases to catalyze PCB/PCE dechlorination. Quantitative assessment of the community assembly process with the modified stochasticity ratio (MST) indicated three different stages in enrichment of OHRB. The second stage, as the only one controlled by stochastic processes (MST > 0.5), required extra attention in monitoring community successional patterns to minimize stochastic variance for enriching the PCB/PCE-dechlorinating OHRB.

In Situ Microbial Degradation of PBDEs in Sediments from an E-Waste Site as Revealed by Positive Matrix Factorization and Compound-Specific Stable Carbon Isotope Analysis.

In the present study, positive matrix factorization (PMF) and compound-specific isotope analysis were used to investigate the in situ biodegradation of polybrominated diphenyl ethers (PBDEs) in sediment cores collected from a pond at an e-waste recycling site in South China. The potential microorganisms relevant to the degradation of PBDEs were also assessed to aid in the understanding of in situ biodegradation. The PMF results suggested that reductive debromination took place in the sediments. The debromination signal (ratio of the concentration of factor 5 (PMF result) to the total PBDE content) was positively correlated with the relative abundance of Dehalococcoidetes at different core depths. The clear 13C enrichment of five PBDE congeners (BDE 28, 47, 49, 99, and 153) with increasing core depth indicated that a measurable change in isotope fractionation might have occurred during PBDE biodegradation. The in situ biodegradation was further validated by the widespread detection of mono-BDE congeners (BDE 2, BDE 3) and diphenyl ether in the sediments. This study provides new evidence to enhance our understanding of the in situ biodegradation of PBDEs and suggests that the extensive removal of bromine from PBDEs was mediated by indigenous microorganisms at the e-waste site.

Enantioselective Dechlorination of Polychlorinated Biphenyls in Dehalococcoides mccartyi CG1.

Reductive dehalogenation mediated by organohalide-respiring bacteria plays a critical role in the global cycling of organohalides. Nonetheless, information on the dehalogenation enantioselectivity of organohalide-respiring bacteria remains limited. In this study, we report the enantioselective dechlorination of chiral polychlorinated biphenyls (PCBs) by Dehalococcoides mccartyi CG1. CG1 preferentially removed halogens from the (-)-enantiomers of the three major environmentally relevant chiral PCBs (PCB174, PCB149, and PCB132), and the enantiomer compositions of the dechlorination products depended on their parent organohalides. The in vitro assays with crude cell extracts or concentrated whole cells and the in vivo experiments with living cells showed similar enantioselectivities, in contrast with the distinct enantiomeric enrichment factors (εER) of the substrate chiral PCBs. Additionally, these results suggest that concentrated whole cells might be an alternative to crude cell extracts in in vitro tests of reductive dehalogenation activities. The enantioselective dechlorination of other chiral PCBs that we resolved via gas chromatography further confirmed the preference of CG1 for the (-)-enantiomers.IMPORTANCE A variety of agrochemicals and pharmaceuticals are chiral. Due to the enantioselectivity in biological processes, enantiomers of chiral compounds may have different environmental occurrences, fates, and ecotoxicologies. Many chiral organohalides exist in anaerobic or anoxic soils and sediments, and organohalide-respiring bacteria play a major role in the environmental attenuation and global cycling of these chiral organohalides. Therefore, it is important to investigate the dehalogenation enantioselectivity of organohalide-respiring bacteria. This study reports the discovery of enantioselective dechlorination of chiral PCBs by Dehalococcoides mccartyi CG1, which provides insights into the dehalogenation enantioselectivity of Dehalococcoides and may shed light on future PCB bioremediation efforts to prevent enantioselective biological side effects.

Effect of toluene concentration and hydrogen peroxide on Pseudomonas plecoglossicida cometabolizing mixture of cis-DCE and TCE in soil slurry.

An indigenous Pseudomonas sp., isolated from the regional contaminated soil and identified as P. plecoglossicida, was evaluated for its aerobic cometabolic removal of cis-1,2-dichloroethylene (cis-DCE) and trichloroethylene (TCE) using toluene as growth substrate in a laboratory-scale soil slurry. The aerobic simultaneous bioremoval of the cis-DCE/TCE/toluene mixture was studied under different conditions. Results showed that an increase in toluene concentration level from 300 to 900 mg/kg prolonged the lag phase for the bacterial growth, while the bioremoval extent for cis-DCE, TCE, and toluene declined as the initial toluene concentration increased. In addition, the cometabolic bioremoval of cis-DCE and TCE was inhibited by the presence of hydrogen peroxide as the additional oxygen source, while the bioremoval of toluene (900 mg/kg) was enhanced after 9 days of incubation. The subsequent addition of toluene did not improve the cometabolic bioremoval of cis-DCE and TCE. The obtained results would help to enhance the applicability of bioremediation technology to the mixed waste contaminated sites.

Pre-exposure of Triclosan compromise tetracycline-derived antibiotic resistance in methanogenic digestion microbiome.

Triclosan (TCS) and tetracycline (TC) are commonly detected antibacterial agents in sewage and environment matrices. Nonetheless, the impact of sequential exposure to TCS and TC on the methanogenic digestion microbiome remains unknown. In this study, TCS was shown to reduce COD removal efficiency to 69.8%, but alleviated the inhibitive effect of consequent TC-amendment on the digestion microbiome. Interestingly, TCS pre-exposure resulted in abundance increase of acetotrophic Methanosaeta to 2.68%, being 2.91 folds higher than that without TCS amendment. Microbial network analyses showed that TCS pre-exposure caused microorganisms to establish a co-ecological relationship against TC disturbance. Further analyses of total antibiotic resistance genes (ARGs) showed the TCS-derived compromise of TC-induced ARGs enrichment in digestion microbiomes, e.g., 238.2% and 152.1% ARGs increase upon TC addition in digestion microbiomes without and with TCS pre-exposure, respectively. This study provides new insights into the impact of antibacterial agents on the methanogenic digestion microbiome.

Insights into the occurrence, spatial distribution, and ecological implications of organophosphate triesters in surface sediments from polluted urban rivers across China.

Organophosphate triesters (tri-OPEs) are a kind of widespread contaminants in the world, particularly in China, which is a major producer and user of tri-OPEs. However, tri-OPE pollution in urban river sediments in China remains unclear. In current work, we carried out the first nationwide investigation to comprehensively monitor 10 conventional and five emerging tri-OPEs in sediments of 173 black-odorous urban rivers throughout China. Concentrations of 10 conventional and five emerging tri-OPEs were 3.8-1240 ng/g dw (mean: 253 ng/g dw) and 0.21-1107 ng/g dw (68 ng/g dw), respectively, and significantly differed among the cities sampled but generally decreased from Northeast and East China to Central and West China. These spatial patterns suggest that tri-OPE pollution was mainly from local sources and was controlled by the industrial and economic development levels in these four areas, as indicated by the significant correlations between tri-OPE concentrations and gross domestic production, gross industrial output, and daily wastewater treatment capacity. Although the tri-OPE composition varied spatially at different sites, which indicated different tri-OPE input patterns, it was commonly dominated by tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, and tris(1-chloro-2-propyl) phosphate (conventional tri-OPEs) and bisphenol A-bis(diphenyl phosphate) and isodecyl diphenyl phosphate (emerging tri-OPEs). A risk assessment indicated that tri-OPEs in most sampling sediments had a low to moderate risk to aquatic organisms.

Spatial distribution, conversion, and ecological risk assessment of hexabromocyclododecanes in the sediments of black-odorous urban rivers nationwide in China.

Hexabromocyclododecanes (HBCDs) have become a global pollution problem, particularly in China-a major producer and user of HBCDs. However, little is known about the HBCD pollution status in urban rivers nationwide in China. In this study, we comprehensively investigated the pollution characteristics of HBCDs in 173 sediment samples from black-odorous urban rivers across China. Total HBCD concentrations ranged from not-detected to 848 ng/g dw, showing significant differences among the various sampling cities, but generally increasing from west to east China. This distribution pattern of HBCDs was strongly associated with the local industrial output, gross domestic product, and daily wastewater treatment capacity. α-HBCD was the predominant diastereoisomer in most sediments, with an average proportion of 63.8 ± 18.8 %, followed by γ-HBCD (23.8 ± 19.5 %) and ß-HBCD (12.4 ± 6.49 %), showing a significant increase of the α-HBCD proportions relative to those in HBCD commercial mixtures and an opposite trend for that of γ-HBCD. These results suggested that HBCDs might undergo isomerization from γ- to α-HBCD and biotic/abiotic degradation with preference for γ-HBCD. Of these conversions, the microbial degradation of HBCDs was further verified by the preferential transformation of (-)-α-, (+)-ß-, and (-)-γ-HBCDs and the detection of HBCD-degrading bacteria, including Dehalococcoides, Bacillus, Sphingobium, and Pseudomonas. A risk assessment indicated that HBCDs pose low to moderate risks to aquatic organisms in most black-odorous urban river sediments.

Occurrence, composition, and spatial distribution of dechlorane plus in surface sediments of black-odorous urban rivers across China.

China, one of the two dechlorane plus (DP) producers, might have become a major area of DP pollution. The environmental contamination status of DP in sediments across the whole of China has not yet been studied. In the current study, the pollution levels, spatial distribution, and compositions of DP were investigated comprehensively in surface sediments from 173 black-odorous urban rivers across China for the first time. Total DP concentrations varied from not-detected to 39.71 ng/g dw, with an average concentration of 3.20 ± 4.74 ng/g dw, which was polluted by local emission sources and presented significant differences among different sampling cities. Among the seven administrative regions of China, DP concentrations were the highest in South China and showed a decreasing trend from southeastern coastal areas to northwest inland regions. Spearman's correlation analysis suggested that the gross industrial output, gross domestic product, and daily wastewater treatment capacity were not the principal factors controlling the spatial distribution of DP. The fanti values (the concentration ratios of anti-DP to the sum of anti-DP and syn-DP) varied from 0.19 to 0.88, with those in most sediments falling in the range of DP technical product (0.60 ~ 0.80), suggesting no apparent stereoselective enrichment occurred. Moreover, the anti-Cl11-DP was detected in sediments (n.d. ~ 0.40 ng/g dw), which showed significantly and insignificantly positive correlation with the anti-DP levels and fanti, respectively, implying it might mainly originate from the byproduct of DP technical product rather than the dechlorination of anti-DP.

Comprehensive exploration of the anaerobic biotransformation of polychlorinated biphenyls in Dehalococcoides mccartyi CG1: Kinetics, enantioselectivity, and isotope fractionation.

Anaerobic microbial transformation is a key pathway in the natural attenuation of polychlorinated biphenyls (PCBs). Much less is known about the transformation behaviors induced by pure organohalide-respiring bacteria, especially kinetic isotope effects. Therefore, the kinetics, pathways, enantioselectivity, and carbon and chlorine isotope fractionation of PCBs transformation by Dehalococcoides mccartyi CG1 were comprehensively explored. The results indicated that the PCBs were mainly dechlorinated via removing their double-flanked meta-chlorine, with their first-order kinetic constants following the order of PCB132 > PCB174 > PCB85 > PCB183 > PCB138. However, PCBs occurred great loss of stoichiometric mass balance during microbial transformation, suggesting the generation of other non-dehalogenation products and/or stable intermediates. The preferential transformation of (-)-atropisomers and generation of (+)-atropisomers were observed during PCB132 and PCB174 biotransformation with the enantiomeric enrichment factors of -0.8609 ± 0.1077 and -0.4503 ± 0.1334 (first half incubation times)/-0.1888 ± 0.1354 (second half incubation times), respectively, whereas no enantioselectivity occurred during PCB183 biotransformation. More importantly, although there was no carbon and chlorine isotope fractionation occurring for studied substrates, the δ13C values of dechlorination products, including PCB47 (-28.15 ± 0.35‰ âˆ¼ -27.77 ± 0.20‰), PCB91 (-36.36 ± 0.09‰ âˆ¼ -34.71 ± 0.49‰), and PCB149 (-28.08 ± 0.26‰ âˆ¼ -26.83 ± 0.10‰), were all significantly different from those of their corresponding substrates (PCB85: -30.81 ± 0.02‰ âˆ¼ -30.22 ± 0.21‰, PCB132: -33.57 ± 0.15‰ âˆ¼ -33.13 ± 0.14‰, and PCB174: -26.30 ± 0.09‰ âˆ¼ -26.01 ± 0.07‰), which further supported the generation of other non-dehalogenation products and/or stable intermediates with enrichment or depletion of 13C. These findings provide deeper insights into the anaerobic microbial transformation behaviors of PCBs.