Potential high-risk release sources of thallium and arsenic from surrounding rocks of a typical thallium and arsenic mining area in southwest China.

Abundant naturally and anthropogenically exposed surrounding rocks (NESRs and AESRs) in mining areas may pose persistent threats as sources of potentially toxic elements (PTEs), but this has been historically overlooked, especially for thallium (Tl) and arsenic (As). Here, the release risks of Tl and As from both NESRs and AESRs in a typical TlAs sulfide mining area were investigated. In a single leaching process, AESRs released 10.4 % of total Tl (157 µg L-1) and 32.5 % of total As (4089 µg L-1), 2-3 orders of magnitude higher than NESRs. Prolonged multiple leaching tests revealed notable and long-term risks of release of Tl and As from AESRs, associated with oxidation and dissolution of iron/sulfur-bearing minerals. Substantial release of PTEs was linked to the transformation/degradation of the -OH functional group and extensive dissolution of secondary sulfate minerals in AESRs. Ultrafiltration and STEM-EDS indicate that 18.4 % of water-extracted As released from AESRs existed as natural nanoparticles consisting of iron/sulfur-bearing minerals. This study highlights the high risks of Tl and As release from anthropogenically exposed surrounding rocks and the importance of nanoparticles in PTE transport, and provides insights into the control of PTEs in mining areas.

Persistent thallium enrichment and its high ecological risks developed from historical carbonaceous Hg-Tl mining waste.

Thallium (Tl) is a priority pollutant with high biotoxicity and has been of great concern worldwide in recent years. The former Lanmuchang Hg-Tl mining site in southwest China is a hotspot of multiple metal(loid)s pollution that previously caused large-scale chronic Tl poisoning, mainly resulting from carbonaceous Tl-bearing mining waste. However, arable land destroyed by historical mining wastes persists at high ecological risks decades after reclamation, but little is known about the solid phase partitioning and species of Tl during soil formation of underlying mining wastes as potential Tl sources. In this study, a representative reclaimed soil profile (100 cm depth) was selected in the lowlands to explore the geochemical cycling and environmental fate of Tl in mining waste-derived subsoil. The Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) analysis revealed an unexpected enrichment of Mn (2920-7250 mg/kg) and Tl (205-769 mg/kg) in the mining waste-derived subsoil. Results from BCR sequential extraction, X-ray Photoelectron Spectroscopy (XPS), and Electron Probe Microanalyses (EPMA) indicate that high Tl loading Mn oxide particulates (up to 15,712 ppm Tl) dominate the sequestration of Tl in the subsoil via oxidation-complexation and have a high potential for migration to both topsoil and groundwater. In addition, insights from microbial fossils and Fe-metabolizing bacteria closely related to Tl indicated that Fe (hydr)oxide particulates showing high Tl levels (up to 3865 mg/kg) point to biomineralization. Detailed mineralogical investigations revealed that hematite-siderite syngenetic particulates could serve as a promising mineralogical proxy for redox oscillations under periodic flooding and recorded the frequent groundwater level fluctuations experienced in the probed profile. Despite the potential for long-term preservation of high Tl loading Fe/Mn (hydr)oxides under HCO3-rich groundwater conditions in karst areas, the reductive release of Tl will be inevitable during flooding, implying that underlying carbonaceous mining waste will pose persistent and severe hazards to the ecosystem.

The non-coevolution of DIC and alkalinity and the CO2 degassing in a karst river affected by acid mine drainage in Southwest China.

Dissolved inorganic carbon (DIC) in mine water generated during coal mining is a large and potential source of atmospheric CO2, however its geochemical behaviors under the influence of AMD in relation to CO2 degassing and carbonate buffering are not well known. In this study, water temperature, pH, DO, alkalinity, Ca2+ concentration, and the carbon isotope of DIC were measured monthly from November 2020 to November 2021 and carbonate chemistry and CO2 emission flux were calculated to reveal the processes of DIC evolution and CO2 degassing from the Chetian River draining a karst region, which is materially affected by the input of large quantities of AMD. The results showed that carbonate erosion, the mineralization of terrestrial organic matter, and domestic sewage input are all identified to contribute DIC to different degrees to the river. Throughout the year, the Chetian River undergoes high-intensity CO2 degassing, which is dominated by HCO3--neutralized degassing and proton-enhanced degassing in different reaches. The pCO2 in the river under the influence of AMD is as high as 237,482 µatm, while the F-CO2 approaches 316.9 g C m-2 d-1. Meanwhile, the carbonate system in the downstream karst river buffers an average of 85.2 % of DIC release at the river's outlet. The input of AMD significantly altered the carbon cycle of the surface watershed in the headwaters of tributaries, and greatly enhanced the release of CO2 from surface water to the atmosphere; meanwhile, the buffering of carbonates on acidity in the water of main streams causes pCO2 to rapidly reduce over a short distance. Obviously, the carbon emission effect generated by the interaction between AMD and carbonate mainly occurs in the tributary water system. Considering the huge amount of AMD worldwide, this large potential source of atmospheric CO2 requires a specific and precise quantitative analysis based on actual observations.

The introduction of nitrogen from coal into the surface watershed nitrogen cycle due to coal mining activity.

Human activity has doubled the turnover rate of the terrestrial nitrogen cycle, leading to a series of environmental problems. A little-studied nitrogen source in terrestrial and aquatic environments is the nitrogen release associated with rock strata. Southwest China features the largest continuous karsts in the world, featuring a fragile ecological environment but abundant coal resources. The current study selected a typical coal mining area to evaluate the migration and transformation of nitrogen related to coal mining in surface watershed. The findings reveal that the total nitrogen in coal seams was as high as 10,162.3 mg/kg, mainly in the form of organic nitrogen, followed by NH4+-N, while the content of NO3--N was negligible. Based on the isotope fractionation and the co-evolution between Δ15NNO3-NH4 and δ15N-NO3-/δ15N-NH4+, coal mining changed the coal seams' oxidation-reduction state, resulting in the mineralization of organic nitrogen to NH4+-N. Next, NH4+-N gradually oxidized to NO3--N. Various forms of coal-origin nitrogen may be leached out by acid mine drainage (AMD), potentially contributing >10 % of NO3--N and 90 % of NH4+-N to the surface river. Another nitrogen source that requires serious consideration is the wide use of ammonium nitrate explosives in coal mining, as blasting residues may contribute about another 10 % to NO3--N in surface water. Since organic nitrogen accounts for >90 % of extractable nitrogen, the release of coal-origin nitrogen may contribute much more to the total nitrogen in surface water than to NO3--N. Based on the fractionation of nitrogen and oxygen isotopes of nitrate, low-pH AMD promotes the volatilization of nitrate in the form of nitric acid. The conversion of different forms of nitrogen in AMD will be the focus of future attention.

Rhizosphere Microbial Communities and Geochemical Constraining Mechanism of Antimony Mine Waste-Adapted Plants in Southwestern China.

Antimony (Sb) and arsenic (As) are two hazardous metalloid elements, and the biogeochemical cycle of Sb and As can be better understood by studying plant rhizosphere microorganisms associated with Sb mine waste. In the current study, samples of three types of mine waste-Sb mine tailing, waste rocks, and smelting slag-and associated rhizosphere microorganisms of adapted plants were collected from Qinglong Sb mine, southwest China. 16S rRNA was sequenced and used to study the composition of the mine waste microbial community. The most abundant phylum in all samples was Proteobacteria, followed by Bacteroidota, Acidobacteriota, and Actinobacteriota. The community composition varied among different mine waste types. Gammaproteobacteria was the most abundant microorganism in tailings, Actinobacteria was mainly distributed in waste rock, and Saccharimonadia, Acidobacteriae, and Ktedonobacteria were mainly present in slag. At the family level, the vast majority of Hydrogenophilaceae were found in tailings, Ktedonobacteraceae, Chthoniobacteraceae, and Acidobacteriaceae (Subgroup 1) were mostly found in slag, and Pseudomonadaceae and Micrococcaceae were mainly found in waste rock. Actinobacteriota and Arthrobacter are important taxa for reducing heavy metal(loid) mobility, vegetation restoration, and self-sustaining ecosystem construction on antimony mine waste. The high concentrations of Sb and As reduce microbial diversity.

Rare earth element geochemistry of Middle Devonian reefal limestones of the Dianqiangui Basin, South China: implications for nutrient sources and expansion of the reef ecosystem.

The Givetian Age witnessed the greatest expansion of stromatoporoid-coral reefs from low to higher latitudes of the Phanerozoic. Multi-proxy seawater surface temperature reconstruction suggests the establishment of a super-greenhouse climate as a major reason for reef expansion, yet many questions remain. This article presents the results of a rare earth element and yttrium (herein referred to as REY, derived from REE + Y) geochemical study as well as mineralogy and oxygen isotope values of two well-documented Middle Givetian reefal carbonate sections (Jiwozhai and Buzhai) of the Jiwozhai Formation of South China. The nearshore Jiwozhai patch reef succession displays greater biodiversity and more abundant coral than the marginal platform Upper Buzhai reef. Reefal and micritic carbonates of the Jiwozhai section are characterized by shale-like post-Archean Australian Shale (PAAS)-normalized REY patterns, by very weak negative Ce anomaly values (Ce/Ce* 0.80-0.96; average = 0.89), slightly elevated Y/Ho values (28.9-39.1; average = 34.1), and near-unity values of (Pr/Yb)N (average = 0.87), (Pr/Tb)N (average = 0.80), and (Tb/Yb)N (average = 1.09). Moreover, REY patterns of deposits of the Jiwozhai section differ markedly from those of modern seawater. The described geochemical aspects of the Jiwozhai section and the positive correlation of REY and Th contents displayed by the section point to a terrestrial siliciclastic contribution contemporaneous with reef-building. In contrast, REY patterns of the Upper Buzhai reef section samples are similar to those of modern seawater characterized by light rare earth element (LREE) depletion (average (Pr/Yb)N = 0.76), negative Ce anomalies (average Ce/Ce* = 0.88), and average super-chondritic Y/Ho ratios (average = 45.4)). Slightly positive Eu anomalies (Eu/Eu* = 0.93-1.94; average = 1.36) of the Upper Buzhai reef section samples are attributed to the negligible effect of hydrothermal fluids. Middle REE (MREE) enrichment (average (Tb/Yb)N = 1.48) of Buzhai section carbonate samples and positive correlation of REY and Th suggest a riverine input. Combined with siliciclastic mineralogy, oxygen isotope values, and reef-building biota morphology of the studied two sections, we suggest that terrestrial nutrients delivered by rivers far outweighed upwelling as a source of nutrients supplied to the Givetian reef ecosystem of South China. Coral and stromatoporoid in tropic oceans thrived in turbid water containing abundant terrestrial sediment and the nutrient-laden water helped expand reef-builder habitats during the Givetian time.

Secondary Sulfate Minerals from Pyrite Oxidation in Lanmuchang Hg-Tl Deposit, Southwest Guizhou Province, China: Geochemistry and Environmental Significance.

Thallium (Tl) is a highly toxic trace metal posing a significant threat to human health. Tl pollution in soils and chronic Tl poisoning related to Tl-rich sulfides weathering in the Lanmuchang mine of southwest Guizhou province, China, have been intensively studied in recent years. And yet, there are few studies on the role of secondary sulfate minerals associated with Tl mobility in this area. The sulfate minerals were characterized by XRD and SEM-EDS. The concentrations of Tl and other elements were determined by ICP-MS. The results show that sulfate minerals are predominantly melanterite, halotrichite, and fibroferrite. The average contents of Tl in rock, sulfate minerals, and soil samples were 156.4, 0.11, and 72.1 µg g-1, respectively. This study suggests that Tl in the mineralized rocks entered soils by pyrite oxidation with less scavenged of the sulfate minerals. The dissolution of the ferric sulfate minerals accelerates pyrite oxidation and maintains soil acidity, and this likely enhances Tl mobility from soil to crops.

Effects of Organic Fertilizers on Cd Activity in Soil and Cd Accumulation in Rice in Three Paddy Soils from Guizhou Province.

A greenhouse pot experiment was conducted to investigate the effects of organic fertilizer application on Cd activity in soil and Cd accumulation in rice in paddy soils with different levels of contamination from varying Cd sources in Guizhou Province (the soil types are NJ, which is a soil with a high geological background of Cd; and QX and JZ, which are anthropogenic Cd-polluted soils). The application of organic fertilizer increased the content of organic matter in the soil and reduced the concentration of acetic acid-extractable Cd in QX and JZ paddy soils. Organic fertilizer increased rice yields and significantly decreased the Cd concentration in brown rice. In the QX and JZ soils, however, the concentration of Cd in brown rice exceeded the allowable maximum levels (MLs) of Cd in China. In contrast, the concentration of Cd in brown rice in NJ soil met the MLs of Cd. Additionally, the average daily dose and the health risk index of Cd in NJ soil were much lower than those in QX and JZ soils. The results indicate that organic fertilizer application is a promising and economic means to control Cd pollution in paddy soil. Moreover, risk assessment shows that the risk of exposure to Cd in the high geological background soil (NJ) was much lower than that in anthropogenically polluted soils (QX and JZ).

Spatial Distribution and Environmental Risk of Arsenic and Antimony in Soil Around an Antimony Smelter of Qinglong County.

The purpose of this study was to investigate the distribution of arsenic (As) and antimony (Sb) in soils around an antimony smelter at Qinglong together with the soil pollution levels and potential ecological risk. The results show that (1) total concentrations of As (23 ~ 539 mg/kg) and Sb (19.7 ~ 5681 mg kg-1) were higher than the Guizhou province-level background values (As, 20; Sb, 2.24), especially Sb. Their dominant geochemical speciation was the residual fraction which accounted for > 90% of the total concentrations. (2) The distribution of As and Sb in soils influenced mainly by land-use type, altitude, predominant wind direction, and distance from the pollution source. (3) The geo-accumulation index shows that the soil was highly contaminated with Sb and moderately with As. The potential ecological risk index shows that As posed a moderate risk and Sb a high risk. The general ecological risk was classified as high risk. However, the risk index coding method shows low environmental risk from As and Sb.

Effects of mining activities on evolution of water chemistry in coal-bearing aquifers in karst region of Midwestern Guizhou, China: evidences from δ13C of dissolved inorganic carbon and δ34S of sulfate.

The generation of acid mine drainage (AMD) may accelerate watershed erosion and promote the migration of heavy metals, then threaten local ecosystems such as aquatic life and even human health. Previous studies have focused primarily on influence of AMD in surface environment. In order to reveal the acidizing processes in karst high-sulfur coalfield in Southwest China, this study, by contrast, focused on the hydrogeochemical evolution process and acidification mechanism of mine water in Zhijin coalfield, western Guizhou Province. The oxidation of pyrite and other sulfides induced strong acidification of mine water according to the water chemical analysis. As a result, a series of geochemical processes such as dissolution of carbonates and silicates, hydrolysis of metal ions, and degassing of CO2 complicated water chemical evolution. The dissolution of silicates controlled the chemical composition of mine water, but more carbonates might be dissolved during the acidification of mine water. The sources of sulfate are quite different in water samples collected from the two selected mine. According to sulfur isotope analysis, the dissolution of gypsum is the primary source of sulfate in samples from Hongfa mine, whereas sulfide oxidation contributed a large amount of sulfate to the mine water in Fenghuangshan mine. The dissolution of carbonates should be an important source of DIC in mine water and CO2 originating from organic mineralization might also have a certain contribution. This study elucidated the groundwater chemical evolution processes in high-sulfur coal-bearing strata and provided a foundation for further study of carbonates erosion and carbon emission during acidification of mine water.