Mine waste classification preceding mining constitutes a proactive solution to classify and segregate mine waste into geo-environmental domains based upon the magnitude of their environmental risks. However, upstream classification requires multi-disciplinary and integrated approaches. This study integrates geological modeling and kinetic modeling to inform upstream mine waste classification based on the pH generated from the main acid-generating and acid-neutralizing reactions once the mine solid waste is stored in oxidizing conditions. Geological models were used to depict the ante-mining spatial distribution of the main reactive minerals: pyrite, albite and calcite. Subsequently, the corresponding block models were created. The dimension of the elementary voxels for each block model was set at 40х40х40 m for this study. The kinetic modeling approach was performed using PHREEQC and VS2DRTI to consider unsaturated conditions. The kinetic modeling simulated a 1D column for each voxel. The column simulates the excavated state of the hosting rock involving kinetic reactions and unsaturated flow under highly oxidizing conditions. Subsequently, the resulting pH for different intervals of time was assigned to its respective voxel. The outcome consists of a spatio-temporal visualization of the pH defining ante-mining geo-environmental domains, thereby providing the opportunity for formulating proactive management measures regarding the hazardous geo-environmental domains.

Large quantities of lead/zinc (Pb/Zn) mine tailings were deposited at tailings impoundments without proper management, which have posed considerable risks to the local ecosystem and residents in mining areas worldwide. Therefore, the geochemical behaviors of potentially toxic elements (PTEs) in tailings were in–depth investigated in this study by a coupled use of batch kinetic tests, statistical analysis and mineralogical characterization. The results indicated that among these studied PTEs, Cd concentration fluctuated within a wide range of 0.83–6.91 mg/kg, and showed the highest spatial heterogeneity. The mean Cd concentrations generally increased with depth. Cd were mainly partitioned in the exchangeable and carbonate fractions. The release potential of PTEs from tailings was ranged as: Cd > Mn > Zn > Pb > As, Cd > Pb > Zn > Mn > As and Cd > Pb > Mn > Zn > As, respectively, under the assumed environmental scenarios, i.e. acid rain, vegetation restoration, human gastrointestinal digestion. The results from mineralogical characterization indicated that quartz, sericite, calcite and pyrite were typical minerals, cumulatively accounting for over 80% of the tailings. Sulfides (arsenopyrite, galena, and sphalerite), carbonates (calcite, dolomite, cerussite and kutnahorite), oxides (limonite) were identified as the most relevant PTEs–bearing phases, which significantly contributed to PTEs release from tailings. A combined result of statistical, geochemical and mineralogical approaches would be provided valuable information for the alteration characteristics and contaminant release of Pb/Zn mine tailings.

Copper export and mobility in acid mine drainage are difficult to understand with conventional approaches. Within this context, Cu isotopes could be a powerful tool and here we have examined the relative abundance of dissolved (<0.22 μm) Cu isotopes (δ⁶⁵Cu) in the Meca River which is an outlet of the Tharsis mine, one of the largest abandoned mines of the Iberian Pyrite Belt, Spain. We followed the chemical and isotopic composition of the upstream and downstream points of the catchment during a 24-h diel cycle. Additional δ⁶⁵Cu values were obtained from the tributary stream, suspended matter (>0.22 μm) and bed sediments samples. Our goals were to 1) assess Cu sources variability at the upstream point under contrasted hydrological conditions and 2) investigate the conservative vs. non conservative Cu behavior along a stream. Average δ⁶⁵Cu values varied from −0.47 to −0.08‰ (n = 9) upstream and from −0.63 to −0.31‰ downstream (n = 7) demonstrating that Cu isotopes are heterogeneous over the diel cycle and along the Meca River. During dry conditions, at the upstream point of the Meca River the Cu isotopic composition was heavier which is in agreement with the preferential release of heavy isotopes during the oxidative dissolution of primary sulfides. The more negative values obtained during high water flow are explained by the contribution of soil and waste deposit weathering. Finally, a comparison of upstream vs. downstream Cu isotope composition is consistent with a conservative behavior of Cu, and isotope mass balance calculations estimate that 87% of dissolved Cu detected downstream originate from the Tharsis mine outlet. These interpretations were supported by thermodynamic modelling and sediment characterization data (X-ray diffraction, Raman Spectroscopy). Overall, based on contrasted hydrological conditions (dry vs flooded), and taking the advantage of isotope insensitivity to dilution, the present work demonstrates the efficiency of using the Cu isotopes approach for tracing sources and processes in the AMD regions.

A large amounts of arable land is facing a high risk of hexavalent chromium (Cr(VI)) pollution, which requires remediation using a low toxic agent. In this study, the remediation effect of amorphous iron pyrite (FeS₂₍ₐₘ₎) on Cr(VI) in Cr(VI)-contaminated soil was evaluated by systematically analyzing the variation of the leachability, bioaccessibility, phytotoxicity, and long-term stability of the remediated soil. The effectiveness of FeS₂₍ₐₘ₎ on the leachability was assessed by alkaline digestion and the toxicity characteristic leaching procedure (TCLP); the effect on the bioaccessibility was evaluated via the physiologically based extraction test (PBET) and the Tessier sequential extraction; the effect on the phytotoxicity was assessed via phytotoxicity bioassay (seed germination experiments) based on rape (Brassica napus L.) and cucumber (Cucumis Sativus L.), and the long-term stability of the Cr(VI)-remediated soil was appraised using column tests with groundwater and acid rain as the influents. The results show that FeS₂₍ₐₘ₎, with a stoichiometry of 4× exhibited a high efficiency in the remediation of Cr(VI) and decreased its leachability and bioaccessibility during the 30-day remediation period. In addition, seed germination rate, accumulation and translocation of Cr, and root and shoot elongation of rape and cucumber of remediated soil are not significantly different from those of clean soil, illustrating that FeS₂₍ₐₘ₎ is suitable for remediating Cr(VI) contaminated arable soil. The stabilization of Cr(VI) in contaminated soil using FeS₂₍ₐₘ₎ was maintained for 1575 days. The long-term effectiveness was further confirmed by the increasing amount of free Fe and Mn in the effluent and the decreasing redox potential. In summary, FeS₂₍ₐₘ₎ has an excellent efficiency for the remediation of Cr(VI), demonstrating it is a very promising alternative for use in the contaminated arable soil.

The N, S, and Fe-tridoped carbon catalysts (NSFe-Cs), Fe/ACNS1 and Fe/ACNS2, were synthesized by wet impregnation with different concentration of ammonium ferrous sulfate solution. The prepared catalysts have a similar textural structure. The N species, S species, Feᴵᴵ and Feᴵᴵᴵ were simultaneously introduced onto the surface of catalysts. Comparison with the only Fe doped catalyst, NSFe-Cs showed greater stability and higher phenol removal in catalytic wet peroxide oxidation at different reaction condition. The main intermediates including p-hydroxybenzoic acid, formic acid, and maleic acid were determined in the treated wastewater. The high catalytic activity for NSFe-C was related to the ability of H₂O₂ decomposition. NSFe-Cs have more amount of Feᴵᴵ partially due to the formation of FeS₂, which promoted the decomposition of H₂O₂ on Fe/ACNS1 and Fe/ACNS2 surface. The generation of ·OH and ·HO₂/·O₂⁻ radicals in the bulk solution was crucial to phenol degradation, and the decomposition of H₂O₂ complied with the pseudo-first-order kinetics. The highly linear relationship between decomposition kinetic constant for H₂O₂ and the amount of surface groups suggested, including Feᴵᴵ species, pyridinic N/Fe-bonded N, pyrrolic N as well as graphitic N were responsible to the high activity of NSFe-Cs.

The Wiśniówka rock strip mining area (south-central Poland) with quartzite quarries, acid water bodies and tailings piles is one of the most unique acid mine drainage (AMD) sites throughout the world. This is due to the occurrence of enormous amounts of pyrite unknown in sedimentary formations worldwide. Of the two mineralization zones, one that is the most abundant in arsenical pyrite occurs in the lowermost Upper Cambrian formation of the Podwiśniówka quarry. The As-rich pyritiferous clastic rocks are exposed as a result of deep quartzite extraction during 2013–2014. In addition, the clayey-silty shale interbeds are enriched in rare earth element (REE) minerals. The mining operation left an acidic lake with a pH of about 2.4–2.6 and increased contents of sulfates, metal(loid)s and REE. The Podwiśniówka pyrite-rich waste material was stacked up in many places of the mining area giving rise to strongly acidic spills that jeopardized the neighboring environment. One of these unexplored tailings piles was a source of extremely sulfate- and metal(loid)-rich pools with unusual enrichments in As (up to 1548 mg L⁻¹) and REE (up to 24.84 mg L⁻¹). These distinctly exceeded those previously reported in the Wiśniówka area. A broad scope of geochemical, mineralogical and petrographic methods was used to document these specific textural and mineralogical properties of pyrite facilitating its rapid oxidation. The pyrite oxidation products reacted with REE-bearing minerals releasing these elements into acid water bodies. Statistical methods were employed to connect the obtained tailings pool hydrogeochemical data with those derived from this and the previous studies of the Podwiśniówka and Wiśniówka Duża acid pit lakes. In contrast to metal(loid) profiles, the characteristic shale-normalized REE concentration patterns turned out to be more suitable for solving different AMD issues including provenance of mine waste material in the tailings pile examined.

A massive and dense textured layer (ca. 35–50 cm thick) of hardpan was uncovered at the top layer, which capped the unweathered sulfidic Cu-Pb-Zn tailings in depth and physically supported gravelly soil root zones sustaining native vegetation for more than a decade. For the purpose of understanding functional roles of the hardpan layer in the cover profile, the present study has characterized the microstructures of the hardpan profile at different depth compared with the tailings underneath the hardpans. A suit of microspectroscopic technologies was deployed to examine the hardpan samples, including field emission-scanning electron microscopy coupled with energy dispersive spectroscopy (FE-SEM-EDS), X-ray diffraction (XRD) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). The XRD and Fe K-edge XAFS analysis revealed that pyrite in the tailings had been largely oxidised, while goethite and ferrihydrite had extensively accumulated in the hardpan. The percentage of Fe-phyllosilicates (e.g., biotite and illite) decreased within the hardpan profile compared to the unweathered tailings beneath the hardpan. The FE-SEM-EDS analysis showed that the fine-grained Ca-sulfate (possibly gypsum) evaporites appeared as platelet-shaped that deposited around pyrite, dolomite, and crystalline gypsum particles, while Fe-Si gels exhibited a needle-like texture that aggregated minerals together and produced contiguous coating on pyrite surfaces. These microstructural findings suggest that the weathering of pyrite and Fe-phyllosilicates coupled with dolomite dissolution may have contributed to the formation of Ca-sulfate/gypsum evaporites and Fe-Si gels. These findings have among the first to uncover the microstructure of hardpan formed at the top layer of sulfidic Cu-Pb-Zn tailings, which physically capped the unweathered tailings in depth and supported root zones and native vegetation under semi-arid climatic conditions.

Pyrite oxidation and sedimentary sulfate dissolution are the primary components of riverine sulfate (SO₄²⁻) and are predominant in global SO₄²⁻ flux into the ocean. However, the proportions of anthropogenic SO₄²⁻ inputs have been unclear, and their tempo-spatial variations due to human activities have been unknown. Thus, field work was conducted in a spatially heterogeneous human-affected area of the Yihe River Basin (YRB) during a wet year (2010) and drought years (2017/2018). Dual sulfate isotopes (δ³⁴S–SO₄²⁻ and δ¹⁸O–SO₄²⁻) and Bayesian isotope mixing models were used to calculate the variable anthropogenic SO₄²⁻ inputs and elucidate their temporal impacts on riverine SO₄²⁻ flux. The results of the mixing models indicated acid mine drainage (AMD) contributions increased from 56.1% to 83.1% of upstream sulfate and slightly decreased from 46.3% to 44.0% of midstream sulfate in 2010 and 2017/2018, respectively, in the Yihe River Basin. The higher upstream contribution was due to extensive metal-sulfide-bearing mine drainage. Sewage-derived SO₄²⁻ and fertilizer-derived SO₄²⁻ inputs in the lower reaches had dramatically altered SO₄²⁻ concentrations and δ³⁴S–SO₄²⁻ and δ¹⁸O–SO₄²⁻ values. Due to climate change, the water flow discharge decreased by about 70% between 2010 and 2017/2018, but the riverine sulfate flux was reduced by only about 58%. The non-proportional increases in anthropogenic sulfate inputs led to decreases in the flow-weighted average values of δ³⁴S–SO₄²⁻ and δ¹⁸O–SO₄²⁻ from 10.3‰ to 9.9‰ and from 6.1‰ to 4.4‰, respectively. These outcomes confirm that anthropogenic SO₄²⁻ inputs from acid mine drainage (AMD) have increased, but sewage effluents SO₄²⁻ inputs have decreased.

Sulfidized nanoscale zero-valent iron (S-nZVI) is a promising material for in situ soil remediation. However, its transformation (i.e., aging) and effects on the microbial community in soil ecosystems are largely unknown. In this study, S-nZVI having low (S-nZVI (L)) and high sulfur-doping (S-nZVI (H)) were incubated in soil microcosms and bare nZVI was used as a control. Their aged products were characterized using microspectroscopic analyses and the changes in the corresponding soil microbial community were determined using high-throughput sequencing analyses. The results indicate that severe corrosion of both bare and S-nZVI occurred over 56 days of aging with significant morphological and mineral changes. Magnetite, lepidocrocite, and goethite were detected as the main aged products. In addition, sulfate ions, pyrite, and iron polysulfide were formed in the aged products of S-nZVI. Cr(VI) removal test results indicated that S-nZVI(L) achieved the best results after aging, likely because of the optimal FeS arrangement on its nanoparticle surfaces. The presence of nZVI and S-nZVI increased the abundance of some magnetotactic microorganisms and altered bacterial and fungal community structures and compositions. Moreover, the addition of S-nZVI enriched some bacterial and fungal genera related to sulfur cycling because of the presence of sulfide-bearing material. The findings reveal the transformation of S-nZVI during aging and its effects on microbial communities in soil ecosystems, thereby helping to the evaluation of S-nZVI application in soil remediation.