Health risk assessment of trace metal(loid)s in agricultural soils based on Monte Carlo simulation coupled with positive matrix factorization model in Chongqing, southwest China

This study aimed to investigate the pollution characteristics, source apportionment, and health risks associated with trace metal(loid)s(TMs) in the major agricultural producing areas in Chongqing, China. We analyzed the source apportionment and assessed the health risk of TMs in agricultural soils by using positive matrix factorization(PMF) model and health risk assessment(HRA) model based on Monte Carlo simulation. Meanwhile, we combined PMF and HRA models to explore the health risks of TMs in agricultural soils by different pollution sources to determine the priority control factors. Results showed that the average contents of cadmium(Cd), arsenic (As), lead(Pb), chromium(Cr), copper(Cu), nickel(Ni), and zinc(Zn) in the soil were found to be 0.26, 5.93, 27.14, 61.32, 23.81, 32.45, and 78.65 mg/kg, respectively. Spatial analysis and source apportionment analysis revealed that urban and industrial sources, agricultural sources, and natural sources accounted for 33.0%, 27.7%, and 39.3% of TM accumulation in the soil, respectively. In the HRA model based on Monte Carlo simulation, noncarcinogenic risks were deemed negligible(hazard index <1), the carcinogenic risks were at acceptable level(10^(-6)<total carcinogenic risk ≤ 10^(-4)), with higher risks observed for children compared to adults. The relationship between TMs, their sources, and health risks indicated that urban and industrial sources were primarily associated with As, contributing to 75.1% of carcinogenic risks and 55.7% of non-carcinogenic risks, making them the primary control factors. Meanwhile, agricultural sources were primarily linked to Cd and Pb, contributing to 13.1% of carcinogenic risks and 21.8% of non-carcinogenic risks, designating them as secondary control factors.

Spatiotemporal simulation and predication of heavy metal(loid) concentrations in coal chemical industrial areas with a soil environmental capacity model

Heavy metal (loid)(HM) accumulation in the soil and the HM spatiotemporal distribution have important implication for soil pollution prevention and remediation. The present study investigated the concentrations and spatiotemporal distributions of lead (Pb), mercury (Hg), cadmium (Cd), chromium (Cr) and arsenic (As) in the topsoil of a coal chemical plant in Ningxia Aulonomous region (Ningxia), China. Topsoil samples (/?= 153) were obtained using the checkerboard method, and the HM concentrations were determined. The soil residual rates of the five HMs were measured with leaching experinients and were applied in a soil environmental capacity model to predict the quarHitiHive variation of the HM concentrations. The predicted results were employed to estimate the HM spatiotemporal distribution within 2() years with the Kriging technique. The number of sampling sites, where all five HM concentratio ns exceed their corresponding background values in Ningxia, would be increased from 0 to 90% within 1() years of the plant operation. In addition, Pb and Cd were distributed along the traffic routes. Mercury and As were distributed near fuel gas emission vents. Chromium was mainly accumulated in slag dumps. The study may provide the theoretical and practical foun d at ion for future HM pollution control in coal chemical plants.

Microbial Remediation of Heavy Metal(loid)Contaminated Soil: A Review

Because of the rapid development of industrial processes, increased urban pollution and agricultural chemicals applied in recent years, heavy metal(loid) pollution in soil has been very serious, and there is an urgent need for fast and efficient removal of heavy metal(loid) pollution. Currently, environmental microorganisms are always used to perform biological alteration or improvement of soils and sewage. Using functional microorganisms that are resistant to toxic heavy metal(loid) ions for alteration and transformation of heavy metal(loid)s in ionic form is an effective measure for microbial remediation of heavy metal(loid)contaminated soil. This paper reviewed the microbial remediation mechanism of heavy metal(loid) contaminated soils, and the approaches for breeding bacteria those can be used for highly efficient removal of heavy metal(loid)s, as well as the application examples of microbial remediation and transformation of heavy metal(loid) contaminated soil, and finally described the future trends and further research work of heavy metal(loid) contaminated soils by microbial remediation.

Contamination and human health risk assessment of heavy metal(loid)s in topsoil and groundwater around mining and dressing factories in Chifeng,North China

Chifeng is a concentrated mining area for non-ferrous metal minerals,as well as a key prevention and control area for heavyduty enterprises.This situation necessitates an efective ecological and human health risk assessment of heavy metal(loid)s driven by the wide distribution of metal ore processing,mining,and smelting factories in Hexigten Banner and Bairin Left Banner.We conducted surveys to assess the levels of heavy metal(loid)s(Cr,As,Pb,Cd,and Hg)in the topsoil and groundwater of the areas.The results indicated that the concentrations of As,Cd,and Pb in partial soil samples exceeded the environmental quality standards of Grade II.Based on contamination assessments,such as geoaccumulation indices and pollution indices,we inferred that Cd,Pb,and As were primary pollutants in topsoil.Potential ecological risks when considered as part of the average risk indices(RI)are up to 1626.40 and 2818.76,respectively,in the two areas.Comparative analysis revealed that Cd posed a very high potential ecological risk,followed by As.Moreover,the evaluation showed that the three exposure pathways of carcinogenic and non-carcinogenic risk followed a descending order:inhalation>ingestion>dermal contact,except for Pb.Arsenic in topsoil posed a potential non-carcinogenic risk to human health,while there were no adverse efects of As in groundwater.In addition,the average total carcinogenic risk for As in the two areas,as well as the risk of Pb in the topsoil of Bairin Left Banner and all the fve heavy metal(loid)s in groundwater,exceeded human tolerance.Pb–Zn mines caused higher human health risks.In addition,the tandem contamination of heavy metal(loid)s in soil and groundwater was not obvious.This research study provides a basis for pollution remediation to control heavy industry-induced ecological and health risks of heavy metal(loid)s.

Single-atom catalysts with anionic metal centers: Promising electrocatalysts for the oxygen reduction reaction and beyond

Ongoing efforts to develop single-atom catalysts(SACs) for the oxygen reduction reaction(ORR) typically focus on SACs with cationic metal centers,while SACs with anionic metal centers(anionic SACs) have been generally neglected.However,anionic SACs may offer excellent active sites for ORR,since anionic metal centers could facilitate the activation of O_(2) by back donating electrons to the antibonding orbitals of O_(2).In this work,we propose a simple guideline for designing anionic SACs:the metal centers should have larger electronegativity than the surrounding atoms in the substrate on which the metal atoms are supported.By means of density functional theory(DFT) simulations,we identified 13 anionic metal centers(Co,Ni,Cu,Ru,Rh,Pd,Ag,Re,Os,Ir,Pt,Au,and Hg) dispersed on pristine or defective antimonene substrates as new anionic SACs,among which anionic Au and Co metal centers exhibit limiting potentials comparable to,or even better than,conventional Pt-based catalysts towards ORR.We also found that anionic Os and Re metal centers on the defective antimonene can electrochemically catalyze the nitrogen reduction reaction(NRR) with a limiting potential close to that of stepped Ru(0001).Overall,our work shows promise towards the rational design of anionic SACs and their utility for applications as electrocatalysts for ORR and other important electrochemical reactions.

Removal of Anionic Metal Ions from Wastewater by Hydroxide-type Adsorbents

Generally speaking,anionic metal concentrations in wastewater from industries and mineral processing plants are well above the allowed limits for effluent set by the Ministry of Environment of Japan. Nowadays,the removal of anionic ions has been considered difficult and development of new process is desperately needed. In this paper,we report the development of three hydroxide-type adsorbents,illustrating their adsorption efficiency in removing As,Se,Mo and Sb ions from aqueous solutions. The main finding of this work was that the adsorption behavior was influenced very much by both the pH and the adsorbent concentration. Nevertheless,the newly developed hydroxide-type adsorbents were very effective in reducing the concentration of those anionic ions.

Mass Spectrometric Studies on Metal-hexafluorobenzene Anionic Complexes(M=Ag, Au, Pd, Pt, Pb and Bi)

The anionic products from the reactions between metal（M=Ag, Au, Pd, Pt, Pb and Bi） vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas（Ar） were studied by means of a homemade reflectron time-of-flight mass spectrometry（RTOF-MS）. Experimental results show that the dominant products were [MmC6F6]^- complexes for the reactions ofAg, Au, Pd and Pt with C6F6, while the dominant products were [MmC6F5]^- complexes for the reactions of Pb and Bi with C6F6. The formation mechanisms of the products, including the adsorption of metal cluster anions on hexafluorobenzene and the C--F cleavage induced by metal cluster anions, were discussed.

Deep dive into anionic metal-organic frameworks based quasi-solid-state electrolytes

The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.

Multiple assessments, source determination, and health risk apportionment of heavy metal(loid)s in the groundwater of the Shule River Basin in northwestern China

Global ecosystems and public health have been greatly impacted by the accumulation of heavy metal(loid)s in water.Source-specific risk apportionment is needed to prevent and manage potential groundwater contamination with heavy metal(loid)s.The heavy metal(loid)s contamination status,water quality,ecological risk,and health risk apportionment of the Shule River Basin groundwater are poorly understood.Therefore,field sampling was performed to explore the water quality and risk of heavy metal(loid)s in the groundwater of the Shule River Basin in northwestern China.A total of 96 samples were collected from the study area to acquire data for water quality and heavy metal(loid)s risk.There was noticeable accumulation of ferrum in the groundwater of the Shule River Basin.The levels of pollution were considered to be moderately low,as evaluated by the degree of contamination,heavy metal evaluation index,heavy metal pollution index,and Nemerow pollution index.The ecological risks were also low.However,an assessment of the water quality index revealed that only 58.34%of the groundwater samples had good water quality.The absolute principal component scores-multiple linear regression model was more suited for this study area than the positive matrix factorization model.There were no obvious noncarcinogenic or carcinogenic concerns for all types of receptors according to the values of the total hazard index and total carcinogenic risk.The human activities and the initial geological environment factor(65.85%)was the major source of noncarcinogenic risk(residential children:87.56%;residential adults:87.52%;recreational children:86.77%;and recreational adults:85.42%),while the industrial activity factor(16.36%)was the major source of carcinogenic risk(residential receptors:87.96%;and recreational receptors:68.73%).These findings provide fundamental and crucial information for reducing the health issues caused by heavy metal(loid)s contamination of groundwater in arid areas.

Assessment of the Level of Metal(loid)s Pollution and Bioactive Compounds Screening of Anthill Soil

The anthill soil is used by hypertensive elderly and teenagers from Oshikoto region (Namibia) and many of them testified stabilization of their blood pressure to normal after consuming the anthill soil-derived aqueous extracts. This study therefore investigated and/or assessed the physicochemical parameters, the contents of some metal(loid)s (and their associated potential health risks) and the qualitative composition of bioactive compounds of this anthill soil. The homogenous soil sample collected from various anthill soils in the Oshikoto region was used to obtain the measurements of physiochemical parameters. The elemental contents were determined (using an Inductively Coupled Plasma Optical Emission Spectrophotometer) after acid digestion in accordance with the EPA method 350B and their potential health risk assessments were performed. Methanol, aqueous methanol, and aqueous-based extracts were generated via maceration extraction process prior to the screening of bioactive compounds using standard diagnostic assays. The oxidation reduction potential (164.4 ± 16.6 mV) was the only physicochemical parameter whose value was within the World Health Organization limits for drinking water whereas, total dissolved solids (23 ± 5.5 mg/L), electrical conductivity (44 ± 10.1 uS/cm) and pH (5.35 ± 0.33) were out of specifications. Phenolic compounds, flavonoids, terpenoids, and cardiac glycosides were present in anthill soil (with respect to the extractants used) to which its antihypertensive properties can be attributed in addition to some of the studied mineral components. With respect to the pH, TDS and EC, and the contents of most metal(loid)s in relation to their health risk assessment values, the results suggest that aqueous extracts derived from this anthill soil can be deemed unsuitable for human consumption.

Novel Properties of Supramolecular Complexes Formed by Pairing Cationic Porphyrin and Anionic Metal-Oxo Cluster

MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.

A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.

Distribution, Mobility, and Health Risks Assessment of Trace Metals in River Sediments from Intense Agricultural Activity Areas in West Africa

The economy of West African countries is mainly based on agriculture. However, the trace metal(loid)s contamination status in rivers is relatively unknown in the region. In this work, 45 surface sediments collected from the Bandama, Comoé, and Bia Rivers in south and south eastern Côte d’Ivoire (West Africa), were analyzed for total metal concentrations and chemical speciation. The results showed that the river sediments were considerably contaminated by Cd and moderately contaminated by As, Cu, Pb, and Zn. Significant spatial variations were observed among the stations but not between the rivers. Metals Cd and Cu were likely to cause more ecological risks. The speciation analysis unravelled that the metal(loid)s partitioned mainly in the residual fraction, with the potential mobile fraction varying from 14% to 28%. The study calls for establishment of strict policies relative to the application of fertilizers and agrochemicals and mining activities to protect the environment and human health risks.

Impact of anions on the heavy metals release from marine sediments

Marine sediments from Lianshan Bay in Huludao, China, were studied in laboratory. A series of simulated experiments were carried out to investigate the influences of three kinds of anions CL^-, SO4^2- and HCO3^- on the release ofCd, Pb, Cu and Zn from the sediments. The results showed that the sequences about the impact of the three anions were Cl^-〉HCO3^-〉SO4^2＋. The release potential of heavy metals in the presence of each anions was in the following order： Cd≥Cu 〉Zn≈Pb. The correlations were positive between CI content and the quantity of Cd released from the marine sediment, whereas there was no significant relationship between CI content and amount of Cu and Zn released. For SO4^2- and HCO3^-, the release of the heavy metals from marine sediments was not obvious.

The activity and kinetic properties of cellulases in substrates containing metal ions and acid radicals

The effects of various metal ions (Na+, K+, Ca2+, Mg2+, Al3+, Co2+) and anions (Cl–, SO2-4 and CH3COO–) on two cellulases were investigated. Fitting of the data to Michaelis-Menten kinetics showed that Al3+ noncom-petitively inhibited cellulase (Km = 22.68 g/L;Vmax = 0.269 mg/min at 5.0 mmol/L AlCl3) and Mg2+ competitively inhibited cellulase (Km = 50.0 g/L;Vmax = 0.434 mg/min at 10.0 mmol/L MgCl2) Different metal ions increased or decreased inhibition of cellulase activity slightly below 1 mmol/L and strongly over 10 mmol/L. The results indicated that filter paper activeity (FPA) was suitable for analysis of enzymatic saccharification with various lignocellulosic substrates whereas crude cellulase was suitable for applications in the biomass industry. Some metal ions were proved to inhibit cellulase reversibly.

Preparation，Characterization and Catalytic Activity of Anionic Clay Pillared by GaW＿9Zn＿3

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Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions

In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of [Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.

Responses of acrocarpous moss communities to heavy metal(Fe,Mn,Cd)and sulfur pollution in the Changgou carbonate manganese ore,SW China

Bryophyte communities have been widely used to monitor and assess heavy metal pollution in soil,air and water.However,the unique value of acrocarpous moss in monitoring environmental pollution and the harm of non-metallic sulfur to human health caused by carbonate manganese mining were seldom considered in previous studies.This study investigated the heavy metal and sulfur pollution level by soil and moss sample collection in Changgou manganese ore and its surrounding environment in the Zunyi area,Guizhou Province,China.By means of cluster analysis,diversity analysis,correlation analysis and redundancy analysis,the relationship between dominant moss communities and major pollutants were analyzed.The results showed that there were pollutants such as iron(Fe),manganese(Mn),cadmium(Cd),sulfur(S)and others in the 500 meters buffer zone centered on Changgou manganese ore.The ore sorting area and waste rock accumulation area were considered as the most seriously polluted,followed by the ore outlet area and ore transport line,at last the miners’living area and vegetable planting area were the least polluted.A total of 23 species of moss communities were identified in the Changgou manganese ore area,among which 9 were dominant,including Bryum blindii Bruch&Schimp.(Bry.bli),Weissia planifolia Dix(Wei.pla)-Bry.bli,Bryum caespiticium Hedw.(Bry.cae),Bryum pallescens Schleicher ex Schw?gr.(Bry.pal),Didymodon longicostatus X.J.Li et Iwats(Did.lon),Weissia brachycarpa(Nees&Hornsch.)Jur.(Wei.bra),Trichostomum brachydontium Bruch.(Tri.bra),Bryum argenteum Hedw.(Bry.arg)Wei.bra and Bryum algovicum Sendt.ex M?ll.Hal.(Bry.alg),all of which are from the acrocarp species.Bry.cae showed a strong tolerance to S,Did.lon to Fe,Bry.pal to Cd and Bry.bli to Mn.There was a significant correlation between the main polluting elements and the dominant bryophyte community(P<0.05),indicating a high biological indicator value.Together,our results can provide the scientific basis for soil pollution monitoring and human health risk assessment in carbonate manganese mining areas.

Quantitation of metallothionein and cadmium in metallothionein in mink livers by anion-exchange HPLC-GFAAS method

Metallothionein (MT) has a great capacity of binding heavy metals showing an interesting connection with metal toxicology, as a biochemical marker for environmental metal pollution. Anino-exchange high per formance liquid chromatography (HPLC) was used to isolate and quantitate MT in livers of minks which were contaminated with heavy metals. MT isoforms (MT-I and MT-II) were eluted at approximately 11.3 and 14.3 min respectively from a DEAE-5 PW anion-exchange column with a Tris-HCl buffer (0.01 -0.25 mol/L, pH 8.6) and detected by UV absorbance at 254 nm. The cadmium concentrations in mink liver MT elutkms were determined by graphite furnace atomic absorption spectrometry (GFAAS) . Obvious increase in liver MT-I concentration rather than liver MT-II was found when the minks were contaminated by feeding contaminated fish captured from the heavy metal-polluted river. The cadmium concentration in mink liver MT-I also increased to some extent as the contaminated level increased.