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Smelting activities are the main pathway for the anthropogenic release of heavy metals (HMs) into the soil-groundwater environment. It is vital to identify the factors affecting HMs pollution to better prevent and manage soil pollution. The present study conducted a comprehensive investigation of HMs in soil from a large abandoned Zn smelting site. An integrated approach was proposed to classify and quantify the factors affecting HMs pollution in the site. Besides, the quantitative relationship between hydrogeological characteristics, pollution transmission pathways, smelting activities and HMs pollution was established. Results showed that the soils were highly contaminated by HMs with a pollution index trend of AsZnCdPbHg. In identifying the pollution hotspots, we conclude that the pollution hotspots of Pb, As, Cd, and Hg present a concentrated distribution pattern. Geo-detector method results showed that the dominant driving factors for HMs distribution and accumulation were the potential pollution source and soil permeability. Additionally, the main drivers are variable for different HMs, and the interaction among factors also enhanced soil HMs contamination. Our analysis illustrates how the confounding influences from complex environmental factors can be distilled to identify key factors in pollution formation to guide future remediation strategies.

Soil-formation process is critical to ecological rehabilitation on bauxite residue disposal areas. In this study, a soil column experiment was taken to assess the dynamic variations of soil-formation indicators in bauxite residue driven by the integration of waste solids and microorganisms. Results showed that the combination of waste solids and microorganisms significantly decreased the alkalinity, accumulated organic carbon content, and improved aggregate stability of bauxite residue. Compared with waste solids treatments, the addition of acid-producing microorganisms enhanced the changes of soil-formation indicators. The integration of waste solids and microorganisms increased the content of aliphatic carbon, presenting low thermal stability in the residues. The integration of waste solids and microorganisms provides a potentially effective method for soil formation and ecological remediation on bauxite residue disposal areas.

Bauxite residue is a highly alkaline waste from alumina refining, and is mainly disposed by stacking with high environmental risks. Here, the migration of alkaline constituents and the restoration evaluation with phosphogypsum were discussed by soil column experiments to investigate the alkaline regulation in bauxite residue disposal areas (BRDAs). The pH, free alkali, exchangeable sodium in the top layer (0-25 cm depth) covered with BR and phosphogypsum mixtures were reduced from 10.89 ± 0.02, 285.45 ± 21.15 mmol/kg, 385.63 ± 30.34 mg/kg to 9.00 ± 0.50, 12.50 ± 1.50 mmol/kg, 97.00 ± 10.50 mg/kg. For the sublayers, including depths of 35, 45, 55 cm, these values dropped to 9.86, 10.06, 10.03; 38.23, 86.12, 148.00 mmol/kg; 152.90, 246.00, 305.00 mg/kg, respectively. These results indicated alkaline indicators for phosphogypsum amended BR declined dramatically, and the parameters for sublayers were also decreased due to the migration of alkaline constituents. The physicochemical properties for amended BR could meet the conditions for plant growth. This research provided a reference for alkalinity regulation in BRDAs by phosphogypsum.

Biomass fermentation provides a potential route toward the ecological disposal for the bauxite residue (BR) with high alkalinity issues. However, how to accelerate the remediation of the alkaline problem with a long-term durability is still a big challenge. Herein, we investigated the acceleration of the decomposition of straw toward organic acid species via a pyrolysis strategy as well as the pH stability during long-term dry-wet aging for the treated BR. The pH of pyrolytic BR at 300 °C is stabilized at around 8.90 after 70 days’ dry-wet aging. During the aging, the main Ca-contained alkaline minerals of calcite and cancrinite are dissolved and the content of exchangeable Na+ is reduced. This pyrolysis process can decompose straw quickly and produce more organic matters that are easily degraded to fulvic and humic acid as evidenced by 3D fluorescence spectrum analysis. Compared to the fermentation with straw under natural conditions, the alkalinity regulation of BR after pyrolysis is featured with shorter period and lower pH as well as long-term pH stability. Therefore, the synergistic pyrolysis of BR with straw provides an alternative method to address the alkaline issues, which is conducive to promoting the soil formation of BR.

Purpose The interaction of minerals and organic matter significantly affects the stability of organic carbon, which is key to the rehabilitation of bauxite residue. However, due to the microscopic structure of minerals and the chemical composition of dissolved organic matter (DOM), the interaction mechanism between alkaline minerals and DOM in the presence of calcium ions that are widely used as amendments is still poorly understood. Methods In this work, the adsorption mechanism of organic matter by sodalite and cancrinite in the presence of calcium ions was investigated by fourier transform infrared spectroscopy (FTIR), excitation-emission matrix fluorescence (EEMs), thermogravimetric analysis (TG-DSC) and atomic force microscope (AFM). Results The calcium ions can act as bridges to connect the negative sites on the mineral surface with the polysaccharide functional groups of organic matter, thus allowing the DOM to enter the pore channels of mineral structure to sequester organic carbon via ligand-exchange and/or electrostatic interactions. Furthermore, DOM located in the pore structure within cancrinite may be better protected due to physical isolation. The 3D view of the interacted minerals-organic matter assemblages provided visual evidence that the adsorption sites distributed on the surface of cancrinite increased by the action of calcium ions, with different adsorption capacity of individual sites for DOM. Conclusions The calcium ions enhance the ability of alkaline minerals to trap dissolved organic carbon, and the work highlighted the significance of organo-mineral associations in the microscopic mineral structure for the organic carbon sequestration in the revegetation process of bauxite residue disposal areas.

Iron-modified biochar (FeOS) is known to be effective at immobilization of arsenic (As) in soils. A pot experiment was conducted to investigate the effects of FeOS on As availability and ttransportation in the soil-rice system at different growth stages of rice with different pollution levels. The results showed that Fe concentration decreased and As concentration increased in paddy soils with the FeOS addition, especially in 120 mg/kg As treatment, the As concentration decreased by 16.46% and 30.56% at the maturity stage with 0.5% and 1% FeOS additions, respectively. Compared with the control, the application of FeOS reduced the arsenic content in rice tissues and increased the biomass, with the root biomass increased by 12.68% and the shoot biomass was increased by 8.94% with the addition of 1% FeOS. This may be related to the promotion of iron plaque formation and the transformation of microbial community structure in FeOS treatments, in accordance with the result of gene abundance and Fe/As contents of iron plaque in the study. This study is expected to provide further support and theoretical basis for the application of FeOS in the remediation of As contaminated paddy soil.

A column experiment was conducted to investigate the effect of phosphogypsum (PG) on the saline- alkalinity, and aggregate stability of bauxite residue. Results showed that: with increasing leaching time, the concentrations of saline-alkali ions decreased while the concentration increased in bauxite residue leachate; compared with CK (control group) treatment, pH, electric conductivity (EC), exchangeable sodium percentage (ESP), sodium absorption ratio (SAR), and exchangeable Na+ content of bauxite residue were reduced following PG treatment; average particle sizes in aggregates following CK and PG treatments were determined to be 155 and 193 nm, respectively. SR-μCT test results also confirmed that bauxite residue following PG treatment acquired larger aggregates and larger pore diameter. These results indicate that the PG treatment could significantly modulate the saline-alkalinity, and simultaneously enhance aggregate stability of bauxite residue, which provides a facile approach to reclaim bauxite residue disposal areas.

Ecological reconstruction on bauxite residue disposal areas is regarded as an effective approach to eliminate potential environmental risks. Establishment of microbial communities and associated functions may improve physical and chemical properties, and may stimulate soil formation in bauxite residue. Spontaneous colonization at a disposal area in Shandong Province, China, over 50 years, indicated that natural weathering can ameliorate residues, and in turn, support the establishment of vegetation communities. Residue samples were collected from unrestored, poorly restored and well restored areas to investigate the development of microbial communities and associated functions. Microbiota significantly developed after long term natural restoration. Microbial biomass, respiration and enzyme activities significantly increased in restored bauxite residue, whereas the metabolic quotient significantly decreased. In addition, the long‐term natural restoration significantly shaped the microbial structure from alkalophilic and halophilic assemblages (Firmicutes and Actinobacteria) to neutrophilic assemblages (Acidobacteria and Planctomycetes). Both microbial communities and associated functions in well restored residue had high similarity with that in natural soil, indicating that long term restoration created diverse soil‐like microbial communities and functions. Redundancy analysis (RDA) revealed that TN, followed by Na+, ESP, SOC, AP and pH were the major influence factors in the development of microbial communities in bauxite residue. These findings provide us a biogeochemical perspective to reveal soil formation in bauxite residue and suggest that nutrient supplement and regulation of salinity‐alkalinity may benefit for the establishment of microbial communities and functions in bauxite residue.

The biogeochemistry of iron (Fe) could affect arsenic (As) fate and change its availability. Fe(II) oxidation mediated by Fe oxidizing bacteria (FeOB) has the potential for As contamination remediation due to the formation of biogenic minerals. However, microbial Fe(II) oxidation coupled with the immobilization of As and the effect of FeOB on As remediation in soils has not been thoroughly investigated. In this study, a FeOB was isolated from a paddy soil and identified as Ochrobactrum sp. EEELCW01. The kinetics reactions were used to investigate how biological and chemical reactions were involved in the Fe(II)‐NO₃⁻‐FeOB system. Microbial Fe(II) oxidation coupled As mineralization, as well as its application in As contaminated paddy soils was studied. The results suggested that biological pathway contributed to the Fe(II) oxidation and NO₃⁻ reduction in the whole process, in which the chemical Fe(II) oxidation by biogenic NO₂⁻ was involved. Meanwhile, Fe(II) facilitated the reduction of NO₂⁻ while inhibited the reduction of NO₃⁻. Adding 2% or more bacteria led to a significant removal effect for aqueous As, resulting in the formation of lepidocrocite and two As‐containing minerals (angelellite, loellingite). With the simultaneous application of FeOB and NO₃⁻, the available As content in soils decreased by 37.6% and stabilized at 0.80 mg kg⁻¹ finally. In addition, the immobilization showed long‐term effect compared to the treatment with Fe(II) or NO₃⁻ alone. The study proved that the isolated FeOB had a significant ability for As mineralization and immobilization, which provided theoretical and application basis for the remediation of As contaminated soils.

The rapid development of the smelting industry increases the release of antimony (Sb) into the soil environment, which threatens human health and ecosystems. A total of 87 samples were collected from an abandoned Sb smelting site to evaluate pollution characteristics and environmental risks of the potentially toxic elements (PTEs). The contents of As, Cu, Ni, Pb, Sb, and Zn in the fresh soils determined by P-XRF were 131, 120, 60, 145, 240, and 154 mg/kg, respectively, whilst following drying, grinding, and sieving pretreatments, the corresponding contents increased to 367, 179, 145, 295, 479, and 276 mg/kg, respectively. There was a significant correlation between the data obtained by P-XRF and ICP-OES in the treated samples, which showed the application feasibility of P-XRF. The average contents of Sb and As were 440.6 and 411.6 mg/kg, respectively, which exceeded the control values of the development land in GB 36600-2018. The ecological risk levels of the six PTEs decreased in the following order: AsSbPbZnNiCu. Non-carcinogenic risk revealed that As, Pb, and Sb posed health risks for children, whilst for carcinogenic risk, the risk values for As and Ni were higher than the limit values for both children and adults. Anthropogenic sources accounted for more than 70.0% of As, Pb, and Sb concentrations in soils, indicating a significant influence on PTEs accumulation. The findings provide a basis for quick determination of the contamination characteristics and risk control of PTEs at Sb smelting sites.

The extreme alkalinity of bauxite residue (BR) leads to difficulty with its reuse. Alkaline leachate and dust generation during the stacking process can pollute surrounding soil, air and water. In this work, co-pyrolysis of bauxite residue and sawdust was applied to rapidly produce a soil-like matrix that met the conditions for plant growth as demonstrated by ryegrass pot experiments. The present study aimed to characterize the detailed changes in physicochemical, mineral weathering, and microbial communities of the pyrolyzed BR with different ratios of saw dust after plant colonization for 2 months. With increasing sawdust addition during co-pyrolysis, the pH of BR decreased from 11.21 to 8.16, the fraction of macro-aggregates 0.25-2 mm in the water-stable agglomerates increased by 29.3%, and the organic carbon concentration increased from 12.5 to 320 mg/kg, whilst facilitating the degree of humification, which were all beneficial to its revegetation performance. The backscattered electron-scanning electron microscope-energy-dispersive X-ray spectrometry (BSE-SEM-EDS) results confirmed the occurrence of sodalite and calcite weathering on aggregate surfaces, and X-ray photoelectron spectroscopy (XPS) results of surface Al and Si compounds identified that some weathering products were clay minerals such as kaolinite. Furthermore, bacterial community composition and structure shifted towards typical soil taxonomic groups. These results demonstrate soil development of treated BR at an early stage. The technique is a combination of alkalinity regulation and agglomerate construction, which accelerates soil formation of BR, thus proving highly promising for potential application as an artificial soil substitute.

Bauxite residue, a typical industrial solid waste which contains a large amount of Na+, is usually physically degraded. Understandings of aggregate formation, which is a critical process in soil development, are essential to facilitate ecological rehabilitation on the disposal areas. However, few studies have investigated the aggregation behavior and mechanisms of key salt ions (Ca2+ and Na+) in residue aggregates. Therefore, an integrated method of Le Bissonnais’ method, the combined determination method, and laser diffraction measurements was applied to evaluate aggregate stability, surface properties and disintegration behavior of bauxite residue following Ca/Na additions. With increasing Ca2+ addition, mean weight diameter (MWD) increased, indicating improved resistance to dispersion. Ca2+ had a positive effect on flocculation of silt‐size microaggregates, whilst disintegration was induced following Na+ addition. Repeated laser diffraction analysis of residue samples circulating in 50 mmol L‐1 electrolyte solution (Ca2+/Na+) provided a detailed view of the changes in particle size distribution as aggregates fragmented. The visualized three‐dimensional surface map revealed that Na+ promoted the disintegration of >250 μm aggregates into finer dispersed particles, whilst Ca2+ protected the microaggregates from fragmenting into smaller particles. Variation in electrochemical properties of aggregate surfaces affected the micro‐morphology significantly. The findings provide a new approach to specify pedogenic aggregate behavior of bauxite residue, whilst revealing the effects of Ca2+/Na+ on aggregate stability, surface electrochemical properties and its micromorphology. The results will provide a detailed understanding of aggregate behavior during soil formation process in bauxite residue.

Large-scale discharge of bauxite residue, an alkaline, saline and nutrient-deficient waste material produced in the process of alumina production, has created extreme environments that are challeng...

Bauxite residues, a large volume solid waste, are in urgent need of effective disposal and management. Especially, strategies to alleviate the high alkalinity of bauxite residue remain a big challenge. Here, we developed a synergistic pyrolysis to neutralize the alkalinity of bauxite residue and upgrade the structure of biomass simultaneously. By cooperating the catalytic feature from bauxite residue, rice straw, a cellulose-enriched biomass, could prefer to produce acidic components under a hypothermal pyrolysis temperature (below 250 °C) and partial oxygen-contained atmosphere as evidenced by the synchronous TGA-FTIR analysis. In return, these in-situ produced acidic components neutralized the bauxite residue profoundly (pH decreased from 11.5 to 7.2) to obtain a neutral product with long-term water leaching stability. Also, a higher pyrolysis temperature led to neutral biochar-based products with well-defined carbonization characteristics. Thus, the biomass-driven pyrolysis strategy provides a potential to dispose the alkalinity issue of bauxite residue and further opportunities for the sustainable reuse and continuing management of bauxite residue.

Bauxite residue has extreme alkalinity, poor aggregate stability, and low organic carbon content, which limits plant growth on large expanses of bauxite residue disposal areas. Soil formation of bauxite residue is one of the effective approaches to transform bauxite residue into a soil‐like medium for revegetation. In order to improve aggregate stability and organic carbon content in the short term, addition of substrate amendments is crucial to accelerate soil formation of bauxite residue. Nevertheless, the effect of different amendments on the stability, organic and humic substances distribution in bauxite residue aggregate is unclear. Therefore, a column experiment was used to investigate the distribution and stability of aggregate, and aggregate‐associated carbon by adding phosphogypsum and vermicompost (PVC), and biosolids and microorganism (BSM). The average particle sizes of CK (control check), PVC, and BSM treatments were observed to be ~114, ~157, and ~188 nm, respectively. Compared with CK treatment, the contents of organic carbon, humic acid, and fulvic acid following PVC treatment increased by 1.65, 1.59, and 1.57 times, respectively, and the increased contents of organic carbon, humic acid, and fulvic acid following BSM treatment reached 2.90, 2.69, and 2.60 times, respectively. Results demonstrated that amendment additions enhanced aggregate stability and carbon sequestration, but the effects of BSM treatment were better than those of PVC treatment. The findings offer an evidence that BSM treatment is a feasible approach to accelerate soil formation of bauxite residue, which shows promising applications to reclaim bauxite residue disposal areas.

Bauxite residue is the industrial waste generated from alumina production and commonly deposited in impoundments. These sites are bare of vegetation due to the extreme high salinity and alkalinity, as well as lack of nutrients. However, long term weathering processes could improve residue properties to support the plant establishment. Here we investigate the development of bacterial communities and the geochemical drivers in bauxite residue, using Illumina high-throughput sequencing technology. Long term weathering reduced the pH in bauxite residue and increased its nutrients content. The bacterial community also significantly developed during long term weathering processes. Taxonomic analysis revealed that natural weathering processes encouraged the populations of Proteobacteria, Chloroflexi, Acidobacteria and Planctomycetes, whereas reducing the populations of Firmicutes and Actinobacteria. Redundancy analysis (RDA) indicated that total organic carbon (TOC) was the dominant factors affecting microbial structure. The results have demonstrated that natural weathering processes improved the soil development on the abandoned bauxite residue disposal areas, which also increased our understanding of the correlation between microbial variation and residue properties during natural weathering processes in Bauxite residue disposal areas.

Ecological succession by microbial activity on bauxite residue disposal areas (BRDAs) would accumulate nutrients and convert the residue into a soil-like material. However, the role of microorganis...

Contaminated sites pose a significant risk to human health and the regional environment. A comprehensive study was dedicated to improving the understanding of the contamination condition of a smelting site by integrating multi-source information through 3D visualization techniques. The results showed that 3D visualization reveals excellent potential for application in the environmental studies to finely depict contamination in soils and establish relationships with geological features, hydrological conditions, and sources of contamination. The contamination plume model revealed that the soil environment at the site was seriously threatened by toxic metals, and dominated by multi-metal contamination, with contamination soil volume ranked as Cd As Pb Zn Hg. The stratigraphic model revealed the heterogeneous geological conditions of the site and identified the mixed fill layer as the primary remediation soil layer. The permeability model revealed that soil permeability significantly influenced contamination dispersion and contributed to delineate the contamination boundary accurately. The ecological hazard model targeted the high ecological hazard area and determined the high hazard contribution of Cd and Hg in the site soil. The outcomes can be directly applied to actual site remediation and provide a reference for the contaminated sites evaluation and restoration in the future.

The deficiencies of certain nutrients limit plant growth in bauxite residue disposal areas. In this study, residue samples at different depths (0-2 cm, 2-10 cm, 10-20 cm, 20-40 cm, and 40-60 cm) and stacking ages were collected to analyze the changes of nutritional conditions following natural vegetation encroachment processes. With the encroachment of natural vegetation, the nutrient components improved greatly. The contents of organic carbon, total nitrogen, and available phosphorus increased from 5.6 g/kg to 10.8 g/kg, 0.07 g/kg to 0.73 g/kg, and 6.3 mg/kg to 24.9 mg/kg, respectively. With the increase of natural weathering time, microbial carbon, nitrogen, and phosphorus increased significantly. Natural weathering process and vegetation encroachment improved the circulation and accumulation of nutrient substances in bauxite residues.

Production of hydrogen peroxide (H2O2) via in situ electrochemical water oxidation possesses great potential applications in the energy and environment fields. In this work, for the first time, we ...

Biomass fermentation has been proposed as a simple and economical strategy to alleviate the high alkalinity of bauxite residue. This study investigates the neutralization of bauxite residue following the application of biomass as an alkali modifier by natural fermentation. Fresh bauxite residue samples were collected from Pingguo refinery (Aluminum Corporation of China). Samples were treated with straw mulching (SC), straw mixing (SM), bagasse mulching (BC), and bagasse mixing (BM), respectively. Treatments were analyzed for pH, EC, metal cations, and soluble alkali (OH−, Al(OH)4− and CO32−). The mineral phase and Na speciation were analyzed by X-ray diffraction (XRD) and near-edge X-ray absorption fine structure (Na-XANES). Optimum application rate for either straw or bagasse was 20% (w/w), reducing leachate pH from 10.26 to 8.56. During biomass transformation, the alkaline mineral grossular was completely dissolved, while calcite and cancrinite were dissolved to a lesser degree. No treatment changed the spatial distribution of Na+, but the basic anions (OH−, CO32−, and Al(OH)4−) were significantly reduced. Following treatment application, soluble alkali in the residues was significantly reduced while the alkaline minerals were slightly dissolved. This was determined as the main cause for the decrease in residue pH.

A column leaching experiment was used to investigate the efficacy of amendments on their ability to remove alkaline anions and metal ions from bauxite residue leachates. Treatments included, simulated acid rain (AR), phosphogypsum + vermicompost (PVC), phosphogypsum + vermicompost + simulated acid rain (PVA), and biosolids + microorganisms (BSM) together with controls (CK). Results indicated that amendment could effectively reduce the leachate pH and EC values, neutralize OH−, CO32−, HCO3−, and water soluble alkali, and suppress arsenic (As) content. Correlation analysis revealed significant linear correlations with pH and concentrations of OH−, CO32−, HCO3−, water-soluble alkali, and metal ions. BSM treatment showed optimum results with neutralizing anions (OH−, CO32−, and HCO3−), water soluble alkali, and removal of metal ions (Al, As, B, Mo, V, and Na), which was attributed to neutralization from the generation of small molecular organic acids and organic matter during microbial metabolism. BSM treatment reduced alkaline anions and metal ions based on neutralization reactions in bauxite residue leachate, which reduced the potential pollution effects from leachates on the soil surrounding bauxite residue disposal areas.

Microbe induced iron (Fe) reduction play an important role in arsenic (As) transformation and the related secondary mineral formation. Meanwhile biochar could react as electron transfer shuttle for this process. Impact of biochar and model electron transfer shuttle anthraquinone-2,6-disulfonate (AQDS) on the chemical/biological iron reduction of As (Ⅲ)-adsorbed ferrihydrite and the solid-liquid redistribution of As in M1 buffer were studied. Fe reduction results in the release of As adsorbed on ferrihydrite into the solution. Under abiogenic conditions, both biochar and AQDS promoted ferrous production, the chemical oxidation of As(III) and As release. Inoculate with Shewanella oneidensis MR-1, AQDS has greater electronic shuttle function than biochar (with the maximum Fe (Ⅱ) contents: 154 mg/L > 76.6 mg/L respectively). However, only 12.8 mg/L As was released in the presence of AQDS, which was much lower than that in the presence of biochar (21.6 mg/L), and may be associated with the transformation of As speciation and the formation of secondary minerals. XRD and EDX-SEM confirmed that the As could be fixed by the generated secondary mineral vivianite. The relative contents of vivianite in biological control and AQDS addition were 2.7% and 18.4%, respectively. This study provides information on the transformation and migration of As and Fe with the addition of biochar under anaerobic conditions, which is potential to understand the mechanism of As(III)-contaminated soil remediation.

Smelting activities pose serious environmental problems due to the local and regional heavy metal pollution in soils they cause. It is therefore important to understand the pollution situation and its source in the contaminated soils. In this paper, data on heavy metal pollution in soils resulting from Pb/Zn smelting (published in the last 10 years) in China was summarized. The heavy metal pollution was analyzed from a macroscopic point of view. The results indicated that Pb, Zn, As and Cd were common contaminants that were present in soils with extremely high concentrations. Because of the extreme carcinogenicity, genotoxicity and neurotoxicity that heavy metals pose, remediation of the soils contaminated by smelting is urgently required. The primary anthropogenic activities contributing to soil pollution in smelting areas and the progressive development of accurate source identification were performed. Due to the advantages of biominerals, the potential of biomineralization for heavy metal contaminated soils was introduced. Furthermore, the prospects of geochemical fraction analysis, combined source identification methods as well as several optimization methods for biomineralization are presented, to provide a reference for pollution investigation and remediation in smelting contaminated soils in the future.

Toxic metal(loid) (TM) soil pollution at large-scale non-ferrous metal smelting contaminated sites is of great concern in China, but there are no detailed reports relating to them. A comprehensive study was conducted to determine contamination characteristics and horizontal and vertical spatial distribution patterns of soils at an abandoned zinc smelting site in Southern China. The spatial distribution of TMs revealed that soil environmental quality was seriously threatened, with Cd, Zn, As, Pb and Hg being the main contaminants present. The distribution of all TMs showed strong spatial heterogeneity and were expressed as a "patchy aggregation" pattern due to strong anthropogenic and production activities. Vertical migration of TMs indicated that the pollutants were mainly concentrated in the fill layers. Different contaminants had various migration depths, with migration occurring as: Cd > Hg > As > Zn > Pb> Cu> Mn> Sb. Analysis of their spatial variability showed that As, Pb, Cd and Hg had strong regional spatial variability. This research provides a new approach to comprehensively analyze TM pollution characteristics of non-ferrous smelting sites. It provides valuable information for guiding post-remediation strategies at abandoned non-ferrous metal smelting sites.

Heavy metals (HMs) pollution is a universal and complex problem at lead smelting sites. Further understanding on the distribution, coexistence relationship and occurrence form of multi-metals in soils should be taken prior to restoration on the contaminated sites. In this study, 222 soil samples in a typical abandoned lead smelting site were investigated to understand the spatial distribution and geochemical partitioning of HMs. The results showed that soil quality was seriously threatened by As, Pb and Cd, which expressed high spatial heterogeneity. Integration of sequential extraction, X-ray photoelectron spectroscopy and mineral liberation analysers were employed to qualify the geochemical partitioning of HMs. The data showed that Pb and As were mainly partitioned in the reducible phase and residue phase, where the maximum of As were 18% and 79%, and the maximum of Pb were 31% and 64%, respectively, whilst Cd was mainly partitioned with residue phase (about 25%) and weakly acid soluble phase (about 18%). Paulmooreite was the major important mineral host for Pb and As, whereas Cd predominantly existed in willemite. These minerals containing HMs could usually with Fe reside in the octahedral layer of clay minerals such as montmorillonite, and may also reside in the interlayer. Quartz, montmorillonite and goethite were closely associated with HMs minerals in contaminated soils, which limited vertical migration of HMs and potential risks to groundwater. The results enhanced the understanding of spatial distribution and occurrence behavior of HMs, whilst providing potential benefits to heavy metal stabilization and risks control at abandoned non-ferrous metal smelting sites.