Photoinduced Nickel-Catalyzed Carbon-Heteroatom Coupling.

Herein, we report visible light-promoted single nickel catalysis for diverse carbon-heteroatom couplings under mild conditions. This mild, general, and robust method to couple diverse nitrogen, oxygen, and sulfur nucleophiles with aryl(heteroaryl)/alkenyl iodides/bromides exhibits a wide functional group tolerance and is applicable to late-stage modification of pharmaceuticals and natural products. On the base of preliminary mechanistic studies, a NiI /NiIII cycle via the generation of active NiI complexes that appear from homolysis of NiII -I rather than NiII -aryl bond was tentatively proposed.

Spatiotemporal characteristics and dynamic risk assessment of a multi-solvents abandoned pesticide-contaminated site with a long history, in China.

With the development of the economy and the adjustment of urban planning and layout, abandoned pesticide sites are widely distributed in major and medium cities in China. Groundwater pollution of a large number of abandoned pesticide-contaminated sites has caused great potential risks to human health. Up to now, few relevant studies concerned the spatiotemporal variation of risks exposure to multi-pollutants in groundwater using probabilistic methods. In our study, the spatiotemporal characteristics of organics contamination and corresponding health risks in the groundwater of a closed pesticide site were systematically assessed. A total of 152 pollutants were targeted for monitoring over a time span up to five years (i.e., June 2016-June 2020). BTEX, phenols, chlorinated aliphatic hydrocarbons, and chlorinated aromatic hydrocarbons were the main contaminants. The metadata was subjected to health risk assessments using the deterministic and probabilistic methods for four age groups, and the results showed that the risks were highly unacceptable. Both methods showed that children (0-5 years old) and adults (19-70 years old) were the age groups with the highest carcinogenic and non-carcinogenic risks, respectively. Compared with inhalation and dermal contact, oral ingestion was the predominant exposure pathway that contributed 98.41%-99.69% of overall health risks. Spatiotemporal analysis further revealed that the overall risks first increased then decreased within five years. The risk contributions of different pollutants were also found to vary substantially with time, indicating that dynamic risk assessment is necessary. Compared with the probabilistic method, the deterministic approach relatively overestimated the true risks of OPs. The results provide a scientific basis and practical experience for scientific management and governance of abandoned pesticide sites.

Source apportionment and health risk assessment of chemicals of concern in soil, water and sediment at a large strontium slag pile area.

Strontium (Sr) is an alkaline earth metal that has adverse effects on bone tissue, but received little attention compared to other often-studied metals. This study analyzed the contents/concentrations of Sr, barium (Ba), sulfate (SO42-), sulfide (S2-), and six common metals in 209 multi-media samples, including slag, soil, groundwater, surface water, and sediment, collected at a large Sr slag pile area. Sr was the dominant chemical of concern (COC) in the soil and groundwater, with contents/concentrations being 35.50-32200 mg/kg and 0.57-152 mg/L, respectively, much higher than those reported in previous research. Contents/concentrations of all COCs in the surface water and sediment were relatively low, except Sr content in the sediment near the slag pile. The LogKd value of Sr was calculated to be lower than those of common metals, indicating relatively high mobility of Sr in the aquatic environment. Contamination assessment using Nemerow index indicated near half of the soil and groundwater sampling locations, especially those within and near the slag pile, were heavily contaminated, and Sr was the dominant COC. The positive matrix factorization model suggested four sources for the COCs in soil, including Sr slag pile/SrCO3 production, agricultural activities, industrial activities, and natural sources, with contribution rates of 66.88%, 5.28%, 7.5%, and 20.34%, respectively. Monte Carlo simulation-based probabilistic health risk assessment revealed that the non-carcinogenic risk of groundwater, and the carcinogenic risk of soil and groundwater, were unacceptable. Notably, Sr was the unique COC posing non-carcinogenic risk among the COCs studied. Our results provide the scientific support needed for managing Sr point source impacted area.

Response of microbial communities in aquifers with multiple organic solvent contamination: Implications for MNA remedy.

The application of Monitored Natural Attenuation (MNA) technology has been widespread, while there is a paucity of data on groundwater with multiple co-contaminants. This study focused on high permeability, low hydraulic gradient groundwater with co-contamination of benzene, toluene, ethylbenzene, and xylenes (BTEX), chlorinated aliphatic hydrocarbons (CAHs), and chlorinated aromatic hydrocarbons (CPs). The objective was to investigate the responses of microbial communities during natural attenuation processes. Results revealed greater horizontal variation in groundwater microbial community composition compared to vertical variation. The variation was strongly correlated with the total contaminant quantity (r = 0.722, p < 0.001) rather than individual contaminants. BTEX exerted a more significant influence on community diversity than other contaminants. The assembly of groundwater microbial communities was primarily governed by deterministic processes (ßNTI < -2) in high contaminant concentration zones, while stochastic processes (|ßNTI| < 2) dominated in low-concentration zones. Moreover, the microbial interactions shifted at different depths indicating the degradation rate variation in the vertical. This study makes fundamental contribution to the understanding for the effects of groundwater flow and material fields on indigenous microbial communities, which will provide a scientific basis for more precise adoption of microbial stimulation/augmentation to accelerate the rate of contaminant removal.

Research on pollution identification and safety thresholds based on the olfactory effect on a halogenated hydrocarbon contaminated site.

To effectively address odor control issues at sites contaminated with halogenated hydrocarbons, it is essential to establish an odor risk prediction system for evaluating potential risks that may impact future planning. This research focuses on a representative halogenated hydrocarbon-contaminated site, examining the spatial and temporal distribution characteristics of key pollutants in soil gas. By analyzing odor contribution rates, the study identifies significant odorants in soil gas, which enables the derivation of both probabilistic and deterministic safety thresholds for soil and groundwater based on olfactory effects. The findings indicate that 1,1-dichloroethylene, vinyl chloride, chloroform, and 1,1-dichloroethane are prevalent throughout the contaminated site, displaying elevated concentration levels and substantially influencing the overall contamination extent. These substances are highlighted as critical pollutants requiring attention. Correlation analysis (P < 0.05) reveals a strong relationship between the concentrations of vinyl chloride, 1,1-dichloroethane, and chloroform with groundwater depth and air temperature. Additionally, the analysis of odor activity values (OAV) identified 1,1-dichloroethene, 1,4-dichlorobenzene, chlorobenzene, chloroform, and vinyl chloride as key olfactory factors at the site. The corresponding probabilistic safety thresholds are 0.68, 1.65, 0.50, 7.87, and 3.72 mg kg-1 for soil, and 9.29, 3.46, and 1.09, 69.55, and 47.01 mg L-1 for groundwater, respectively. Among them, the odor risks of chlorobenzene and 1,1-dichloroethylene warrant more attention than soil contamination risks; regarding 1,4-dichlorobenzene, it is recommended to concurrently consider odor risks during human health risk assessment; as for vinyl chloride and chloroform, their odor risks can be largely eliminated based on human health-oriented pollution management.

Risk assessment and source analysis of heavy metals in soil around an asbestos mine in an arid plateau region, China.

Asbestos is widely used in construction, manufacturing, and other common industrial fields. Human activities such as mining, processing, and transportation can release heavy metals from asbestos into the surrounding soil environment, posing a health hazard to the mining area's environment and its surrounding residents. The purpose of the present study was to determine the extent of ecological and human health damage caused by asbestos pollution, as well as the primary contributors to the contamination, by examining a large asbestos mine and the surrounding soil in China. The level of heavy metal pollution in soil and sources were analyzed using methods such as the geo-accumulation index (Igeo), potential ecological risk index (RI), and positive matrix factorization (PMF) model. A Monte Carlo simulation-based health risk model was employed to assess the health risks of heavy metals in the study area's soil to human beings. The results showed that the concentrations of As, Pb, Cr, Cu, and Ni in the soil were 1.74, 0.13, 13.31, 0.33, and 33.37 times higher than the local soil background values, respectively. The Igeo assessment indicated significant accumulation effects for Ni, Cr, and As. The RI evaluation revealed extremely high comprehensive ecological risks (RI ≥ 444) in the vicinity of the waste residue heap and beneficiation area, with Ni exhibiting strong individual potential ecological risk (Eir ≥ 320). The soil health risk assessment demonstrated that As and Cr posed carcinogenic risks to adults, with mean carcinogenic indices (CR) of 1.56E - 05 and 4.14E - 06, respectively. As, Cr, and Cd posed carcinogenic risks to children, with mean CRs of 1.08E - 04, 1.61E - 05, and 2.68E - 06, respectively. Cr also posed certain non-carcinogenic risks to both adults and children. The PMF model identified asbestos contamination as the primary source of heavy metals in the soil surrounding the asbestos mining area, contributing to 79.0%. According to this study, it is recommended that management exercise oversight and regulation over the concentrations of Ni, Cr, Cd, and As in the soil adjacent to asbestos mines, establish a designated control zone to restrict population activities, and locate residential zones at a safe distance from the asbestos mine production zone.

Can we redevelop ammonia nitrogen contaminated sites without remediation? The key role of subsurface pH in human health risk assessment.

Nitrogen fertilizer supports global food production, but its manufacturing results in substantial ammonia nitrogen (AN) contaminated sites which remain largely unexplored. In this study, ten representative AN contaminated sites were investigated, covering a wide range of subsurface pH, temperature, and AN concentration. A total of 7232 soil samples and 392 groundwater samples were collected to determine the concentration levels, migration patterns, and accurate health risks of AN. The results indicated that AN concentrations in soil and groundwater reached 12700 mg/kg and 12600 mg/L, respectively. AN concentrations were higher in production areas than in non-production areas, and tended to migrate downward from surface to deeper soil. Conventional risk assessment based on AN concentration identified seven out of the ten sites presenting unacceptable risks, with remediation costs and CO2 emissions amounting to $1.67 million and 17553.7 tons, respectively. A novel risk assessment model was developed, which calculated risks based on multiplying AN concentration by a coefficient fNH3 (the ratio of NH3 to AN concentration). The mean fNH3 values, primarily affected by subsurface pH, varied between 0.02 and 0.25 across the ten sites. This new model suggested all investigated sites posed acceptable health risks related to AN exposure, leading to their redevelopment without AN-specific remediation. This research offers a thorough insight into AN contaminated site, holds great realistic significance in alleviating global economic and climate pressures, and highlights the need for future research on refined health risk assessments for more contaminants.

Natural attenuation of BTEX and chlorobenzenes in a formerly contaminated pesticide site in China: Examining kinetics, mechanisms, and isotopes analysis.

Groundwater contamination from abandoned pesticide sites is a prevalent issue in China. To address this problem, natural attenuation (NA) of pollutants has been increasingly employed as a management strategy for abandoned pesticide sites. However, limited studies have focused on the long-term NA process of co-existing organic pollutants in abandoned pesticide sites by an integrated approach. In this study, the NA of benzene, toluene, ethylbenzene, and xylene (BTEX), and chlorobenzenes (CBs) in groundwater of a retired industry in China was systematically investigated during the monitoring period from June 2016 to December 2021. The findings revealed that concentrations of BTEX and CBs were effectively reduced, and their NA followed first-order kinetics with different rate constants. The sulfate-reducing bacteria, nitrate-reducing bacteria, fermenting bacteria, aromatic hydrocarbon metabolizing bacteria, and reductive dechlorinating bacteria were detected in groundwater. It was observed that distinct environmental parameters played a role in shaping both overall and key bacterial communities. ORP (14.72%) and BTEX (12.89%) were the main drivers for variations of the whole and key functional microbial community, respectively. Moreover, BTEX accelerated reductive dechlorination. Furthermore, BTEX and CBs exhibited significant enrichment of 13C, ranging from +2.9 to +27.3‰, demonstrating their significance in situ biodegradation. This study provides a scientific basis for site management.

An Analysis of the Spatial Characteristics and Transport Fluxes of BTEX in Soil and Atmospheric Phases at a Decommissioned Steel Mill Site in China with a Long History.

BTEX (benzene, toluene, ethylbenzene, and xylene), as characteristic pollutants in chemical plant sites, are widely present in the environment and pose a serious threat to the health and safety of nearby residents. Studying the spatial distribution characteristics and transport fluxes of BTEX in soil and air at contaminated sites and the health risks they pose to humans is of great significance for fine pollution control and environmental management. This study took a typical decommissioned steel plant as a case study. A total of 23 soil and air samples were collected from different locations to investigate the spatial distribution characteristics of BTEX in soil and air. The transport and fate of BTEX in soil and air were evaluated using the fugacity model, and finally, a human health risk assessment was conducted. The results indicate a relatively severe level of benzene pollution in both soil and air. The maximum exceedance factor of benzene in soil samples is 31.5, with the concentration exceedance depth at 1.5 m. The maximum concentration of benzene in air samples is 4.98 µg·m-3. Benzene, at 5.9% of the site, shows a low flux with negative values, while other components at various locations all exhibit a trend of transport from the soil phase to the atmospheric phase. Benzene is the pollutant that contributes the most to the transport flux from soil to air within the site. The coking area and sewage treatment area are key areas within the steel mill where BTEX accumulate easily in the soil. The non-carcinogenic risk values of the individual components of BTEX in the soil are below the acceptable risk level. However, the carcinogenic risk value of benzene in the children's exposure scenario exceeds the carcinogenic risk level of 10-6. The carcinogenic risk range of various components of BTEX in the air is 2.63 × 10-6~3.88 × 10-5, with 28.6% of the locations exceeding the threshold of 10-6. The range of the total HI (hazard index) is 2.08 × 10-4~1.81 × 10-1, all of which is below the safety threshold of 1. The results of this study will provide scientific support for the fine pollution control and environmental management of industrial contaminated sites with BTEX as their typical pollutants.

Asbestos-Environment Pollution Characteristics and Health-Risk Assessment in Typical Asbestos-Mining Area.

Asbestos has been confirmed as a major pollutant in asbestos-mining areas that are located in western China. In general, asbestos-fibre dust will is released into the environment due to the effect of intensive industrial activities and improper environmental management, such that the health of residents in and around mining areas is jeopardised. A typical asbestos mining area served as an example in this study to analyse the content and fibre morphology of asbestos in soil and air samples in the mining area. The effects of asbestos pollution in and around the mining areas on human health were also assessed based on the U.S. Superfund Risk Assessment Framework in this study. As indicated by the results, different degrees of asbestos pollutions were present in the soil and air, and they were mainly concentrated in the mining area, the ore-dressing area, and the waste pile. The concentration of asbestos in the soil ranged from 0.3% to 91.92%, and the concentration of asbestos fibres in the air reached 0.008-0.145 f·cc-1. The results of the scanning-electron microscope (SEM) energy suggested that the asbestos was primarily strip-shaped, short columnar, and granular, and the asbestos morphology of the soils with higher degrees of pollution exhibited irregular strip-shaped fibre agglomeration. The excess lifetime cancer risk (ELCR) associated with the asbestos fibres in the air of the mining area was at an acceptable level (10-4-10-6), and 40.6% of the monitoring sites were subjected to unacceptable non-carcinogenic risks (HQ > 1). Moreover, the waste pile was the area with the highest non-carcinogenic risk, followed by the ore dressing area, a residential area, and a bare-land area in descending order. In the three scenarios of adult offices or residences in the mining area, adults' outdoor activities in the peripheral residence areas, and children's outdoor activities, the carcinogenic-and non-carcinogenic-risk-control values in the air reached 0.1438, 0.2225 and 0.1540 f·cc-1, and 0.0084, 0.0090 and 0.0090 f·cc-1, respectively. The results of this study will lay a scientific basis for the environmental management and governance of asbestos polluted sites in China.

Prediction of Dichloroethene Concentration in the Groundwater of a Contaminated Site Using XGBoost and LSTM.

Chlorinated aliphatic hydrocarbons (CAHs) are widely used in agriculture and industries and have become one of the most common groundwater contaminations. With the excellent performance of the deep learning method in predicting, LSTM and XGBoost were used to forecast dichloroethene (DCE) concentrations in a pesticide-contaminated site undergoing natural attenuation. The input variables included BTEX, vinyl chloride (VC), and five water quality indicators. In this study, the predictive performances of long short-term memory (LSTM) and extreme gradient boosting (XGBoost) were compared, and the influences of variables on models' performances were evaluated. The results indicated XGBoost was more likely to capture DCE variation and was robust in high values, while the LSTM model presented better accuracy for all wells. The well with higher DCE concentrations would lower the model's accuracy, and its influence was more evident in XGBoost than LSTM. The explanation of the SHapley Additive exPlanations (SHAP) value of each variable indicated high consistency with the rules of biodegradation in the real environment. LSTM and XGBoost could predict DCE concentrations through only using water quality variables, and LSTM performed better than XGBoost.

Paeoniflorin alleviates liver injury in hypercholesterolemic rats through the ROCK/AMPK pathway.

Paeoniflorin (PF) is the main active component in Paeonia lactiflora Pall, and it has multiple effects. However, the precise mechanism of PF in hypercholesterolemia is unclear. In this study, rats were either fed a high-cholesterol diet (HCD) for 4 weeks to establish the hypercholesterolemic model or administered normal saline or PF (20 mg/kg/day). PF significantly reduced liver weight and the liver index. PF reduced hepatic lipid deposition and inflammation, improved serum lipid metabolism, and significantly inhibited serum and hepatic oxidative stress and the inflammatory response. PF treatment caused a marked decrease in the phosphorylated myosin phosphatase target subunit (p-MYPT)-1, nuclear sterol regulatory element-binding protein-1c (SREBP-1c), fatty acid synthase (FAS) levels, and an increase in the low-density lipoprotein receptor (LDLR) and phosphorylated-AMP-activated protein kinase (p-AMPK). Thus, PF could alleviate liver injury in hypercholesterolemic rats, and the specific mechanism may be related to the antioxidant, anti-inflammatory properties, and ROCK/AMPK/SREBP-1c signaling pathway.

Assessing the environmental impacts and costs of biochar and monitored natural attenuation for groundwater heavily contaminated with volatile organic compounds.

Although biochar (BC) and monitored natural attenuation (MNA) are regarded as green technologies for remediating volatile organic compounds (VOCs) contaminated groundwater, their life cycle environmental impacts and costs have not been systematically quantified. This work assessed the primary and secondary environmental impacts and the cost of three options for remediating the groundwater at a closed pesticide manufacturing plant site, which was contaminated by high levels of multiple VOCs and is undergoing MNA. The studied options include a combination of MNA and BC (MNA + BC), BC, and pump and treat (PT). The environmental impacts were examined through a Life Cycle Assessment (LCA) using the ReCiPe 2016 method. The costs were evaluated using a Life Cycle Cost (LCC) method created in the SimaPro. The LCA results show that the overall environmental impacts follow the sequence of PT > BC > MNA + BC, but MNA + BC shows evident primary impacts. The CO2 eq emissions generated from PT are more than five times of MNA + BC or BC. The cement, electricity, and steel for construction, and the operation energy are the environmental hotspots in PT. In MNA + BC and BC, the electricity for feedstock pyrolysis is the environmental hotspot, while the use of BC by-products to generate heat and power has positive environmental credit that compensates other negative environmental burdens. Incorporating institutional controls, using renewable energy and recycled or alternative materials, and developing BC with superior adsorption capacity are recommended to optimize the remediation strategies. The LCC results show that PT renders the highest cost, with cement and electricity being the two most expensive items. Electricity is the dominant contributor to the costs of MNA + BC and BC, while the avoided heat and power generation can save the cost of other items. Overall, this study provides scientific support to develop and optimize green remediation solutions for VOCs contaminated groundwater.

Ecological-health risks assessment and source apportionment of heavy metals in agricultural soils around a super-sized lead-zinc smelter with a long production history, in China.

Smelting activities are considered as the primary cause of heavy metal (HM) accumulation in soils, and the human health around the smelter has been a great concern worldwide. In this study, a total of 242 agricultural soil samples were collected around a large scale Pb/Zn smelter in China, and eight HMs (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) were analyzed to assess HMs status, ecological -health risks, and identify source. Monte Carlo simulation was utilized to evaluate the probabilistic health risks, and positive matrix factorization (PMF) was employed to identify sources. The results revealed the average contents of five heavy metals (Cd 5.28 mg/kg, Pb 203.36 mg/kg, Hg 0.39 mg/kg, Zn 293.45 mg/kg, Cu 37.14 mg/kg) are higher than their background values in Hunan province. Cd had the highest mean pollution index (PI) of 41.8 and the greatest average ecological risk index (Er) of 1256.34, indicating that Cd was the primary enriched pollutant and had a higher ecological risk than other HMs. The mean hazard index (HI) through exposure to eight HMs was 2.95E-01 and 9.74E-01 for adults and children, respectively, with 35.94% of HI values for children exceeding the risk threshold of 1. Moreover, the mean total cancer risks (TCR) were 2.75E-05 and 2.37E-04 for adults and children, respectively, with 75.48% of TCR values for children exceeding the guideline value of 1E-04. In addition, the positive matrix factorization results showed smelting activities, natural sources, agricultural activities and atmospheric deposition were the three sources in soils, with the contribution rate of 48.62%, 22.35%, and 29.03%, respectively. The uncertainty analysis of the PMF indicated that the three-factor solution is reliable. This work will provide scientific reference for the comprehensive prevention of soil HM pollution adjacent to the large smelter.

Metaphire guillelmi gut as hospitable micro-environment for the potential transmission of antibiotic resistance genes.

Earthworm gut played an important role in the transformation of various contaminants in the soil environments. With the increasing application of organic fertilizer recently, the ingestion of antibiotics, antibiotic resistance bacteria (ARB), and antibiotic resistance genes (ARGs) made the earthworm gut a potential favorable micro-environment for the transmission of ARGs in the soil. In this work, the conventional plate incubation and high-throughput sequencing methods were both employed to investigate the composition of the cultivable and overall ARB/ARGs in the Metaphire guillelmi earthworm gut. A total of 87 cultivable isolates that resisted tetracycline (TC) and/or sulfadiazine (SD) were obtained, most of which belonged to phylum Firmicutes, genus Bacillus. Meanwhile, the counts of isolates with TC-SD dual resistance were higher than those with sole SD or TC resistance. Moreover, higher ARB counts and diversity were detected in the earthworm gut by high-throughput sequencing technique than those by the classical plate cultivation. Overall, the combination of conventional cultivable bacteria isolation and high-throughput sequencing methods provided a comprehensive understanding of the ARB composition in the earthworm gut. The results demonstrate that the earthworm gut is a hospitable micro-environment for ARB colonization. The potential role of earthworm intestinal ARB and ARGs proliferation in soil environments warrants further research.

Biochar combined with polyvalent phage therapy to mitigate antibiotic resistance pathogenic bacteria vertical transfer risk in an undisturbed soil column system.

The vertical migration of antibiotic resistance pathogenic bacteria (ARPB) and antibiotic resistance genes (ARGs) in the surface soil-vadose soil system has become a new threat to ecological safety and public health; there is an imperative need to develop an efficient technique for targeted control and inactivation of ARPB in these systems. In this work, undisturbed soil columns (0 ∼ -5 m) were constructed to investigate the impact of biochar amendment or/and polyvalent bacteriophage (ΦYSZ-KK) therapy on the vertical control and inactivation of tetracycline-resistant Escherichia coli K-12 and chloramphenicol-resistant Klebsiella pneumonia K-6. The simultaneous application of polyvalent phage and biochar impeded the vertical migration of ARPB from the top soil to lower soil layers and stimulated the ARPB dissipation in the soil column. After 60-day incubation, levels of ARPB and ARGs decreased significantly in the soil column by magnitudes of 2-6. Additionally, high throughput sequencing indicated that the simultaneous application of biochar and phage clearly maintained the structure and diversity of the soil microbial communities (p < 0.05). This work therefore demonstrates that the application of a biochar/phage combination is an environmentally friendly, efficacious measure for the control and inactivation of ARPB/ARGs in vertical soil column systems.