The loss of B7-H4 expression in breast cancer cells escaping from T cell cytotoxicity contributes to epithelial-to-mesenchymal transition.

BACKGROUND: B7 homology 4 (B7-H4), a potential target for cancer therapy, has been demonstrated to inhibit T cell cytotoxicity in the early stages of breast cancer. However, B7-H4 manipulating breast tumor immune microenvironment (TIME) in the tumor progression remains unknown. METHODS: We engineered T cells with B7-H4-specific chimeric antigen receptors (CARs) and performed a T cell co-culture assay to characterize B7-H4 expression level in breast cancer cells escaping from T cell cytotoxicity. We generated B7-H4 knockout (KO) and overexpression (OE) breast cancer cells to determine the epithelial-to-mesenchymal transition (EMT) and stemness characteristics in vitro and in vivo, including tumor proliferation, migration, metastasis and chemoresistance. The Cancer Genome Atlas breast cancer database was accessed to investigate the correlation between B7-H4 expression levels and EMT characteristics in patients with breast cancer. RESULTS: Our result found that B7-H4 expression level was significantly reduced in a subset of breast cancer cells that escaped from the cytotoxicity of B7-H4 CAR-T cells. Compared with wild type cells, B7-H4 KO cells prompt EMT and stemness characteristics, including migration, invasion and metastasis, and OE cells vice versa. The increase in H3K27me3 in KO cells confirmed the epigenetic reprogramming of cancer stem cells. The IC50 of doxorubicin or oxaliplatin significantly increased in KO cells, which was in agreement with a decrease in OE cells. Moreover, a trend of downregulated B7-H4 from stage I to stage II breast cancer patients indicates that the low-expressing B7-H4 breast cancer cells escaping from TIME have spread to nearby breast lymph nodes in the cancer progression. CONCLUSIONS: Our study illuminates the novel role of renouncing B7-H4 in breast cancer cells through immune escape, which contributes to EMT processes and provides new insights for breast cancer treatments.

Fluorogenic methodology for visualization of phase separation in chemical biology.

Phase separation is a common biological phenomenon in the liquid environment of organisms. Phase separation has been shown to be a key cause of many existing incurable diseases, such as the protein aggregates formed by phase separation of Alzheimer's Disease, Amyotrophic Lateral Sclerosis, Parkinson's disease, etc. Tracking the occurrence of phase separation in vivo is critical to many disease detection methods and solving many treatment problems. Its physicochemical properties and visual detection methods have flourished in the last few years in chemical biology, among which the fluorogenic toolbox has great application potential compared to the traditional detection methods that cannot visualize the phase separation process intuitively, but just show some parameters indirectly. This paper reviews the mechanism and disease correlation proven in recent years for phase separation and analyzes the detection methods for phase separation, including functional microscope imaging techniques, turbidity monitoring, macromolecule congestion sensing, in silico analysis, etc. It is worth mentioning that the qualitative and quantitative analysis of aggregates formed by phase separation using in vitro parameters has successfully provided basic physical and chemical properties for phase separation aggregates, and is an important cornerstone for researchers to carry forward the past and break through the existing technical shackles to create new in vivo monitoring methods such as fluorescence methodology. Crucially, fluorescence methods for cell microenvironment imaging based on different mechanisms are discussed, such as AIE-based probes, TICT-based probes and FRET-based probes, etc.

Quantifying Carbon Cycling across the Groundwater-Stream-Atmosphere Continuum Using High-Resolution Time Series of Multiple Dissolved Gases.

The quantification of carbon cycling across the groundwater-stream-atmosphere continuum (GSAC) is crucial for understanding regional and global carbon cycling. However, this quantification remains challenging due to highly coupled carbon exchange and turnover in the GSAC. Here, we disentangled carbon cycling processes in a representative groundwater-stream-atmosphere transect by obtaining and numerically simulating high-resolution time series of dissolved He, Ar, Kr, O2, CO2, and CH4 concentrations. The results revealed that groundwater contributed ∼60% of CO2 and ∼30% of CH4 inputs to the stream, supporting stream CO2 and CH4 emissions to the atmosphere. Furthermore, diurnal variations in stream metabolism (-0.6 to 0.6 mol O2 m-2 day-1) induced pronounced carbonate precipitation during the day and dissolution at night. The significant diurnal variability of biogeochemical processes emphasizes the importance of high-resolution time series investigations of carbon dynamics. This study shows that dissolved gases are promising environmental tracers for discerning and quantifying carbon cycling across the GSAC with high spatiotemporal resolution. Our high-resolution carbon exchange and turnover quantification provides a process-oriented and mechanistic understanding of carbon cycling across the GSAC.

Spatial variability and source analysis of typical soil trace elements at permafrost section along national highway 214 in the eastern Qinghai-Tibet Plateau.

This paper attempts to reveal the enrichment status, spatial characteristics and material sources of typical soil trace elements at permafrost section along National Highway 214 on the Qinghai-Tibet Plateau. Therefore, the samples of typical trace elements in surface soil, being located at the northern slope of Bayan Kara Mountains, were collected and tested. The concentrations of typical trace elements in soil were analysed by mathematical statistics, spatial analysis and ecological assessment. The results show that: (1) the concentrations of As, Cd and Hg in the soil are higher than the local background values, and their degrees of variation were high. There was a certain degree of accumulation. Soil As and Hg elements constitute "slight pollution", indicating there is a none-to-slight ecological hazard. (2) The distributions of soil As, Cd, Pb and Zn concentrations are lower near the highway and increase with distance from it and then become relatively low further away. The distributions of Cr, Cu, Hg and Ni concentrations show no obvious trends in any direction. (3) The spatial heterogeneity of typical trace elements in soil is affected by soil organic matter (SOM), cation exchange capacity (CEC), pH, slope curvature and aspect. At the local scale, soil texture and topography were the main affecting factors. Concentrations of Cd, Cr, Cu, Ni, Pb and Zn were mainly affected by natural factors, while those of As and Hg were affected by both natural and human factors.

Complete Reductive Dechlorination of 4-Hydroxy-chlorothalonil by Dehalogenimonas Populations.

Chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile, TePN) is one of the most widely used fungicides all over the world. Its major environmental transformation product 4-hydroxy-chlorothalonil (4-hydroxy-2,5,6-trichloroisophthalonitrile, 4-OH-TPN) is more persistent, mobile, and toxic and is frequently detected at a higher concentration in various habitats compared to its parent compound TePN. Further microbial transformation of 4-OH-TPN has never been reported. In this study, we demonstrated that 4-OH-TPN underwent complete microbial reductive dehalogenation to 4-hydroxy-isophthalonitrile via 4-hydroxy-dichloroisophthalonitrile and 4-hydroxy-monochloroisophthalonitrile. 16S rRNA gene amplicon sequencing demonstrated that Dehalogenimonas species was enriched from 6% to 17-22% after reductive dechlorination of 77.24 µmol of 4-OH-TPN. Meanwhile, Dehalogenimonas copies increased by one order of magnitude and obtained a yield of 1.78 ± 1.47 × 108 cells per µmol Cl- released (N = 6), indicating that 4-OH-TPN served as the terminal electron acceptor for organohalide respiration of Dehalogenimonas species. A draft genome of Dehalogenimonas species was assembled through metagenomic sequencing, which harbors 30 putative reductive dehalogenase genes. Syntrophobacter, Acetobacterium, and Methanosarcina spp. were found to be the major non-dechlorinating populations in the microbial community, who might play important roles in the reductive dechlorination of 4-OH-TPN by the Dehalogenimonas species. This study first reports that Dehalogenimonas sp. can also respire on the seemingly dead-end product of TePN, paving the way to complete biotransformation of the widely present TePN and broadening the substrate spectrum of Dehalogenimonas sp. to polychlorinated hydroxy-benzonitrile.

Investigating transport kinetics of polystyrene nanoplastics in saturated porous media.

Understanding the fate and transport of polystyrene nanoparticles (PSNPs) in porous media under various conditions is necessary for evaluating and predicting environmental risks caused by microplastics. The transport kinetics of PSNPs are investigated by column experiment and numerical model. The surface of DLVO interaction energy is calculated to analyze and predict the adsorption and aggregation of PSNPs in porous media, which the critical ionic strength of PSNPs can be accurately investigated. The results of the DLVO energy surface suggest that when the concentration of Na+ increases from 1 mM to 50 mM, the DLVO energy barrier of PSNPs-silica sand (SS) decreases from 78.37 kT to 5.46 kT. As a result, PSNPs are easily adsorbed on the surface of SS and the mobility of PSNPs is reduced under the condition of a high concentration of Na+ (PSNPs recovery rate decreases from 62.16% to 3.65%). When the concentration of Ca2+ increases from 0.1 mM to 5 mM, the DLVO energy barrier of PSNPs-SS decreases from 12.10 kT to 1.90 kT, and PSNPs recovery rate decreases from 82.46% to 4.27%. Experimental and model results showed that PSNPs mobility is enhanced by increasing initial concentration, flow velocity and grain size of SS, while the mobility of PSNPs with larger particle diameter is lower. Regression analysis suggests that kinetic parameters related to PSNPs mobility are correlated with DLVO energy barriers. The environmental behavior and mechanism of PSNPs transport in porous media are further investigated in this study, which provides a scientific basis for the systematic and comprehensive evaluation of the environmental risk and ecological safety of nano-plastic particles in the groundwater system.

Effects of nanometer alumina and humic acid on the retention and transport of hexavalent chromium in porous media.

Column experiments were conducted to investigate the effects of ion type, ion strength, humic acid (HA), and nanometer alumina (NA) particles on the transport of hexavalent chromium (HC) in saturated porous media. A one-dimensional model is developed to simulate the migration of HC affected by NA particles. The results show that nano-alumina particles would enhance the mobility of HC in saturated porous media. However, the influence of NA on the migration of HC in porous media is complex. When the concentration of NA reaches 30 mg/L, HC has minimum retention parameter and best mobility. The transport of HC also is affected by ion strength and ion type. Higher ionic strength would decrease the retention of HC and enhance its mobility. Compared with sodium ion, calcium ion has larger effects on the transport of HC. Moreover, HA can improve the mobility of HC in saturated porous media, but the corresponding promoting effect decreases with the increase of HA concentration. As nanometer contaminants and HC come into the subsurface environment, findings from this study elucidate the key factors and processes controlling the transport of HC in porous media, which can promote the prediction and assessment of HC in the groundwater system.

Enriched environment improves post-stroke cognitive impairment and inhibits neuroinflammation and oxidative stress by activating Nrf2-ARE pathway.

INTRODUCTION: Neuroinflammation and oxidative stress are major mechanisms of post-stroke cognitive impairment (PSCI) neural injury and decreased spatial and memory capacity. Enriched environment (EE) is an effective method to improve cognitive dysfunction. However, the regulation by EE of neuroinflammation, oxidative stress and associated mechanisms in animal models remains unclear. MATERIALS AND METHODS: In this study, a rat PSCI model was established by middle cerebral artery occlusion (MCAO). Rats were randomly divided into the control group, standard environment (SE) group and EE group for 28 days. A Morris water-maze test was used to measure cognitive function at 7, 14 and 28 days after MCAO. Rats were sacrificed on the 28th day. Quantitative PCR, immunohistochemistry and ELISA were respectively used to detect mRNA expression of NF-E2-related factor 2 (Nrf2) and Nrf2 response genes, the expression of IL-1ß and levels of proinflammatory cytokines in the hippocampus. RESULTS: EE improved mNSS scores and cognitive ability in PSCI rats. EE increased mRNA expression of the Nrf2 and Nrf2 response genes, including heme oxygenase-1 (HO-1) and NAD(P)H:quinone oxidoreductase 1 (NQO1). EE significantly decreased the level of malondialdehyde (MDA) and increased the levels of superoxide dismutase (SOD) and glutathione (GSH), in the hippocampus of PSCI rats. EE reduced the number of IL-1ß positive cells in the hippocampus, and IL-1ß levels in the hippocampus and serum. EE increased GFAP-positive astrocytes in the hippocampus, and BDNF levels in the hippocampus and serum. CONCLUSIONS: EE can improve cognitive function in PSCI rats by inhibiting neuroinflammation and oxidative stress.

A conjunctive management framework for the optimal design of pumping and injection strategies to mitigate seawater intrusion.

Coastal aquifer management (CAM) considering conjunctive optimization of pumping and injection system for seawater intrusion (SI) mitigation poses significant decision-making challenges. CAM needs to pose multiple objectives and massive decision variables to explore tradeoff strategies between the conflicting resources, economic, and environmental requirements. Here, we investigate a joint artificial injection scheme for ameliorating SI by establishing an evolutionary multi-objective decision-making framework that combines simulation-optimization (S-O) modelling with a cost-benefit analysis, and demonstrate the framework on a large-scale CAM case in Baldwin County, Alabama. First, a SI numerical model, using SEAWAT, was configured to predict the vulnerable region as an SI encroachment area with the scenarios of minimum and maximum pumping capacity. As a result, a smaller number of candidate sites were selected in the SI encroachment area for implementing groundwater injection to avoid the computationally infeasible SI optimization with an inordinate number of injection related decision variables. Second, the effective S-O methodology of niched Pareto tabu search combined with a genetic algorithm (NPTSGA), which considers the moving-well option, was applied to discover optimal pumping/injection (P/I) strategies (including P/I rates and injection well locations) between three conflicting management objectives under complicated SI constraints. Third, for practical operation of the P/I schemes, a cost-benefit analysis provides judgment criteria to allow decision-makers to implement more sustainable P/I strategies to capture the different realistic preferences. The implementation of three extreme optimization solutions for the case study indicates that, compared to the initial unoptimized scheme, a maximum increase of a factor of 3 in groundwater extraction rates, a maximum reduction of 17% in extent of SI, and a maximum 82.3 million US dollars in comprehensive benefits are specifically achieved by conjunctive P/I optimization. The robustness in the decision alternatives attributed to the uncertainty in physical parameters of hydraulic conductivity was discovered through global sensitivity analysis. The proposed framework provides a decision support system for multi-objective CAM with combined pumping control and engineering measures for SI mitigation.

Microbial Communities Associated with Sustained Anaerobic Reductive Dechlorination of α-, ß-, γ-, and δ-Hexachlorocyclohexane Isomers to Monochlorobenzene and Benzene.

Intensive historical and worldwide use of pesticide formulations containing hexachlorocyclohexane (HCH) has led to widespread contamination. We derived four anaerobic enrichment cultures from HCH-contaminated soil capable of sustainably dechlorinating each of α-, ß-, γ-, and δ-HCH isomers stoichiometrically to benzene and monochlorobenzene (MCB). For each isomer, the dechlorination rates, inferred from production rates of the dechlorinated products, MCB and benzene, increased progressively from <3 to ∼12 µM/day over 2 years. The molar ratio of benzene to MCB produced was a function of the substrate isomer and ranged from ß (0.77 ± 0.15), α (0.55 ± 0.09), γ (0.13 ± 0.02), to δ (0.06 ± 0.02) in accordance with pathway predictions based on prevalence of antiperiplanar geometry. Data from 16S rRNA gene amplicon sequencing and quantitative PCR revealed significant increases in the absolute abundances of Pelobacter and Dehalobacter, most notably in the α-HCH and δ-HCH cultures. Cultivation with a different HCH isomer resulted in distinct bacterial communities, but similar archaeal communities. This study provides the first direct comparison of shifts in anaerobic microbial communities induced by the dechlorination of distinct HCH isomers. It also uncovers candidate microorganisms responsible for the dechlorination of α-, ß-, γ-, and δ-HCH, a key step toward better understanding and monitoring of natural attenuation processes and improving bioremediation technologies for HCH-contaminated sites.

A probabilistic modeling framework for assessing the impacts of large reservoirs on river thermal regimes - A case of the Yangtze River.

Hydrological and thermal river regimes have changed greatly due to the construction of reservoirs and dams. Water temperature changes have important significance for aquatic habitats and freshwater ecosystems. To investigate the impact of large reservoirs on the water temperature regime along the middle reach of the Yangtze River, we present a probabilistic modeling framework to ascertain the joint dependence structures of air-water temperature and discharge-water temperature between pre-reservoir and post-reservoir periods based on the copula theory. The results show that the principle of maximum entropy (POME) method can better estimate the marginal distributions of temperature regimes. Reservoir operation disturbed the dependence structures of air-water temperature, especially after the Three Gorges Reservoir (TGR) was put into operation. Different shifts in the occurrence probabilities of high or low water temperatures at the downstream and upstream stations under extreme air temperature and discharge are observed, indicating the great effects of reservoirs on the dependence structures of the downstream river flow and thermal regime. Relying on the developed model, we propose the appropriate ranges of air temperature and discharge to maintain a suitable water temperature for Chinese sturgeon (Acipenser sinensis) spawning activity. The results of this study demonstrate the influence of dams on the thermal regime and can be helpful for optimizing reservoir operations to enhance biological conservation in the Yangtze River.

Quantifying the change in streamflow complexity in the Yangtze River.

Hydrological processes of the Yangtze River have changed over the past decades due to environmental change and human activity. This paper uses sample entropy to investigate the spatial distribution and dynamic change in streamflow series complexity in the Yangtze River, China. In this study, the complexity of the streamflow series is quantified by entropy analysis. Daily streamflow series for four stations located in the mainstem and two control stations of the two largest freshwater lakes were analysed for the past 60 years. The results showed that the complexity of the streamflow series showed an obvious spatial difference and an increasing trend from upstream to downstream in the Yangtze River. There was a negative relationship between the annual streamflow and the corresponding sample entropy, and their peak-to-valley values showed well-corresponding relationships. The complexity of the runoff series at the Cuntan, Yichang, and Datong stations showed a continuous increasing trend, while that of the Hankou station showed a decreasing trend. The Three Gorges Dam changed the streamflow series complexity in the middle reach of the Yangtze River during the initial impoundment stage, while it had only slight impacts during the fully operational stage. Compared to the mainstem reaches, the streamflow series complexity of the two lakes showed no obvious change. The complexity of the streamflow series in the mainstem of the Yangtze River has been influenced by dam construction. The study could provide a scientific reference for understanding the flow dynamic evolution in the Yangtze River.

Developing a dual entropy-transinformation criterion for hydrometric network optimization based on information theory and copulas.

Hydrometric information collected by monitoring networks is fundamental for effective management of water resources. In recent years, entropy-based multi-objective criterions have been developed for the evaluation and optimization of hydrometric networks, and copula functions have been frequently used in hydrological frequency analysis to model multivariate dependence structures. This study developed a dual entropy-transinformation criterion (DETC) to identify and prioritize significant stations and generate candidate network optimization solutions. The criterion integrated an entropy index computed with mathematical floor function and a transinformation index computed with copula entropy through a tradeoff weight. The best fitted copula models were selected from three Archimedean copula families, i.e., Gumbel, Frank and Clayton. DETC was applied to a streamflow monitoring network in the Fenhe River basin and two rainfall monitoring networks in the Beijing Municipality and the Taihu Lake basin, which covers different network classification, network scale, and climate type. DETC was assessed by the commonly used dual entropy-multiobjective optimization (DEMO) criterion and was compared with a minimum transinformation (MinT) based criterion for network optimization. Results showed that DETC could effectively prioritize stations according to their significance and incorporate decision preference on information content and information redundancy. Comparison of the isohyet maps of two rainstorm events between DETC and MinT showed that DETC had advantage of restoring the spatial distribution of precipitation.

Improved comprehensive ecological risk assessment method and sensitivity analysis of polycyclic aromatic hydrocarbons (PAHs).

Based on the existing comprehensive ecological risk assessment methods of PAHs, this paper proposed an improved hierarchical Archimedean copula integral assessment (HACIA) model with the optimization in the model selection mechanism and accelerating the calculation speed, and according to which performed the sensitivity analysis of the integrated risk relative to the underlying grouped risk probability. Taihu Lake in China and the Bay of Santander in Spain were taken as study areas, whose samples were obtained and extracted concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs). After briefly analyzing their concentration characteristics and source, their comprehensive ecological risks were evaluated by the improve HACIA model and their sensitivity was also analyzed. The results proved that, for Taihu Lake, pyrogenic sources occupied the dominance, especially grass, coal and wood combustion, while the risk proportion of 5-rings PAHs was the lowest indeed based on the improved HAICA model. For the Bay of Santander, source apportionment indicated both petrogenic and pyrogenic sources, mainly from vehicle emissions including gasoline and diesel engines, and 4-ring PAHs were urgently needed to be managed. However, the sensitivity analysis results of two study areas showed that the most effective control target for reducing integral risk has no obvious relationship with the maximum grouped risk. And a clear linear relationship between the maximum sensitivity range and the logarithm of the initial overall risk only presented in one of study areas, which required further research to clarify. In brief, the improved HACIA model is helpful to evaluate the comprehensive ecological risk of 16 PAHs, and formulate risk management strategies based on grouped risk assessment and sensitivity analysis, with the former points out the admonitory risk and the latter helps to find the most effective mitigation measures.

Effects of Temperature, Solution pH, and Ball-Milling Modification on the Adsorption of Non-steroidal Anti-inflammatory Drugs onto Biochar.

This study explored the adsorption of representative non-steroidal anti-inflammatory drugs (NSAIDs), acetaminophen (AP), ibuprofen (IB), and salicylic acid (SA) by biochars. The sorption kinetics were fitted with six commonly used kinetic models, and the isotherm data was well described by both Langmuir and Freundlich models. Biochars of longer pyrolysis time showed better performance with the Langmuir maximum sorption capacities for AP, IB, and SA of 196 mg/g, 132 mg/g, and 48.8 mg/g, respectively. Variation in temperature hardly affected the adsorption performances, while the influence of pH exhibited pronounced dependency on physicochemical properties of both NSAIDs and biochars. Eighteen ball-milled (BM) biochars were then produced under different ball-milling conditions and examined for NSAIDs removal. Compared with unmilled biochars, BM-biochars produced under optimum conditions showed higher removal efficiencies. Electrostatic interaction and pore width of biochars greatly affected the NSAIDs adsorption onto biochars.

Evaluation of information transfer and data transfer models of rain-gauge network design based on information entropy.

Rainfall is one of the most fundamental components of the water cycle and is one of the fundamental inputs of hydrological models. A well-designed network can not only depict the regional precipitation characteristics, but also economically yield maximum needed rainfall information. In regions where either there is limited data or data is not available, it is a common challenge to add stations. The entropy theory-based information transfer model and geostatistical interpolation techniques are two solutions to meet the challenge. In this study, we used a representative rain gauge network to do the network design. Two models, based on information transfer and data transfer, were compared for network design. Other rain gauges in the study area were used as reference ("true values") for assessing the model. Results showed that the information transfer model estimated transinformation between station pairs better than did the data transfer model. Different representative gauges were evaluated separately by the directional information transfer index (DIT). The candidate gauges selected with least information redundancy were similar for both information transfer and data transfer models. Though both models captured some least information-redundant areas, other areas may be bypassed because of model errors or estimation errors.

Suspect and Nontarget Screening of Per- and Polyfluoroalkyl Substances in Wastewater from a Fluorochemical Manufacturing Park.

Although per- and polyfluoroalkyl substances (PFASs) have always been a key issue in the global environmental field, there are still a lot of undiscovered PFASs in the environment due to new PFAS alternatives developed by manufacturers. Wastewater treatment plants (WWTPs), as one of the sources for PFASs, are an important part of the process of releasing new PFASs into the environment. In this study, suspect screening and PFAS homologue analysis with quadrupole time-of-flight tandem mass spectrometry were used to discover PFASs in wastewater from a WWTP near Yangtze River. Fifteen classes with 90 PFASs were identified, including 12 legacy PFASs (2 classes), 41 previously reported PFASs (7 classes), and 37 new PFASs (6 classes), and 18 of these PFASs were also detected in the nearby Yangtze River. Only 1 PFAS class was removed through the treatment processes (fold change < 1/6). Conversely, 4 PFAS classes increased through the treatment processes (fold change > 6), which could be the transformation products of PFAS precursors. These results implied that most discovered PFASs were not effectively removed in the WWTP. Chlorine-substituted perfluoroalkyl carboxylates (Cl-PFCAs) as the main component of wastewater were detected only in downstream, meaning that Cl-PFCAs in downstream possibly originated from the WWTP.

A Dehalogenimonas Population Respires 1,2,4-Trichlorobenzene and Dichlorobenzenes.

Chlorobenzenes are ubiquitous contaminants in groundwater and soil at many industrial sites. Previously, we demonstrated the natural attenuation of chlorobenzenes and benzene at a contaminated site inferred from a 5 year site investigation and parallel laboratory microcosm studies. To identify the microbes responsible for the observed dechlorination of chlorobenzenes, the microbial community was surveyed using 16S rRNA gene amplicon sequencing. Members of the Dehalobacter and Dehalococcoides are reported to respire chlorobenzenes; however, neither were abundant in our sediment microcosms. Instead, we observed a significant increase in the relative abundance of Dehalogenimonas from <1% to 16-30% during dechlorination of 1,2,4-trichlorobenzene (TCB), 1,2-dichlorobenzene (DCB), and 1,3-DCB over 19 months. Quantitative PCR (qPCR) confirmed that Dehalogenimonas gene copies increased by 2 orders of magnitude with an average yield of 3.6 ± 2.3 g cells per mol Cl- released ( N = 12). In transfer cultures derived from sediment microcosms, dechlorination of 1,4-DCB and monochlorobenzene (MCB) was carried out by Dehalobacter spp. with a growth yield of 3.0 ± 2.1 g cells per mol Cl- released ( N = 5). Here we show that a Dehalogenimonas population respire 1,2,4-TCB and 1,2-/1,3-DCB isomers. This finding emphasizes the need to monitor a broader spectrum of organohalide-respiring bacteria, including Dehalogenimonas, at sites contaminated with halogenated organic compounds.

Natural Attenuation and Anaerobic Benzene Detoxification Processes at a Chlorobenzene-Contaminated Industrial Site Inferred from Field Investigations and Microcosm Studies.

A five-year site investigation was conducted at a former chemical plant in Nanjing, China. The main contaminants were 1,2,4-trichlorobenzene (TCB) reaching concentrations up to 7300 µg/L, dichlorobenzene (DCB) isomers, monochlorobenzene (MCB), and benzene. Over time, these contaminants naturally attenuated to below regulatory levels under anaerobic conditions. To confirm the transformation processes and to explore the mechanisms, a corresponding laboratory microcosm study was completed demonstrating that 1,2,4-TCB was dechlorinated to 1,2-DCB, 1,3-DCB, and 1,4-DCB in approximately 2%/10%/88% molar proportions. The DCB isomers were dechlorinated via MCB to benzene, and, finally, benzene was degraded under prevailing sulfate-reducing conditions. Dechlorination could not be attributed to known dechlorinators Dehalobacter or Dehalococcoides, while anaerobic benzene degradation was mediated by microbes affiliated to a Deltaproteobacterium ORM2, previously associated with this activity. Unidentified organic compounds, possibly aromatic compounds related to past on-site production processes, were fueling the dechlorination reactions in situ. The microcosm study confirmed transformation processes inferred from field data and provided needed assurance for natural attenuation. Activity-based microcosm studies are often omitted from site characterization in favor of rapid and less expensive molecular surveys. However, the value of microcosm studies for confirming transformation processes, establishing electron balances, assessing cocontaminant inhibition, and validating appropriate monitoring tools is clear. At complex sites impacted by multiple compounds with poorly characterized transformation mechanisms, activity assays provide valuable data to incorporate into the conceptual site model to most effectively inform remediation alternatives.

Hydroxyl Radical Based Photocatalytic Degradation of Halogenated Organic Contaminants and Paraffin on Silica Gel.

Photochemical materials are of scientific and practical importance in the field of photocatalysis. In this study, the photochemistry of several organic contaminants, including decabromodiphenyl ether (BDE-209), halogenated phenols (C6 X5OH, X = F, Cl, Br) and paraffin, on silica gel (SG) surface was investigated under simulated solar irradiation conditions. Photolysis of these compounds at the solid/air interface proceeds with different rates yielding various hydroxylation products, and hydroxyl radical was determined as the major reactive species. According to density functional theory (DFT) calculations, the reaction of physically adsorbed water with reactive silanone sites (>Si═O) on silica was indispensable for the generation of •OH radical, where the required energy matches well with the irradiation energy of visible light. Then, the BDE-209 was selected as a representative compound to evaluate the photocatalytic performance of SG under different conditions. The SG material showed good stability in the photodegradation process, and was able to effectively eliminate BDE-209 under natural sunlight. These findings provide new insights into the potential application of SG as a solid surface photocatalyst for contaminants removal.