Dissolution Of Sulfides Research Articles

A Multifunctional Additive for Long‐Cycling Lithium‐Sulfur Batteries Under Lean‐Ether‐Electrolyte Conditions

AbstractThe failure of lithium‐sulfur (Li‐S) batteries operating under lean‐ether‐electrolyte conditions can be ascribed to the deterioration of electrolytes, the passivation of cathodes, and the degeneration of lithium anodes. Efforts to address these challenges by exploring alternative electrolytes beyond commonly used ether‐based systems often introduce new complications. In this study, the utilization of a multifunctional additive, 2‐Bromoacetamide (BA), for ether electrolytes is proposed to achieve stable Li‐S batteries under lean‐electrolyte conditions. These investigations reveal that the amide bond in BA forms hydrogen bonds with sulfur atoms, promoting the dissolution of lithium sulfides (Li2S) in ether electrolytes and mediating the conversion of lithium polysulfides. This enhanced solubility of Li2S facilitates 3D deposition (vertical to the substrate) rather than the typical 2D deposition (parallel to the substrate) of Li2S, and thus alleviates the passivation of cathodes. Furthermore, the incorporation of BA promotes uniform and dense lithium deposition. The use of the BA‐containing electrolyte enables stable cycling of a Li‐S pouch cell for 40 cycles, even under a low electrolyte‐to‐sulfur ratio of 4 µL mg−1. This multifunctional strategy offers an effective solution to extend the lifetime of Li‐S batteries under lean‐electrolyte conditions, thereby paving the way for practical applications of Li‐S battery technology.

The behavior of nickel isotopes during mantle melting

Mantle-derived mafic rocks show relatively large variations in nickel (Ni) isotopes and mostly isotopically light compared to the bulk silicate Earth (BSE). Whether this signature is due to the source heterogeneity or controlled by melting processes has been a debatable issue. Here, we analyzed Ni isotopic compositions of 18 intraplate basalts from the Sabzevar region, northern Iran and 16 serpentinized peridotites from Cyprus and South China. The Sabzevar basalts were likely sourced from a sulfur-free/barren mantle domain with recycled pyroxenites involved, manifested by their high Cu contents (127–265 ppm), FeT/Mn (58.2–77.4) and Zn/FeT ratios (11.9–16.4). The Ni isotopic compositions of the Sabzevar basalts (average δ60/58Ni = +0.15 ± 0.08 ‰; 2SD) are slightly heavier than the BSE value (average δ60/58Ni = +0.11 ± 0.06 ‰; 2SD), consistent with equilibrium Ni isotope fractionation during mantle silicate melting as predicted by ionic model calculations. Our new data of serpentinized peridotites (average δ60/58Ni = +0.16 ± 0.06 ‰; 2SD), together with previously reported data for oceanic sediments and metabasalts, suggest that recycled lithologies have mantle-like or relatively heavy Ni isotopic compositions. Thus, the isotopically light Ni in mafic rocks is unlikely to be caused by crustal recycling-induced mantle heterogeneity. Rather, the light Ni isotopic signature is caused by the dissolution of recycled sulfides into the mantle melts. We suggest two sulfide dissolution models (“dissolve and go” and “dissolve and equilibrium”) to describe the δ60/58Ni and Cu systematics in terrestrial basalts. In both models, the initial sulfide content (Sinitial) and oxygen fugacity (fO2) exert a major control on Ni isotopic compositions of resulting melts. These two parameters vary among different geological settings. Basalts derived from mantle sources with high Sinitial and fO2 are characterized by light Ni isotopic compositions, whereas basalts sourced from sulfur-free/barren and reduced mantle domains are likely characterized by heavy Ni isotopic compositions, aligning with the characteristic observed in natural samples.

Kinetic characteristics of bornite and chalcopyrite dissolution in nitric acid

The kinetic characteristics of dissolution of copper-bearing sulfides – chalcopyrite (CuFeS₂) and bornite (Cu₅FeS₄) – in nitric acid were studied. The kinetics of the dissolution process was described using a compressible nucleus model. Chalcopyrite of the Vorontsovskoye deposit and bornite of the Karabash deposit were used as research objects. Solution and cake samples were analyzed by optical emission spectrometry and X-ray fluorescence analysis, respectively. The results obtained were processed in the MS Excel software package. The influence of various factors, including temperature, solvent concentration, particle size, and process duration on the dissolution degree of minerals was studied. The process parameters were varied as follows: temperature – from 35 to 95°C; HNO₃ concentration – from 1 to 9 mol/dm³; particle size – from +0.1 to 0.056 mm; duration – from 0 to 60 min. It was established that an increase in temperature and acid concentration leads to a significant increase in the degree of dissolution of both chalcopyrite and bornite. A decrease in particle size also contributes to a more efficient dissolution of both minerals in nitric acid. The calculated activation energy values were 55 kJ/mol for chalcopyrite and 43 kJ/mol for bornite, which is characteristic of the kinetic region of the process. The reaction orders in terms of reactant were determined: 1.62 for chalcopyrite and 1.57 for bornite. In terms of particle size, these were -1.16 for chalcopyrite and -2.53 for bornite. On this basis, generalized equations of dissolution kinetics for both minerals were derived. The results obtained allow an assumption about the kinetic nature of dissolution of chalcopyrite and bornite under the studied conditions.

Kinetics of regeneration of oxidative Cu(II) and Fe(III) species in aerated acid chloride leaching solutions at 75 °C

In the leaching of copper sulfide ores or refractory gold ores in chloride solutions, the regeneration of oxidative agents such as Cu (II) and Fe (III) is a key aspect for a sustainable process over time. This regeneration is carried out from the oxidation of Cu (I) and Fe (II) with O2, which helps to maintain a conveniently high oxidative potential in solution and a high leaching efficiency. In this context, Cu (I) and Fe (II) oxidation are affected by the accumulation of Cu or Fe species resulting from sulfide dissolution during the process. Therefore, a good understanding of the interaction mechanism of O2 with Cu (I), Cu (II), Fe (II), and Fe (III) species is necessary to describe the oxidation kinetics in this complex environment. The present work reports a study of the Cu (I) and Fe (II) oxidation at 75 °C in solutions containing 4.0 M NaCl and 0.1 M HCl. The solutions used in the experiments contained different initial concentrations of Cu (I), Cu (II), Fe (II), and Fe (III) with values in the range of 0.0001 – 0.1 M. Experiments were conducted in a thermostatized reactor containing 0.5 L solution agitated with a magnetic stirrer at 450 rpm, while oxygenated by air bubbling at 3.5 L/min. The evolution of the concentration of Cu (I), Cu (II), Fe (II), and Fe (III) during oxidation was determined by an electrochemical method, which was mainly based on Eh measurements of solution over time. A reaction mechanism was proposed for the oxidation of Cu (I) and Fe (II) with O2 in the presence of Cu and Fe species, which described very well the results obtained in the oxidation experiments under various conditions. Based on the proposed mechanism, a kinetic model was developed that could predict the concentration of Fe (II), Fe (III), Cu (I), Cu (II), O2, HO2–, H2O2, OH– and H+ in acid aerated chloride solutions satisfactorily. These proved to be a valuable tool to approach the modeling of chloride-leaching reactors.

Engineering interfacial sulfur migration in transition-metal sulfide enables low overpotential for durable hydrogen evolution in seawater

Hydrogen production from seawater remains challenging due to the deactivation of the hydrogen evolution reaction (HER) electrode under high current density. To overcome the activity-stability trade-offs in transition-metal sulfides, we propose a strategy to engineer sulfur migration by constructing a nickel-cobalt sulfides heterostructure with nitrogen-doped carbon shell encapsulation (CN@NiCoS) electrocatalyst. State-of-the-art ex situ/in situ characterizations and density functional theory calculations reveal the restructuring of the CN@NiCoS interface, clearly identifying dynamic sulfur migration. The NiCoS heterostructure stimulates sulfur migration by creating sulfur vacancies at the Ni3S2-Co9S8 heterointerface, while the migrated sulfur atoms are subsequently captured by the CN shell via strong C-S bond, preventing sulfide dissolution into alkaline electrolyte. Remarkably, the dynamically formed sulfur-doped CN shell and sulfur vacancies pairing sites significantly enhances HER activity by altering the d-band center near Fermi level, resulting in a low overpotential of 4.6 and 8 mV at 10 mA cm−2 in alkaline freshwater and seawater media, and long-term stability up to 1000 h. This work thus provides a guidance for the design of high-performance HER electrocatalyst by engineering interfacial atomic migration.

Recovery and enrichment of valuable metals from zinc oxide dust and mitigation of toxicity based on tartaric acid and hydrogen peroxide

Considering the lack of some valuable metal resources and the toxicity of zinc oxide dust. In this study, firstly, sulfuric acid and tartaric acid were used as solvents to dissolve zinc, germanium, indium, and tin or produce soluble complex dissolution under the action of ultrasonic wave. In addition, the introduction of tartaric acid can not only effectively decompose zinc ferrite, release germanium and indium in its lattice, but also reduce Fe3+ (Ferri ion, Ⅲ) and overcome the defects of Fe3+ hydrolysis-coprecipitation. Then, sulfuric acid and hydrogen peroxide were used to promote the dissolution of metal sulfides, thereby improving the comprehensive recovery rate of metals. The study demonstrates that the final recovery rate of metals was 97.44 %, 97.01 %, 91.26 %, and 90.86 %, respectively, and the slag rate was 30.36 % under optimal conditions. The grade of lead and argentum in the residue were increased to 50.68 % and 691.63 g·t−1. During the reaction, about 50 % of arsenic and 95 % of cadmium entered the solution and were removed. Compared with the enterprise, this process shortens the total leaching time to 90 min, greatly reduces the amount of sulfuric acid, significantly improves the recovery rate of valuable metals, and reduces the toxicity of slag.

High-Grade REE accumulation in regolith: Insights from supergene alteration of an apatite-rich vein at the Kapunda Cu mine, South Australia

AbstractThe stratiform and vein-hosted Kapunda Cu deposit in South Australia contains a saprolitized hydrothermal vein with 12.37 wt.% total rare earth oxide (TREO). The vein was analyzed by X-ray diffraction, scanning electron microscopy, synchrotron-based X-ray fluorescence microscopy and electron backscatter diffraction to understand the controls that govern high-grade REE accumulation during periods of intense weathering. Petrological assessments indicate the transformation of an apatite-calcite-aluminosilicate-bearing protolith to a supergene assemblage of Fe-oxides, kaolinite and REE-phosphate minerals that include rhabdophane-(Ce), monazite-(Ce) and florencite-(Ce). This transformation was facilitated by progressive acidification of the weathering fluid, which is indicated by: 1) the increasing crystallinity of authigenic Fe-oxides and kaolinite, which led to REE desorption; 2) the textural evolution and increase in grain size of authigenic REE-phosphates from nanoscopic crystallites, to acicular needles, to micro-scale hexagonal prisms; 3) the late dissolution of REE-phosphates; and 4) the replacement of goethite by jarosite, whose sulfate component originated from the oxidation and weathering of proximal sulfide minerals. Alongside the depletion of pH-buffering carbonate minerals that are indicated by the preservation of calcite menisci, this sulfide dissolution also facilitated acid generation. Results illustrate how highly acidic weathering fluids might facilitate either REE mobilization or REE accumulation in regolith. High-grade REE accumulation under acidic supergene conditions is prioritized when the host-rock contains a significant source of depositional ligands (i.e., phosphate in the form of apatite) that can be readily leached during intense weathering. Exploration companies should therefore assay routinely for REEs in any heavily weathered phosphatic rock, due to the observed efficiency of phosphate minerals as geochemical traps for REE accumulation.

Sulfur Encapsulation into Carbon Nanospheres as an Effective Technique to Limit Sulfide Dissolution and Extend the Cycle Life of Lithium–Sulfur Batteries

Sulfur Encapsulation into Carbon Nanospheres as an Effective Technique to Limit Sulfide Dissolution and Extend the Cycle Life of Lithium–Sulfur Batteries

Cable bacteria delay euxinia and modulate phosphorus release in coastal hypoxic systems.

Cable bacteria are long, filamentous bacteria with a unique metabolism involving centimetre-scale electron transport. They are widespread in the sediment of seasonally hypoxic systems and their metabolic activity stimulates the dissolution of iron sulfides (FeS), releasing large quantities of ferrous iron (Fe2+) into the pore water. Upon contact with oxygen, Fe2+ oxidation forms a layer of iron(oxyhydr)oxides (FeOx), which in its turn can oxidize free sulfide (H2S) and trap phosphorus (P) diffusing upward. The metabolism of cable bacteria could thus prevent the release of H2S from the sediment and reduce the risk of euxinia, while at the same time modulating P release over seasonal timescales. However, experimental support for this so-called 'iron firewall hypothesis' is scarce. Here, we collected natural sediment in a seasonally hypoxic basin in three different seasons. Undisturbed sediment cores were incubated under anoxic conditions and the effluxes of H2S, dissolved iron (dFe) and phosphate (PO4 3-) were monitored for up to 140 days. Cores with recent cable bacterial activity revealed a high stock of sedimentary FeOx, which delayed the efflux of H2S for up to 102 days. Our results demonstrate that the iron firewall mechanism could exert an important control on the prevalence of euxinia and regulate the P release in coastal oceans.

Risk assessment for the long-term stability of fly ash-based cementitious material containing arsenic: Dynamic and semidynamic leaching

Fly ash from municipal solid waste incineration (MSWIFA) contains leachable heavy metals (HMs), and the environmental risk of contained HMs is an important concern for its safe treatment and disposal. This paper presents a dynamic leaching test of fly ash-based cementitious materials containing arsenic (FCAC) in three particle sizes based on an innovative simulation of two acid rainfall conditions to investigate the long-term stability of FCAC under acid rain conditions. As well as semi-dynamic leaching test by simulating FCAC in three scenarios. Furthermore, the long-term stability risk of FCAC is evaluated using a sequential extraction procedure (SEP) and the potential risk assessment index. Results showed that the Al3+ in the FCAC dissolved and reacted with the OH− in solution to form Al(OH)3 colloids as the leaching time increased. Moreover, the oxidation of sulfide minerals in the slag produced oxidants, such as H2SO4 and Fe2(SO4)3, which further aggravated the oxidative dissolution of sulfides, thereby resulting in an overall decreasing pH value of the leachate. In addition, due to the varying particle sizes of the FCAC, surface area size, and adsorption site changes, the arsenic leaching process showed three stages of leaching characteristics, namely, initial, rapid, and slow release, with a maximum leaching concentration of 2.42 mg/L, the cumulative release of 133.78 mg/kg, and the cumulative release rate of 2.32%. The SEP test revealed that the reduced state of HMs in the raw slag was lowered substantially, and the acid extractable state and residual state of HMs were increased, which was conducive to lessening the risk of FCAC. Overall, the geological polymerization reaction of MSWIFA is a viable and promising solution to stabilize mining and industrial wastes and repurpose the wastes into construction materials.

Removal of arsenic from realgar-containing water by Spirogyra: Implications for in situ remediation of arsenic in the mine area

Realgar (As4S4) is an arsenic sulfide mineral, occurring widely in metamorphic-hydrothermal deposits, reductive soil and wetland sediments. The dissolution of realgar releases arsenic, which is toxic to the environment, so the process that causes this problem deserves attention. Native Spirogyra sp. was collected and cultured from a realgar mine area and used to create varying concentrations of algae to investigate the dissolution of realgar using a photosynthesis microcosm. Separately the dynamic adsorption and uptake processes of arsenic (III) and arsenic (V) were investigated. The dissolution rate equation of realgar under Spirogyra sp. is R = 10−6.36[DO]1.84[H+]−0.60. The diurnal growth of Spirogyra sp. increases arsenic release by as much as three times than the control group and significantly changes aqueous arsenic species by varying the dissolved oxygen and pH. The amounts of arsenic (III) and arsenic (V) removed from living Spirogyra sp. were 14605 μg⋅g−1⋅h−1 and 6511 μg⋅g−1⋅h−1. Increasing amounts of –COOH, CO and carbonyl groups from the live Spirogyra sp. also promoted the dissolution of realgar. The results suggest that filament Spirogyra sp. would be an effective method for in situ acceleration of arsenic sulfide dissolution and remediation of arsenic pollution in environments such as paddy soil.

Oxidative Dissolution of Sulfide Minerals Tends to Accumulate More Dissolved Heavy Metals in Deep Seawater Environments than in Shallow Seawater Environments.

Deep-sea mining magnifies the release of heavy metals into seawater through oxidative dissolution of seafloor massive sulfide (SMS). At present, there is little information about how the metals released into seawater might be affected by the mineral assemblages, seawater conditions, and solid percentages. Here, leaching experiments were carried out to examine the behavior of three sulfides from the Southwest Indian Ridge, under conditions that replicated deep and shallow seawater environments at three solid-liquid ratios. The results demonstrated that sphalerite dissolved rapidly, and the metals released in both experimental conditions were comparable, potentially reflecting galvanic interactions between the sulfide minerals. Large quantities of the released metals were removed from the solutions when hydrous ferric oxides formed, especially for shallow seawater conditions. A comparison of metal concentrations in the leachates with the baseline metal concentrations in natural seawater indicated that most of the released metals, when diluted with seawater, would not have widespread impacts on ecosystems. Based on the obtained unique oxidative dissolution properties of each SMS at variable solid-liquid ratios, targeted wastewater discharge treatments are proposed to minimize impacts from the dissolved metals. This study will support the development of robust guidelines for deep-sea mining activities.

Leaching behavior of germanium presented in different phases from zinc oxide dust under atmospheric acid leaching conditions

Abstract Recovering germanium from zinc oxide dust (ZOD) produced from Pb–Zn smelter is an important pathway to extract germanium. However, the leaching efficiency of industrial germanium production is not satisfactory (usually less than 75 %). Therefore, the leaching behavior of Ge in different phases was discovered in this work. Ge in the ZOD mainly occurs in oxide, sulfide, silicate, and solid insoluble. The potential decides the oxidative dissolution of sulfide. The leaching recovery of zinc and germanium were 90 % and 80 % with oxidant, and 78 % and 80 % without oxidant, respectively. The effect sequence of oxidant type on the Zn leaching efficiency was MnO2 > H2O2 ≈ oxygen > air, but the type and addition of oxidant had no obvious effect on the leaching recovery of germanium. The final pH of leaching slurry limits the dissolution of oxide and hydrolysis-polymerization of impurity ions (such as Fe(III) and Si). Decreasing the final pH is beneficial to the leaching reaction of Zn and Ge. The germanium presented in oxide and sulfide is easy to leach, while the leaching of germanium existed in silicate and solid insoluble is relatively difficult. The structure of aluminate can be destroyed effectively using a 40 g/L HF solution. When the leaching percent of SiO2 is 86.82 %, the leaching recovery of Ge is 96.57 %. For the ZOD with higher content of Fe and Si, germanium leaching is negatively correlated with the content of Fe and Si in the ZOD. The results provide a scientific basis for improving the leaching recovery of germanium.

Removal of heavy metals from mine tailings by in-situ bioleaching coupled to electrokinetics

This work utilizes a combined biological-electrochemical technique for the in-situ removal of metals from polluted mine tailings. As the main novelty point it is proposed to use electrokinetics (EK) for the in-situ activation of a bioleaching mechanism into the tailings, in order to promote biological dissolution of metal sulphides (Step 1), and for the subsequent removal of leached metals by EK transport out of the tailings (Step 2). Mine tailings were collected from an abandoned Pb/Zn mine located in central-southern Spain. EK-bioleaching experiments were performed under batch mode using a lab scale EK cell. A mixed microbial culture of autochthonous acidophilic bacteria grown from the tailings was used. Direct current with polarity reversal vs alternate current was evaluated in Step 1. In turn, different biological strategies were used: biostimulation, bioaugmentation and the abiotic reference test (EK alone). It was observed that bioleaching activation was very low during Step 1, because it was difficult to maintain acidic pH in the whole soil, but then it worked correctly during Step 2. It was confirmed that microorganisms successfully contributed to the in-situ solubilization of the metal sulphides as final metal removal rates were improved compared to the conventional abiotic EK (best increases of around 40% for Cu, 162% for Pb, 18% for Zn, 13% for Mn, 40% for Ni and 15% for Cr). Alternate current seemed to be the best option. The tailings concentrations of Fe, Al, Cu, Mn, Ni and Pb after treatment comply with regulations, but Pb, Cd and Zn concentrations exceed the maximum values. From the data obtained in this work it has been observed that EK-bioleaching could be feasible, but some upgrades and future work must be done in order to optimize experimental conditions, especially the control of soil pH in acidic values.

A unified intensity of the magnetic field in the protoplanetary disk from the Winchcombe meteorite

AbstractOne key feature of our protoplanetary disk that shaped its transformation into a system of planetary bodies was its vast magnetic field. Unique constraints on the properties of this field can be gleaned from paleomagnetic measurements of certain meteorites. Here, we apply this approach to the recent CM chondrite fall Winchcombe with the aim of constructing the most complete and reliable record to date of the behavior of the disk field in the outer solar system. We find that the interior of Winchcombe carries a stable, pre‐terrestrial magnetization that likely dates from the period of aqueous alteration of the CM chondrite parent body. This remanence corresponds to a paleointensity of 31 ± 17 μT accounting for the average effect of parent body rotation. Winchcombe is rich in framboids and plaquettes of magnetite, which formed via precipitation following the dissolution of iron sulfide. This contrasts with most other CM chondrites, where magnetite formed predominantly via pseudomorphic replacement of FeNi metal. Accounting for the potential differences in recording fidelities of these types of magnetite, we find that the reported paleointensities from all CM chondrites to date are likely underestimates of the disk field intensity in the outer solar system, and use our measurements to calculate a unified intensity estimate of ~78 μT. This paleointensity is consistent with two independent values from recent studies, which collectively argue that the disk field could have played a larger role in shaping the behavior of the disk in the outer solar system than previously considered.

Dissolution of anthropogenic and natural hydrogen sulfide in deep-ocean conditions

ABSTRACT Natural and anthropogenic event information helped to simulate the physical–chemical behavior of hydrogen sulfide (H2S) in a deep oil spill and a hypothetical deep-ocean hydrothermal discharge. This research led to the development of the Lagrangian model of the discharge plumes in both cases and also analyzed the profiles of the H2S concentration at different depths taking into account its dissolution in ocean water and oceanographic conditions, such as thermohaline stratification, current fields, as well as the characteristics of the spilled hydrocarbon and the hydrothermal. The results revealed a first approximation in the identification of the dynamic behavior of the concentration profiles of H2S as a function of the oceanographic conditions. Hydrogen sulfide concentrations vary between natural and anthropogenic discharges at various depths, leading to a numerical model for applying in chemical oceanography.

Identifying the origin and fate of dissolved U in the Boeun aquifer based on microbial signatures and C, O, Fe, S, and U isotopes

The uranium inventory in the Boeun aquifer is situated near an artificial reservoir (40–70 m apart) intended to supply water to nearby cities. However, toxic radionuclides can enter the reservoir. To determine the U mobility in the system, we analyzed groundwater and fracture-filling materials (FFMs) for environmental tracers, including microbial signatures, redox-sensitive elements and isotopes. In the site, U mass flux ranged from only 9.59 × 10–7 µg/L/y to 1.70 × 10–4 µg/L/y. The δ18O-H2O and 14C signatures showed that groundwater originated mainly from upland recharges and was not influenced by oxic surface water. We observed U accumulations (∼157 mg/kg) in shallow FFMs and Fe enrichments (∼226798 mg/kg) and anomalies in the 230Th/238U activity ratio (AR), 230Th/234U AR, δ56Fe and δ57Fe isotopes, suggesting that low U mobility in shallow depths is associated with a Fe-rich environment. At shallow depths, anaerobic Fe-oxidizers, Gallionella was prevalent in the groundwater, while Acidovorax was abundant near the U ore deposit depth. The Fe-rich environment at shallow depths was formed by sulfide dissolution, as demonstrated by δ34S-SO4 and δ18O-SO4 distribution. Overall, the Fe-rich aquifer including abundant sulfide minerals immobilizes dissolved U through biotic and abiotic processes, without significant leaching into nearby reservoirs.

Surface Coal Mine Soils: Evidence for Chronosequence Development

Anthropogenic changes to soil properties and development can dominate soil systems, particularly in coal mining-impacted landscapes of the Appalachian region of the United States. Historical mining operations deposited spoils which are developing into mine soils in chronosequences, allowing for a correlation between emplacement age and rates of change in soil properties. The study site was in the Huff Run Watershed (Mineral City, OH, USA) with a series of eleven spoil piles that were deposited over a 30-year time period. Surface soils were analyzed for bulk density, loss on ignition (LOI) as a proxy for organic matter, particle size, and bulk mineralogical (by X-ray diffraction) and elemental (by X-ray fluorescence) compositions. The following linear trends were observed across the transect from older to younger mine soils: bulk density increased from 1.0 cm−3 to 1.5 g cm−3; LOI decreased from ~20% to 5%; the content of sand-sized particles and quartz decreased from ~50% to 30% and 50% to 25%, respectively, with a corresponding increase in the contribution of clay mineral from ~25% to 60%; and Fe and other trace metals (Cu, Ni, Pb, Sb, Sn, and Te) decreased in concentration, while Al, Mg, and K increased in concentration. These trends are likely the result of: (1) organic matter accumulation as vegetation becomes more abundant over time; (2) transport of clays out of more recently emplaced waste; and (3) oxidative dissolution of primary sulfides releasing Fe and other trace metals followed by re-precipitation of secondary Fe-phases and trace metal sequestration. The findings presented here provide insight into the future behavior of these materials and can potentially be used to assess the inferred age of previously unexamined mine soils across a wider geographic area. These results can also inform decisions related to reclamation activities and ecosystem restoration.

Biochar inhibited hydrogen radical-induced Cd bioavailability in a paddy soil

Herein, hydrogen (H·) radical was observed as a new pathway to produce hydroxyl (OH·) radicals that promoted cadmium sulfide (CdS) dissolution and thus Cd solubility in paddy soils. In soil incubation experiments, the bioavailable Cd concentrations in flooded paddy soils were increased by 8.44 % as the soil was aerated for 3d. For the first time, the H· radical was observed in aerated soil sludge. The association of CdS dissolution with free radicals was thereafter confirmed in an electrolysis experiment. Both H· and OH· radicals in electrolyzed water were confirmed by the electron paramagnetic resonance analysis. In the system with CdS, water electrolysis increased soluble Cd2+ concentration by 60.92 times, which was compromised by 43.2 % when the radical scavenger was introduced. This confirmed the free radicals can lead to oxidative dissolution of CdS. The H· radical was generated in systems with fulvic acid or catechol irradiated by ultraviolet lights, indicating soil organic carbon could be an important precursor for H· and OH· radicals. Biochar application decreased soil DTPA-Cd by 22–56 % invoking mechanisms besides adsorption. First, biochar quenched radicals and reduced CdS dissolution by 23.6 % in electrolyzed water in which -C-OH of biochar was oxidized to CO. Second, biochar boosted Fe/S-reducing bacteria and thus compromised CdS dissolution, as affirmed by a reversal correlation between soil available Fe2+ and DTPA-Cd concentrations. A similar phenomenon occurred in Shewanella oneidensis MR-1-inoculated soils. This study provided new insights into the bioavailability of Cd and offered feasible measures to remediate Cd-contaminated paddy soils with biochars.

Contaminant release from massive copper metallurgical slags: Insights from long-term monolithic leaching tests

Compared to compliance leaching tests performed on granular materials, leaching experiments on monolithic slags are more suitable for predicting the contaminant release when large boulders or poured slag layers are submerged in water, a specific environmental scenario typical for many smelting sites. We conducted EN 15863 dynamic monolithic leaching tests on massive copper slags over a prolonged period of 168 d. The patterns of the major contaminant (Cu, Co) fluxes indicated an initial diffusion process followed by the dissolution of primary sulfides with the maximum cumulative releases attaining 75.6 mg/m2 Cu and 4.20 mg/m2 Co. A multi-method mineralogical investigation showed that lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) started to form on the slag surface already after 9 d of leaching and partly immobilized Cu (but not Co). Vanadium and other trace elements (Zn, Pb, Cd) were leached to a much lower extent, initially controlled by diffusion followed by depletion and/or sorption to Fe oxyhydroxides. The results of the long-term leaching of the monolithic slag provide new information about the key processes affecting the release of metal (loid) contaminants under specific submerged conditions and have implications for the environmental management of slag disposal sites and/or potential reuse of slags in civil engineering.