Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the sol...Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.展开更多
As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal...As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.展开更多
Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and ...Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.展开更多
The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious int...The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.展开更多
Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testifie...Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.展开更多
The effects of five amendments such as acetic acid(AA), citric acid (CA), ethylenediamine tetraacetic acid (EDTA), sepiolite and phosphogypsum on growth and metal uptake of giant reed (Arundo donax L.) grown o...The effects of five amendments such as acetic acid(AA), citric acid (CA), ethylenediamine tetraacetic acid (EDTA), sepiolite and phosphogypsum on growth and metal uptake of giant reed (Arundo donax L.) grown on soil contaminated by arsenic (As), cadmium (Cd) and lead (Pb) were studied. The results showed that the shoot biomass of giant reed was enhanced by 24.8% and 15.0%, while superoxide mutase and catalase activities slightly varied when adding 5.0 mmol/kg CA and 2.5 mol/kg EDTA to soil as compared to the control, respectively. The concentrations of As, Cd and Pb in shoots were remarkably increased by the addition of 2.5 mmol/kg AA and CA, 5.0 mmol/kg EDTA, and 4.0 g/kg sepiolite as compared to the control. The accumulations of As and Cd were also significantly enhanced in the above condition, while the shoot Pb accumulation was noticeably enhanced by amending with 4.0 g/kg sepiolite and 8.0 g/kg phosphogysum, respectively. The results suggested that AA, CA and sepiolite could be used as optimum soil amendments for giant reed remediation system.展开更多
The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations o...The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations of Pb, Cd and Zn exceeded corresponding limits of the Chinese National Soil Environmental Quality Standard III. The soil was extremely polluted by Cd(Iego=5.26), moderately to heavily polluted by Zn(Iego=2.38), heavily to extremely polluted by Pb(Iego=4.13). The results of BCR three-step sequential extraction procedure show that the active Cd, Pb and Zn were relatively high and might exert adverse effects on the plants grown in the soil, while Cu and Ni existed in soil with a relatively stable form. Potential ecological risk results indicate that soils were engaging in a high potential ecological risk by pollution of Cd and should be given rise to concern.展开更多
It is less known whether and how soil metal lead (Pb) impacts the invasion of exotic plants. A greenhouse experiment was conducted to estimate the effects of lead on the growth and mycorrhizae of an invasive species...It is less known whether and how soil metal lead (Pb) impacts the invasion of exotic plants. A greenhouse experiment was conducted to estimate the effects of lead on the growth and mycorrhizae of an invasive species (Solidago canadensis L.) in a microcosm system. Each microcosm unit was separated into HOST and TEST compartments by a replaceable mesh screen that allowed arbuscular mycorrhizal (AM) fungal hyphae rather than plant roots to grow into the TEST compartments. Three Pb levels (control, 300, and 600 mg/kg soil) were used in this study to simulate ambient soil and two pollution sites where S. canadensis grows. Mycorrhizal inoculum comprised five indigenous arbuscular mycorrhizal fungal species ( Glomus mosseae, Glomus versiform, Glomus diaphanum, Glomus geosporum, and Glomus etunicatum). The ^15N isotope tracer was used to quantify the mycorrhizally mediated nitrogen acquisition of plants. The results showed that S. canadensis was highly dependent on mycorrhizae. The Pb additions significantly decreased biomass and arbuscular mycorrhizal colonization (root length colonized, RLC%) but did not affect spore numbers, N (including total N and ^15N) and P uptake. The facilitating efficiency of mycorrhizae on nutrient acquisition was promoted by Pb treatments. The Pb was mostly sequestered in belowground of plant (root and rhizome). The results suggest that the high efficiency of mycorrhizae on nutrient uptake might give S. canadensis a great advantage over native species in Pb polluted soils.展开更多
In this work, a thorough examinations on the extractability of zinc and lead present in the steelmaking dusts using alkaline leaching process and the effectiveness of the zinc and lead separation in the resultant leac...In this work, a thorough examinations on the extractability of zinc and lead present in the steelmaking dusts using alkaline leaching process and the effectiveness of the zinc and lead separation in the resultant leaching solutions using sulfide precipitation method were made. It was found that only about 53% of zinc and over 70% of the lead could be leached out of the dusts, while the other 47% of zinc and 30% of lead were left in the leaching residues. The zinc and lead in the resultant leaching solution can be effectively and selectively separated. When the weight ratio of sodium sulfide (M.W. = 222-240) to Pb was kept at 1.8, the lead in the solution could be precipitated out quantitatively while all the zinc was remained in the solution. The zinc left in the solution can be further recovered by the addition of extra sodium sulfide with a weight ratio of sodium sulfide to the zinc over 2.6. The resultant filtrate can be recycled to the leaching of dust in the next leaching process.展开更多
Agrogyron elongatum were grown in nutrient solution containing moderate to high amounts of separate heavy metal of Cd, Cu, Ni and Ph in a greenhouse for a 9 - day. Cd, Cu, Ni and Ph generally led to decrease in the el...Agrogyron elongatum were grown in nutrient solution containing moderate to high amounts of separate heavy metal of Cd, Cu, Ni and Ph in a greenhouse for a 9 - day. Cd, Cu, Ni and Ph generally led to decrease in the elongation of roots although the length of seedlings exposed to Cd and Ph at 0.05 and 0.5 mg/L showed to be slightly greater than that of controls. Of the four metals in the experiment, Ph was absorbed and accumulated to the highest level, with the concentrations of 92754 mg/kg dry weight (DW) in roots and 11683 mg/kg DW in shoots. Cd was moderately accumulated in Agrogyron elongatum, but the maximum bioaccumulation coefficients (BCs) for roots and shoots were observed. The patterns for Cu and Ni uptake and distribution in plants differed from those of Ph and Cd, as it was showed that the shoot accumulation of Cu and Ni was significantly higher than in roots. A. elongation had the highest Ni concentration in shoots (30261 mg/kg DW) at the external concentration of 250 mg/L. Cu ranked second, with a shoot concentration of 12230 mg/kg DW when 50 mg/L Cu in solution was applied. For the four trace elements tested, the highest concentrations in shoots decreased by the order of Ni > Cu > Ph > Cd (mg/kg DW), and those in roots were Ph > Cd > Ni > Cu (mg/kg DW). Malic, oxalic and citric acids exuded by roots exposed to 1 and 50 mg/L of the metals were detected. Release of organic acids from plants significantly differed among the metal treatments. Cu was most effectively in inducing root exudation of the three types of organic acids. Cd, and Ni were also the inducers of secretion of malic and oxalic acids. With reference of Pb, a small amounts of malic and oxalic acids were detected in the root exudates, but few quantities, of citric acid were. found. However, no correlation between alternations in root exudation of organic acids and metal accumulation could be established.展开更多
Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemi...Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface(0 to 20 cm) soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations(Pb, Zn, Cd and Cu) with clay content revealed a strongly significant relationship while significant relationship( P 〈 0.001 ) was also obtained between Cd + Zn and Pb + Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order: residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb(29.1% ) to its total concentration in the soils was higher than those of Zn(4.70% ), Cd(3.16% ) and Cu(9.50% ). The percentages of the water soluble and the exchangeable fractions of Pb(1.80% ) and Cd(2.74% ) were markedly greater than those of Zn(0.10% ) and Cu(0.15% ), suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.展开更多
A type of carbonate-hosted lead–zinc(Pb–Zn)ore deposits, known as Mississippi Valley Type(MVT)deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to...A type of carbonate-hosted lead–zinc(Pb–Zn)ore deposits, known as Mississippi Valley Type(MVT)deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to account for metal precipitation mechanism of the MVT ore deposits, in which fluids with metal-chloride complexes happen to mix with fluids with reduced sulfur, producing metal sulfide deposition. In this hypothesis, however, the detailed chemical kinetic process of mixing reactions, and especially the controlling factors on the metal precipitation are not yet clearly stated. In this paper, a series of mixing experiments under ambient temperature and pressure conditions were conducted to simulate the fluid mixing process, by titrating the metal-chloride solutions, doping withor without dolomite, and using NaHS solution. Experimental results, combined with the thermodynamic calculations, suggest that H_2S, rather than HS^-or S^(2-),dominated the reactions of Pb and/or Zn precipitation during the fluid mixing process, in which metal precipitation was influenced by the stability of metal complexes and the pH. Given the constant concentrations of metal and total S in fluids, the pH was a primary factor controlling the Pb and/or Zn metal precipitation. This is because neutralizing or neutralized processes for the ore-forming fluids can cause instabilities of Pb and/or Zn chloride complexes and re-distribution of sulfur species, and thus can facilitate the hydrolysis of Pb and Zn ions and precipitation of sulfides. Therefore, a weakly acidic to neutral fluid environment is most favorable for the precipitation of Pb and Zn sulfides associated with the carbonate-hosted Pb–Zn deposits.展开更多
A field experiment was conducted to compare the growth and metal accumulation of Vetiveria zizanioides, Paspalum notatum, Cynodon dactylon and Imperata cylindraca var. major on the tailings, amended with 10 cm domesti...A field experiment was conducted to compare the growth and metal accumulation of Vetiveria zizanioides, Paspalum notatum, Cynodon dactylon and Imperata cylindraca var. major on the tailings, amended with 10 cm domestic refuse + complex NPK fertilizer(Treatment A), 10 cm domestic refuse(Treatment B) and complex NPK fertilizer(Treatment C) respectively, and without any amendment used as control(Treatment D). The results indicated that V. zizanioides was a typical heavy metal excluder, because the concentrations in shoots of the plants were the lowest among the four plants tested. The most of metal accumulated in V. zizanioides distributed in its root, and transportation of metal in this plant from root to shoot was restricted. Therefore, V. zizanioides was more suitable for phytostabilization of toxic mined lands than P. notatum and C. dactylon, which accumulated a relatively high level of metals in their shoots and roots. It was also found that I. cylindraca var. major accumulated lower amounts of Pb, Zn and Cu than C. dactylon and P. notatum, and could also be considered for phytostalilisaton of tailings. Although the metal(Pb, Zn and Cu) concentrations in shoots and roots of V. zizanioides were the lowest, the total amounts of heavy metals accumulated in shoots of V. zizanioides were the highest among the four tested plants due to the highest dry weight yield of it. The results indicated that V. zizanioides was the best choice among the four species used for phytoremediation(for both phytostabilization and phytoextraction) of metal contaminated soils.展开更多
The contents of Pb, Cd, Cr, As, and Hg was investigated in the neighboring areas of a lead smelting enterprise and the metals contamination of soil was evaluated with the methodologies of the single factor index and N...The contents of Pb, Cd, Cr, As, and Hg was investigated in the neighboring areas of a lead smelting enterprise and the metals contamination of soil was evaluated with the methodologies of the single factor index and Nemerow integrated index. It is found that the content of heavy metals in the neighboring areas has no obvious difference from the reference points. And the soil contamination of heavy metals varies by elements, the contamination index follows the pollution order: Cd>Hg>Cr>As>Pb. The pollution degree of Cd is at high level and Hg at low level, but Cr and As reached the warning level. Therefore, the lead smelting enterprises should not only control lead but also other heavy metals as Cd.展开更多
This study focused on the influence of base metal mining on heavy metal levels in soils and plants in the vicinity of Arufu lead-zinc mine, Nigeria. Soil samples (0-15 cm depth) and plant samples were collected from c...This study focused on the influence of base metal mining on heavy metal levels in soils and plants in the vicinity of Arufu lead-zinc mine, Nigeria. Soil samples (0-15 cm depth) and plant samples were collected from cul-tivated farmlands in and around the mine, the unmineralized site and a nearby forest (the control site). The samples were analyzed for heavy metals (Fe, Zn, Mn, Cu, Pb, Cr and Cd) by Atomic Absorption Spectrophotometry (AAS). The physical properties of soils (pH and LOI) were also measured. Results showed that soils from cultivated farm-lands have neutral pH values (6.5-7.5), and low organic matter contents (<10%). Levels of Zn, Pb and Cd in culti-vated soils were higher than the concentrations obtained from the control site. These heavy metals are most probably sourced from mining and agricultural activities in the study area. Heavy metal concentrations measured in plant parts decreased in the order of rice leaves>cassava tubers>peelings. In the same plant species, metal levels decreased in the order of Zn>Fe>Mn>Cu>Pb>Cr>Cd. Most heavy metals were found in plant parts at average concentrations normally observed in plants grown in uncontaminated soil, however, elevated concentrations of Pb and Cd were found in a few cassava samples close to the mine dump. A stepwise linear regression analysis identified soil metal contents, pH and LOI as some of the factors influencing soil-plant metal uptake.展开更多
The heavy metal(such as Cr,Ni,Cu,Cd,Pb,and Zn)concentration,speciation,and pollution source in 43 sediment samples from the Xiangjiang River were investigated using sequential extraction combined with Pb isotope analy...The heavy metal(such as Cr,Ni,Cu,Cd,Pb,and Zn)concentration,speciation,and pollution source in 43 sediment samples from the Xiangjiang River were investigated using sequential extraction combined with Pb isotope analysis.Cu,Cd,Pb,and Zn concentrations are higher than their background values,while Cr and Ni concentrations are close to those.Sequential extraction demonstrates that heavy metals have different fractions,showing different bioavailabilities.The w(206Pb)/w(207Pb)ratio increases with decreasing bioavailability in the order of exchangeable<carbonate≈Fe-Mn oxides≈organic<residual(p<0.05).Wastewater,dust,and slag from mining and smelting areas,and the residual Pb are assumed to be the primary anthropogenic and natural sources of Pb,respectively.The percentages of anthropogenic Pb in the exchangeable,carbonate,Fe-Mn oxides,and organic fractions are(91.5±16.7)%,(61.1±13.9)%,(57.4±11.1)%,and(55.5±11.2)%,respectively,suggesting a significant input of anthropogenic Pb in these four fractions.展开更多
[Objectives] The research was conducted to study characteristics of bioavailable levels pollution of heavy metals in the surface soil of the lead-zinc mine in Changhua.[Methods] A total of 56 surface samples were coll...[Objectives] The research was conducted to study characteristics of bioavailable levels pollution of heavy metals in the surface soil of the lead-zinc mine in Changhua.[Methods] A total of 56 surface samples were collected from the 3 study zones (peripheral zone, reclamation zone and tailing zone) located at the lead-zine mine in Changhua. Based on total and bioavailable heavy metals (Pb, Zn, Cu and Cd) in soils, the correlation of total content with bioavailable content was analyzed, and their pollution characteristics were assessed by methods of single factor pollution index, Nemerow pollution index, geological accumulation index and potential ecological risk index.[Results] (i) The surface soils were polluted by Pb, Zn, Cu, Cd in different degrees, and the overall trend of the contents of the 4 heavy metals was in order of Cd 〉 Pb 〉 Zn 〉 Cu. The average excess multiple of heavy metals of total and bioavailable content in soils were in the order of peripheral zone 〉 tailing zone 〉 reclaimed zone, and their pollution degrees were tailing zone 〉 peripheral zone 〉 reclaimed zone. (ii) In general, the total and bioavailable contents of Pb, Zn, Cu, Cd showed a significant correlation, but were not correlated in each study zone. (iii) Pollution degrees of the study zones were in the order of tailing zone 〉 peripheral zone 〉 reclamation zone. The pollutions of heavy metals Pb and Cd were more serious, especially Cd reached high levels of pollution degree, and the pollution degrees of Zn, Cu were lighter. Contributors of ecological risk were mainly Cd, Pb and Cu, and the contribution of Cd achieved more than 90 %, making it the main source of pollution.[Conclusions] The results not only revealed the pollution status of heavy metals in the surface soil of the abandoned coal mine, but also could provide scientific guidance for reasonable utilization and ecological recovery of the land.展开更多
Difference of montmorillonite (Mt), illite (It) and kaolinite (Kt) in lead sorption characteristics and the effects of amorphous Fe and Al oxide coatings on the characteristics were experimentally studied with logisti...Difference of montmorillonite (Mt), illite (It) and kaolinite (Kt) in lead sorption characteristics and the effects of amorphous Fe and Al oxide coatings on the characteristics were experimentally studied with logistic model. The sorption curves had sigmoid feature due to use of acetate-type buffer solution. With the model the sorption process could be divided into four stages and the sorption characteristics at the stages were discussed. The results showed that, after Mt, It and Kt were coated by amorphous Fe oxide, their maximum sorption capacity (MSC) and percentage of high-SSC concentration scope (HCS) of Pb2+ increased markedly, but the specific sorption capacity (SSC) decreased. With regard to effects of amorphous Al oxide coating, except for It+AI, the SSC of other samples showed a downtrend, despite that their MSC remained unchanged. Eventually, the gray correlation degrees to Pb2+ sorption for different physicochemical characteristics of the clay minerals were indicated to be higher for hydronium, zero point of surface charge and hydroxy, but lower for specific surface area, density of surface charge and amount of surface charges.展开更多
A novel metal-organic framework(MOF) compound of Pb(C5H4NCOO)2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell: orthorhombic space group Pccn,...A novel metal-organic framework(MOF) compound of Pb(C5H4NCOO)2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell: orthorhombic space group Pccn, a=1.0325(2) nm, b=1.3597(3) nm, c=0.8499(2) nm, V=1.1931(4) nm^3, Z=4, Dc=2.513 g/cm^3, R1=0.047 were obtained on the basis of 1365 reflections with Fo〉2σ(Fo). PbN2O6 polyhedron adopts the distorted cubic configuration which is assigned to the holodirected geometry. These PbN2O6 polyhedra can form the zigzag chain by edge-sharing mode along(001) direction. Pb atom is connected by six nicotinic acid molecules, leading neutral 3D metal-organic framework with a channel defined by four Pb atoms and four nicotinic acid molecules.展开更多
Exploring transport patterns of soil contaminants is essential for solving the problem of heavy metal contamination in mine soils.In this study,contamination of Pb,Zn,and Cd in the mountain soils of the lead–zinc ore...Exploring transport patterns of soil contaminants is essential for solving the problem of heavy metal contamination in mine soils.In this study,contamination of Pb,Zn,and Cd in the mountain soils of the lead–zinc ore mines in Ganxi Township,Hengdong County,Hunan Province,China was investigated,and their transport patterns were further explored using a soil-column model and numerical simulation techniques.In total,111 mine soil samples were collected and placed into six experimental soil columns.By controlling the water flow,a control soil column group(CK),two mixed soil columns X1 with daily water flows of 1 and 5 L,and three mixed soil columns X3 with daily water flows of 2,3,and 4 L were evaluated.The results showed that the residual fraction of Pb accounted for 71.93%of the content on average,whereas the exchangeable fractions of Zn,Cd,and Fe-Mn oxide-bound fractions of Zn and Cd accounted for 28.60%,31.07%,and 43.2%and 53.54%of the content,respectively.Pb,Zn,and Cd in the soils of the CK,X1,and X3 groups mainly were accumulated at a depth from approximately 0 to 20 cm,and the content at this depth accounted for 60.09%of that at a 0~40 cm depth.The soil at a depth range of 0~10 cm was most seriously contaminated,and the proportion of content was 32.39%of that at a 0~40 cm depth.Numerical simulation showed that on the 5 th day,the pollutant transport range was 0~24 cm,and on the 9 th day,the pollutant transport range exceeded 40 cm.On the 15 th day,the transport capacity of pollutants at depths of 0~40 cm was close to the stable state,but the soil at a depth of 0~10 cm was still heavily polluted.These results reflect the transport pattern of heavy metal pollutants in the soil of lead–zinc ore mines and may provide a reliable scientific support for the prevention of heavy metal contamination in mine environments.展开更多
基金support from the National Natural Science Foundation of China(No.U2333210)the Sichuan Science and Technology Program,China(No.21SYSX0011)。
文摘Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.
基金financially supported by the National Key R&D Program of China(No.2022YFE0121300)the National Natural Science Foundation of China(No.52374376)the Introduction Plan for High-end Foreign Experts(No.G2023105001L)。
文摘As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.
基金financially supported by the Original Exploration Project of the National Natural Science Foundation of China(No.52150079)the National Natural Science Foundation of China(Nos.U22A20130,U2004215,and 51974280)+1 种基金the Natural Science Foundation of Henan Province of China(No.232300421196)the Project of Zhongyuan Critical Metals Laboratory of China(Nos.GJJSGFYQ202304,GJJSGFJQ202306,GJJSGFYQ202323,GJJSGFYQ202308,and GJJSGFYQ202307)。
文摘Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.
基金supported by the National Natural Science Foundation of China(Nos.52172214,52272221,52171182)the Postdoctoral Innovation Project of Shandong Province(No.202102003)+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01)the Qilu Young Scholar ProgramHPC Cloud Platform of Shandong University are also thanked.
文摘The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.
基金supported by the National Natural Science Foundation of China(No.92372123)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515012057,2022B1515020005,2023B1515130004)Guangzhou Basic and Applied Basic Research Foundation(No.202201011342).
文摘Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.
基金Project (2012BAC09B04) supported by National Key Technology Research and Development Program of the Ministry of Science and Technology of ChinaProject (2010-277-027) supported by Science and Technology Foundation of Environmental Protection in Hunan Province,ChinaProject (2011SK3262) supported by Science and Technology Planning of Hunan Province,China
文摘The effects of five amendments such as acetic acid(AA), citric acid (CA), ethylenediamine tetraacetic acid (EDTA), sepiolite and phosphogypsum on growth and metal uptake of giant reed (Arundo donax L.) grown on soil contaminated by arsenic (As), cadmium (Cd) and lead (Pb) were studied. The results showed that the shoot biomass of giant reed was enhanced by 24.8% and 15.0%, while superoxide mutase and catalase activities slightly varied when adding 5.0 mmol/kg CA and 2.5 mol/kg EDTA to soil as compared to the control, respectively. The concentrations of As, Cd and Pb in shoots were remarkably increased by the addition of 2.5 mmol/kg AA and CA, 5.0 mmol/kg EDTA, and 4.0 g/kg sepiolite as compared to the control. The accumulations of As and Cd were also significantly enhanced in the above condition, while the shoot Pb accumulation was noticeably enhanced by amending with 4.0 g/kg sepiolite and 8.0 g/kg phosphogysum, respectively. The results suggested that AA, CA and sepiolite could be used as optimum soil amendments for giant reed remediation system.
基金Project(2012FJ1010)supported by the National Science and Technology Major Project,ChinaProject(2012BAC09B04)supported by the National"Twelfth Five-Year"Plan for Science&Technology,ChinaProject(2012AA06202)supported by the National High-tech Research and Development Program of China
文摘The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations of Pb, Cd and Zn exceeded corresponding limits of the Chinese National Soil Environmental Quality Standard III. The soil was extremely polluted by Cd(Iego=5.26), moderately to heavily polluted by Zn(Iego=2.38), heavily to extremely polluted by Pb(Iego=4.13). The results of BCR three-step sequential extraction procedure show that the active Cd, Pb and Zn were relatively high and might exert adverse effects on the plants grown in the soil, while Cu and Ni existed in soil with a relatively stable form. Potential ecological risk results indicate that soils were engaging in a high potential ecological risk by pollution of Cd and should be given rise to concern.
基金This work was supported by the National Basic Research Program(973)of China(No.2006CB 100206)the Zhejiang Provincial Natural Science Foundation of China(No.R505024,Y307418).
文摘It is less known whether and how soil metal lead (Pb) impacts the invasion of exotic plants. A greenhouse experiment was conducted to estimate the effects of lead on the growth and mycorrhizae of an invasive species (Solidago canadensis L.) in a microcosm system. Each microcosm unit was separated into HOST and TEST compartments by a replaceable mesh screen that allowed arbuscular mycorrhizal (AM) fungal hyphae rather than plant roots to grow into the TEST compartments. Three Pb levels (control, 300, and 600 mg/kg soil) were used in this study to simulate ambient soil and two pollution sites where S. canadensis grows. Mycorrhizal inoculum comprised five indigenous arbuscular mycorrhizal fungal species ( Glomus mosseae, Glomus versiform, Glomus diaphanum, Glomus geosporum, and Glomus etunicatum). The ^15N isotope tracer was used to quantify the mycorrhizally mediated nitrogen acquisition of plants. The results showed that S. canadensis was highly dependent on mycorrhizae. The Pb additions significantly decreased biomass and arbuscular mycorrhizal colonization (root length colonized, RLC%) but did not affect spore numbers, N (including total N and ^15N) and P uptake. The facilitating efficiency of mycorrhizae on nutrient acquisition was promoted by Pb treatments. The Pb was mostly sequestered in belowground of plant (root and rhizome). The results suggest that the high efficiency of mycorrhizae on nutrient uptake might give S. canadensis a great advantage over native species in Pb polluted soils.
文摘In this work, a thorough examinations on the extractability of zinc and lead present in the steelmaking dusts using alkaline leaching process and the effectiveness of the zinc and lead separation in the resultant leaching solutions using sulfide precipitation method were made. It was found that only about 53% of zinc and over 70% of the lead could be leached out of the dusts, while the other 47% of zinc and 30% of lead were left in the leaching residues. The zinc and lead in the resultant leaching solution can be effectively and selectively separated. When the weight ratio of sodium sulfide (M.W. = 222-240) to Pb was kept at 1.8, the lead in the solution could be precipitated out quantitatively while all the zinc was remained in the solution. The zinc left in the solution can be further recovered by the addition of extra sodium sulfide with a weight ratio of sodium sulfide to the zinc over 2.6. The resultant filtrate can be recycled to the leaching of dust in the next leaching process.
文摘Agrogyron elongatum were grown in nutrient solution containing moderate to high amounts of separate heavy metal of Cd, Cu, Ni and Ph in a greenhouse for a 9 - day. Cd, Cu, Ni and Ph generally led to decrease in the elongation of roots although the length of seedlings exposed to Cd and Ph at 0.05 and 0.5 mg/L showed to be slightly greater than that of controls. Of the four metals in the experiment, Ph was absorbed and accumulated to the highest level, with the concentrations of 92754 mg/kg dry weight (DW) in roots and 11683 mg/kg DW in shoots. Cd was moderately accumulated in Agrogyron elongatum, but the maximum bioaccumulation coefficients (BCs) for roots and shoots were observed. The patterns for Cu and Ni uptake and distribution in plants differed from those of Ph and Cd, as it was showed that the shoot accumulation of Cu and Ni was significantly higher than in roots. A. elongation had the highest Ni concentration in shoots (30261 mg/kg DW) at the external concentration of 250 mg/L. Cu ranked second, with a shoot concentration of 12230 mg/kg DW when 50 mg/L Cu in solution was applied. For the four trace elements tested, the highest concentrations in shoots decreased by the order of Ni > Cu > Ph > Cd (mg/kg DW), and those in roots were Ph > Cd > Ni > Cu (mg/kg DW). Malic, oxalic and citric acids exuded by roots exposed to 1 and 50 mg/L of the metals were detected. Release of organic acids from plants significantly differed among the metal treatments. Cu was most effectively in inducing root exudation of the three types of organic acids. Cd, and Ni were also the inducers of secretion of malic and oxalic acids. With reference of Pb, a small amounts of malic and oxalic acids were detected in the root exudates, but few quantities, of citric acid were. found. However, no correlation between alternations in root exudation of organic acids and metal accumulation could be established.
文摘Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface(0 to 20 cm) soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations(Pb, Zn, Cd and Cu) with clay content revealed a strongly significant relationship while significant relationship( P 〈 0.001 ) was also obtained between Cd + Zn and Pb + Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order: residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb(29.1% ) to its total concentration in the soils was higher than those of Zn(4.70% ), Cd(3.16% ) and Cu(9.50% ). The percentages of the water soluble and the exchangeable fractions of Pb(1.80% ) and Cd(2.74% ) were markedly greater than those of Zn(0.10% ) and Cu(0.15% ), suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.
基金supported jointly by the National Key R&D Program of China (No. 2016YFC0600408)the National Natural Science Foundation of China (Nos. 41572060, 41773054, U1133602, 41802089)+3 种基金China Postdoctoral Science Foundation (No. 2017M610614)projects of YM Lab (2011)Innovation Team of Yunnan Province and KMUST (2008 and 2012)Yunnan and Kunming University of Science and Technology Postdoctoral Sustentation Fund
文摘A type of carbonate-hosted lead–zinc(Pb–Zn)ore deposits, known as Mississippi Valley Type(MVT)deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to account for metal precipitation mechanism of the MVT ore deposits, in which fluids with metal-chloride complexes happen to mix with fluids with reduced sulfur, producing metal sulfide deposition. In this hypothesis, however, the detailed chemical kinetic process of mixing reactions, and especially the controlling factors on the metal precipitation are not yet clearly stated. In this paper, a series of mixing experiments under ambient temperature and pressure conditions were conducted to simulate the fluid mixing process, by titrating the metal-chloride solutions, doping withor without dolomite, and using NaHS solution. Experimental results, combined with the thermodynamic calculations, suggest that H_2S, rather than HS^-or S^(2-),dominated the reactions of Pb and/or Zn precipitation during the fluid mixing process, in which metal precipitation was influenced by the stability of metal complexes and the pH. Given the constant concentrations of metal and total S in fluids, the pH was a primary factor controlling the Pb and/or Zn metal precipitation. This is because neutralizing or neutralized processes for the ore-forming fluids can cause instabilities of Pb and/or Zn chloride complexes and re-distribution of sulfur species, and thus can facilitate the hydrolysis of Pb and Zn ions and precipitation of sulfides. Therefore, a weakly acidic to neutral fluid environment is most favorable for the precipitation of Pb and Zn sulfides associated with the carbonate-hosted Pb–Zn deposits.
文摘A field experiment was conducted to compare the growth and metal accumulation of Vetiveria zizanioides, Paspalum notatum, Cynodon dactylon and Imperata cylindraca var. major on the tailings, amended with 10 cm domestic refuse + complex NPK fertilizer(Treatment A), 10 cm domestic refuse(Treatment B) and complex NPK fertilizer(Treatment C) respectively, and without any amendment used as control(Treatment D). The results indicated that V. zizanioides was a typical heavy metal excluder, because the concentrations in shoots of the plants were the lowest among the four plants tested. The most of metal accumulated in V. zizanioides distributed in its root, and transportation of metal in this plant from root to shoot was restricted. Therefore, V. zizanioides was more suitable for phytostabilization of toxic mined lands than P. notatum and C. dactylon, which accumulated a relatively high level of metals in their shoots and roots. It was also found that I. cylindraca var. major accumulated lower amounts of Pb, Zn and Cu than C. dactylon and P. notatum, and could also be considered for phytostalilisaton of tailings. Although the metal(Pb, Zn and Cu) concentrations in shoots and roots of V. zizanioides were the lowest, the total amounts of heavy metals accumulated in shoots of V. zizanioides were the highest among the four tested plants due to the highest dry weight yield of it. The results indicated that V. zizanioides was the best choice among the four species used for phytoremediation(for both phytostabilization and phytoextraction) of metal contaminated soils.
文摘The contents of Pb, Cd, Cr, As, and Hg was investigated in the neighboring areas of a lead smelting enterprise and the metals contamination of soil was evaluated with the methodologies of the single factor index and Nemerow integrated index. It is found that the content of heavy metals in the neighboring areas has no obvious difference from the reference points. And the soil contamination of heavy metals varies by elements, the contamination index follows the pollution order: Cd>Hg>Cr>As>Pb. The pollution degree of Cd is at high level and Hg at low level, but Cr and As reached the warning level. Therefore, the lead smelting enterprises should not only control lead but also other heavy metals as Cd.
文摘This study focused on the influence of base metal mining on heavy metal levels in soils and plants in the vicinity of Arufu lead-zinc mine, Nigeria. Soil samples (0-15 cm depth) and plant samples were collected from cul-tivated farmlands in and around the mine, the unmineralized site and a nearby forest (the control site). The samples were analyzed for heavy metals (Fe, Zn, Mn, Cu, Pb, Cr and Cd) by Atomic Absorption Spectrophotometry (AAS). The physical properties of soils (pH and LOI) were also measured. Results showed that soils from cultivated farm-lands have neutral pH values (6.5-7.5), and low organic matter contents (<10%). Levels of Zn, Pb and Cd in culti-vated soils were higher than the concentrations obtained from the control site. These heavy metals are most probably sourced from mining and agricultural activities in the study area. Heavy metal concentrations measured in plant parts decreased in the order of rice leaves>cassava tubers>peelings. In the same plant species, metal levels decreased in the order of Zn>Fe>Mn>Cu>Pb>Cr>Cd. Most heavy metals were found in plant parts at average concentrations normally observed in plants grown in uncontaminated soil, however, elevated concentrations of Pb and Cd were found in a few cassava samples close to the mine dump. A stepwise linear regression analysis identified soil metal contents, pH and LOI as some of the factors influencing soil-plant metal uptake.
基金Project(2009ZX07212-001)supported by the Major Science and Technology Program for Water Pollution Control and Treatment of ChinaProject(51079002)supported by the National Natural Science Foundation of China
文摘The heavy metal(such as Cr,Ni,Cu,Cd,Pb,and Zn)concentration,speciation,and pollution source in 43 sediment samples from the Xiangjiang River were investigated using sequential extraction combined with Pb isotope analysis.Cu,Cd,Pb,and Zn concentrations are higher than their background values,while Cr and Ni concentrations are close to those.Sequential extraction demonstrates that heavy metals have different fractions,showing different bioavailabilities.The w(206Pb)/w(207Pb)ratio increases with decreasing bioavailability in the order of exchangeable<carbonate≈Fe-Mn oxides≈organic<residual(p<0.05).Wastewater,dust,and slag from mining and smelting areas,and the residual Pb are assumed to be the primary anthropogenic and natural sources of Pb,respectively.The percentages of anthropogenic Pb in the exchangeable,carbonate,Fe-Mn oxides,and organic fractions are(91.5±16.7)%,(61.1±13.9)%,(57.4±11.1)%,and(55.5±11.2)%,respectively,suggesting a significant input of anthropogenic Pb in these four fractions.
基金Supported by the Natural Science Foundation of Hainan Province(411102)the Scientific Research Innovation Project for College Graduates of Hainan Normal University(Hsyx2015-33)the College Students Science and Technology Innovation Project in Hainan Province(cxcyxj2017016)
文摘[Objectives] The research was conducted to study characteristics of bioavailable levels pollution of heavy metals in the surface soil of the lead-zinc mine in Changhua.[Methods] A total of 56 surface samples were collected from the 3 study zones (peripheral zone, reclamation zone and tailing zone) located at the lead-zine mine in Changhua. Based on total and bioavailable heavy metals (Pb, Zn, Cu and Cd) in soils, the correlation of total content with bioavailable content was analyzed, and their pollution characteristics were assessed by methods of single factor pollution index, Nemerow pollution index, geological accumulation index and potential ecological risk index.[Results] (i) The surface soils were polluted by Pb, Zn, Cu, Cd in different degrees, and the overall trend of the contents of the 4 heavy metals was in order of Cd 〉 Pb 〉 Zn 〉 Cu. The average excess multiple of heavy metals of total and bioavailable content in soils were in the order of peripheral zone 〉 tailing zone 〉 reclaimed zone, and their pollution degrees were tailing zone 〉 peripheral zone 〉 reclaimed zone. (ii) In general, the total and bioavailable contents of Pb, Zn, Cu, Cd showed a significant correlation, but were not correlated in each study zone. (iii) Pollution degrees of the study zones were in the order of tailing zone 〉 peripheral zone 〉 reclamation zone. The pollutions of heavy metals Pb and Cd were more serious, especially Cd reached high levels of pollution degree, and the pollution degrees of Zn, Cu were lighter. Contributors of ecological risk were mainly Cd, Pb and Cu, and the contribution of Cd achieved more than 90 %, making it the main source of pollution.[Conclusions] The results not only revealed the pollution status of heavy metals in the surface soil of the abandoned coal mine, but also could provide scientific guidance for reasonable utilization and ecological recovery of the land.
文摘Difference of montmorillonite (Mt), illite (It) and kaolinite (Kt) in lead sorption characteristics and the effects of amorphous Fe and Al oxide coatings on the characteristics were experimentally studied with logistic model. The sorption curves had sigmoid feature due to use of acetate-type buffer solution. With the model the sorption process could be divided into four stages and the sorption characteristics at the stages were discussed. The results showed that, after Mt, It and Kt were coated by amorphous Fe oxide, their maximum sorption capacity (MSC) and percentage of high-SSC concentration scope (HCS) of Pb2+ increased markedly, but the specific sorption capacity (SSC) decreased. With regard to effects of amorphous Al oxide coating, except for It+AI, the SSC of other samples showed a downtrend, despite that their MSC remained unchanged. Eventually, the gray correlation degrees to Pb2+ sorption for different physicochemical characteristics of the clay minerals were indicated to be higher for hydronium, zero point of surface charge and hydroxy, but lower for specific surface area, density of surface charge and amount of surface charges.
基金Supported by the National Natural Science Foundation of China(No.20571032)
文摘A novel metal-organic framework(MOF) compound of Pb(C5H4NCOO)2 was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction. The data of unit cell: orthorhombic space group Pccn, a=1.0325(2) nm, b=1.3597(3) nm, c=0.8499(2) nm, V=1.1931(4) nm^3, Z=4, Dc=2.513 g/cm^3, R1=0.047 were obtained on the basis of 1365 reflections with Fo〉2σ(Fo). PbN2O6 polyhedron adopts the distorted cubic configuration which is assigned to the holodirected geometry. These PbN2O6 polyhedra can form the zigzag chain by edge-sharing mode along(001) direction. Pb atom is connected by six nicotinic acid molecules, leading neutral 3D metal-organic framework with a channel defined by four Pb atoms and four nicotinic acid molecules.
基金funded by the Natural Science Foundation of Hunan Province,grant number“2021JJ30679”the Hunan Provincial Department of Education General Project,grant number“19C1744”。
文摘Exploring transport patterns of soil contaminants is essential for solving the problem of heavy metal contamination in mine soils.In this study,contamination of Pb,Zn,and Cd in the mountain soils of the lead–zinc ore mines in Ganxi Township,Hengdong County,Hunan Province,China was investigated,and their transport patterns were further explored using a soil-column model and numerical simulation techniques.In total,111 mine soil samples were collected and placed into six experimental soil columns.By controlling the water flow,a control soil column group(CK),two mixed soil columns X1 with daily water flows of 1 and 5 L,and three mixed soil columns X3 with daily water flows of 2,3,and 4 L were evaluated.The results showed that the residual fraction of Pb accounted for 71.93%of the content on average,whereas the exchangeable fractions of Zn,Cd,and Fe-Mn oxide-bound fractions of Zn and Cd accounted for 28.60%,31.07%,and 43.2%and 53.54%of the content,respectively.Pb,Zn,and Cd in the soils of the CK,X1,and X3 groups mainly were accumulated at a depth from approximately 0 to 20 cm,and the content at this depth accounted for 60.09%of that at a 0~40 cm depth.The soil at a depth range of 0~10 cm was most seriously contaminated,and the proportion of content was 32.39%of that at a 0~40 cm depth.Numerical simulation showed that on the 5 th day,the pollutant transport range was 0~24 cm,and on the 9 th day,the pollutant transport range exceeded 40 cm.On the 15 th day,the transport capacity of pollutants at depths of 0~40 cm was close to the stable state,but the soil at a depth of 0~10 cm was still heavily polluted.These results reflect the transport pattern of heavy metal pollutants in the soil of lead–zinc ore mines and may provide a reliable scientific support for the prevention of heavy metal contamination in mine environments.