Pb/As simultaneous removal from soil leachate of Pb/Zn smelting sites by magnetic biochar.

Lead (Pb) and arsenic (As) contaminated soils, caused by Pb and zinc (Zn) smelting activities, pose an urgent environmental issue. Magnetic biochar (MB) has been regarded as an increasingly appealing candidate for the remediation of multi-metals in contaminated soils or their leachate. Finding economically feasible preparation methods for MB and demonstrating its remediation potential is desperately required for the remediation of such complex smelting sites. In this study, a modified MB was prepared using an optimized co-precipitation method, and its application potential for Pb/As simultaneous removal based on the basic properties of a typical Pb/Zn smelting site was evaluated. The surface modifications of MB facilitated the encapsulation of various ultrafine iron oxide particles, predominantly γ-Fe2O3 and Fe3O4, whilst notably enhancing the presence of oxygen-containing surface functional groups. The adsorption of Pb(II) and As(III) by MB was well-described using the pseudo-second-order adsorption and Langmuir models. The existence of SO42- and Ca2+ in the soil leachate competed with the adsorption sites for Pb(II) and As(III). Notably, within the pH range of 5-9, the adsorption efficiency of Pb(II) by MB increased with the rising solution pH, whereas alterations in pH minimally affected the removal rate of As(III), maintaining a consistent removal rate exceeding 95%. Furthermore, dissolved organic matter (DOM) abundant in organic functional groups, particularly CO and CC groups, significantly augmented the adsorption affinity for both Pb(II) and As(III). An application rate of 2 g/L could effectively reduce the concentration of Pb(II) and As(III) in soil leachate to <0.05 mg/L. The findings demonstrated the potential of the prepared MB for simultaneous removal of As(III) and Pb(II) in soil leachate, which should be beneficial to multi-metals polluted soil remediation in Pb/Zn smelting sites.

Spatial distribution, chemical fractionation and risk assessment of Cr in soil from a typical industry smelting site in Hunan Province, China.

The closure or relocation of many industrial enterprises has resulted in a significant number of abandoned polluted sites enriched in heavy metals to various degrees, causing a slew of environmental problems. Therefore, it is essential to conduct research on heavy metal contamination in the soil of industrial abandoned sites. In this study, soils at different depths were collected in a smelting site located in Hunan Province, China, to understand the Cr distribution, speciation and possible risks. The results revealed that the high-content Cr and Cr(VI) contamination centers were mainly concentrated near S1 (Sample site 1) and S5. The longitudinal migration law of chromium was relatively complex, not showing a simply uniform trend of decreasing gradually with depth but presenting a certain volatility. The vertical distribution characteristics of chromium and Cr(VI) pollution suggest the need for attention to the pollution from chromium slag in groundwater and deep soil layers. The results of different speciation of Cr extracted by the modified European Community Bureau of Reference (BCR) method showed that Cr existed primarily in the residual state (F4), with a relatively low content in the weak acid extraction state (F1). The correlation analysis indicated that Cr was affected by total Cr, pH, organic matter and total carbon during the longitudinal migration process. The RSP results revealed that the smelting site as a whole had a moderate level of pollution. Soil at depths of 2-5 m was more polluted than other soil layers. Consequently, it is necessary to treat the site soil as a whole, especially the subsoil layer (2-5 m). Health risk assessment demonstrated that the soil chromium pollution was hazardous to both adults and children, and the probability of carcinogenic and non-carcinogenic risk was relatively high in the latter group. As a result, children should be a group of special concern regarding the assessment and remediation of soil contaminated with Cr. This study can provide some insight into the contamination characteristics, ecological and health risks of chromium in contaminated soils and offer a scientific basis for the prevention and control of chromium pollution at abandoned smelting sites.

The formation of multi-metal(loid)s contaminated groundwater at smelting site: Critical role of natural colloids.

The occurrence and migration of colloids at smelting sites are crucial for the formation of multi-metal(loid)s pollution in groundwater. In this study, the behavior of natural colloids (1 nm-0.45 µm) at an abandoned smelting site was investigated by analyzing groundwater samples filtered through progressively decreasing pore sizes. Smelting activities in this site had negatively impacted the groundwater quality, leading to elevated concentrations of zinc (Zn), lead (Pb), arsenic (As), and cadmium (Cd). The results showed that heavy metal(loid)-bearing colloids were ubiquitous in the groundwater with the larger colloidal fractions (∼75 -450 nm) containing higher abundances of pollutants. It was also observed that the predominant colloids consisted of Zn-Al layered double hydroxide (LDH), sphalerite, kaolinite, and hematite. By employing multiple analytical techniques, including leaching experiments, soil colloid characterization, and Pb stable isotope measurements, the origin of groundwater colloids was successfully traced to the topsoil colloids. Most notably, our findings highlighted the increased risk of heavy metal(loid)s migration from polluted soils into adjacent sites through the groundwater because of colloid-mediated transport of contaminants. This field-scale investigation provides valuable insights into the geochemical processes governing heavy metal(loid) behavior as well as offering pollution remediation strategies specifically tailored for contaminated groundwater.

Polymetallic contamination drives indigenous microbial community assembly dominated by stochastic processes at Pb-Zn smelting sites.

Indigenous microbial communities in smelting areas are crucial for maintaining fragile ecosystem functions. However, the community assembly process and their responses to polymetallic pollution are poorly understood, especially the taxa in each bin from the amplicons that contributed to the assembly process. Herein, microbial diversity, co-occurrence patterns, assembly process and the intrinsic mechanisms across contamination gradients at a typical PbZn smelting site were systematically unravelled by high-throughput sequencing. The results showed a consistent compositional profile among the indigenous communities across sampling sites, wherein genera KD4-96 from Chloroflexi and Sphingomonas from Proteobacteria emerged as the most abundant taxa. Network modularity of the high- and middle-contaminated communities at Pb and Zn smelting sites was >0.44, indicating that community populations were clustered into modules to resist high heavy metal stress. Stochastic processes dominated the community assembly, with the greatest contribution from drift (DR), which was significantly correlated with Pb, Zn, Cr and Cu contents. What's particular was that the DR-controlled bins were dominated by Proteobacteria (typical r-strategists), while the HoS-controlled bins were by Chloroflexi (typical K-strategists). Furthermore, the proportion of DR in the bins dominated by Sphingomonadaceae (phylum Proteobacteria) increased gradually with the increase of heavy metal contents. These discoveries provide essential insights for community control in restoring and mitigating soil degradation at PbZn smelting sites.

Driving factors for distribution and transformation of heavy metals speciation in a zinc smelting site.

Heavy metal pollution at an abandoned smelter pose a significant risk to environmental health. However, remediation strategies are constrained by inadequate knowledge of the polymetallic distribution, speciation patterns, and transformation factors at these sites. This study investigates the influence of soil minerals, heavy metal occurrence forms, and environmental factors on heavy metal migration behaviors and speciation transformations. X-ray diffraction analysis revealed that the minerals associated with heavy metals are mainly hematite, franklinite, sphalerite, and galena. Sequential extraction results suggest that lead and zinc are primarily present in the organic-sulfide fractions (F4) and residual form (F5) in the soil, accounting for over 70% of the total heavy metal content. Zinc displayed greater instability in carbonate-bound (16%) and exchangeable (2%) forms. The migration and diffusion patterns of heavy metals in the subsurface environment were visualized through the simulation of labile state heavy metals, demonstrating high congruence with groundwater pollution distribution patterns. The key environmental factors influencing heavy metal stable states (F4 and F5) were assessed by integrating random forest models and redundancy analysis. Primary factors facilitating Pb transformation into stable states were available phosphorus, clay content, depth, and soil organic matter. For Zn, the principal drivers were Mn oxides, soil organic matter, clay content, and inorganic sulfur ions. These findings enhance understanding of the distribution and transformation of heavy metal speciation and can provide valuable insights into controlling heavy metal pollution at non-ferrous smelting sites.

Sb/As immobilization and soil function improvement under the combined remediation strategy of modified biochar and Sb-oxidizing bacteria at a smelting site.

Antimony (Sb) and arsenic (As) lead to soil pollution and structural degradation at Sb smelting sites. However, most sites focus solely on Sb/As immobilization, neglecting the restoration of soil functionality. Here, we investigated the effectiveness of Fe/H2O2 modified biochar (Fe@H2O2-BC) and Sb-oxidizing bacteria (Bacillus sp. S3) in immobilizing Sb/As and enhancing soil functional resilience at an Sb smelting site. Over a twelve-month period, the leaching toxicity of As and Sb was reduced to 0.05 and 0.005 mg L-1 (GB3838-2002) respectively, with 1% (w/w) Fe@H2O2-BC and 2% (v/v) Bacillus sp. S3 solution. Compared to CK, the combination of Fe@H2O2-BC and Bacillus sp. S3 significantly reduced the bioavailable As/Sb by 98.00%/93.52%, whilst increasing residual As and reducible Sb fractions by 210.31% and 96.51%, respectively. The combined application generally improved soil aggregate structure, pore characteristics, and water-holding capacity. Fe@H2O2-BC served as a pH buffer and long-term reservoir of organic carbon, changing the availability of carbon substrates to bacteria. The inoculation of Bacillus sp. S3 facilitated the transformation of Sb(III)/As(III) to Sb(V)/As(V) and differentiated the composition and functional roles of bacterial communities in soils. The combination increased the abundance of soil saprotrophs by 164.20%, whilst improving the relative abundance of N- and S-cycling bacteria according to FUNGuild and FAPROTAX analysis. These results revealed that the integrated application was instrumental in As/Sb detoxification/immobilization and soil function restoration, which demonstrating a promising microbially-driven ecological restoration strategy at Sb smelting sites.

Standardized framework for assessing soil quality at antimony smelting site by considering microbial-induced resilience and heavy metal contamination.

Antimony smelting activities damage the soil and vegetation surroundings while generating economic value. However, no standardized methods are available to diagnose the extent of soil degradation at antimony smelting sites. This study developed a standardized framework for assessing soil quality by considering microbial-induced resilience and heavy metal contamination at Xikuangshan antimony smelting site. The soil resilience index (SRI) and soil contamination index (SCI) were calculated by Minimum Data Set and geo-accumulation model, respectively. After standardized by a multi-criteria quantitative procedure of modified Nemerow's pollution index (NPI), the integrated assessment of soil quality index (SQI), which is the minimum of SRINPI and SCINPI, was achieved. The results showed that Sb and As were the prominent metal(loid) pollutants, and significant correlations between SQI and SRI indicated that the poor soil quality was mainly caused by the low level of soil resilience. The primary limiting factors of SRI were Fungi in high and middle contaminated areas, and Skermanella in low contaminated area, suggesting that the weak soil resilience was caused by low specific microbial abundances. Microbial regulation and phytoremediation are greatly required to improve the soil quality at antimony smelting sites from the perspectives of pollution control and resilience improvement. This study improves our understanding of ecological effects of antimony smelting sites and provides a theoretical basis for ecological restoration and sustainable development of mining areas.