Weathering Of Sulfides Research Articles

Permafrost impacts on chemical weathering and CO2 budgets in the Tibetan Plateau: Micro-watershed perspective on a headwater catchment

Understanding the balance between alkalinity generation from carbonate and silicate weathering, and the effect of sulfide weathering, is crucial for comprehending the impact of these processes on atmospheric CO2 levels. However, the sequestration potential and the net balance of CO2 between the release from sulfide weathering and the consumption by silicate weathering in permafrost environments remain contentious. This study examines the Shaliu River, a typical permafrost-dominated headwater catchment in the Northeast Tibetan Plateau, from a micro-watershed perspective to elucidate the effects of permafrost on chemical weathering and CO2 budgets during ablation period. Silicate weathering in the Shaliu River contributes 25–32 % to solute load, while carbonate weathering contributes 39–45 %. Sulfuric acid (H2SO4) plays a key role in carbonate weathering, accounting for 74 % of it and 37 % of the river’s solute load, especially in the permafrost-covered upstream areas. In contrast, bicarbonate (HCO3–) impacts are more evident in the lower reaches without permafrost. By integrating silicate and carbonate weathering with H2SO4-driven reactions, CO2 budget analysis indicates that the Shaliu River basin acts as a carbon source. The MEANDIR inversion model consistently depicts the watershed as a carbon source, influenced by permafrost and lithology. This implies that sulfide oxidation to produce sulfuric acid (H2SO4) drives carbonate weathering may significantly counterbalance the carbon sequestration associated with silicate weathering over geological timescales. The study provides a comprehensive understanding of the carbon budget dynamics within the permafrost-dominated watersheds of the Tibetan Plateau, enhancing the comprehension of carbon cycle processes in high-altitude ecosystems.

Validating the rhenium proxy for rock organic carbon oxidation using weathering profiles

Chemical weathering over geological timescales acts as a source or sink of atmospheric carbon dioxide (CO2), while influencing long-term redox cycling and atmospheric oxygen (O2) at Earth's surface. There is a growing recognition that the oxidative weathering of rock organic carbon (OCpetro) can release more CO2 than is locally drawn down by silicate weathering, and may vary due to changes in erosion and climate. The element rhenium (Re) has emerged as a proxy to track the oxidative weathering of OCpetro, yet uncertainties in its application remain namely that we lack a systematic assessment of the comparative mobility of Re and OCpetro during sedimentary rock weathering. Here we measure Re and OCpetro loss across gradients in rock weathering at 12 global sites, spanning a range of initial OCpetro values from ~0.2 % to >10 %. At nine sites we use titanium to account for volume changes during weathering and assess Re and OCpetro loss alongside major elements that reflect silicate (Na, Mg), carbonate (Ca, Mg) and sulfide (S) weathering. Across the dataset, Re loss is correlated with OCpetro loss but not with loss of any other major element. Across the weathering profiles, the average molar ratio of OCpetro to Re loss was 0.84 ± 0.15, with 8 out of 9 sites having a ratio >0.74. At one site (Marcellus Shale), the average ratio was lower at 0.58 ± 0.11. The excess loss of Re matches expectations that, typically, between ~0 and 20 % of the Re liberated by sedimentary rock weathering derives from silicate or sulfide phases, while some OCpetro may be physically or chemically protected from weathering. Overall, our measurements provide validation for the Re proxy of OCpetro oxidation and allow future work to further improve our knowledge of regional and global-scale rates of this important source of CO2 in the geochemical carbon cycle.

Germanium distribution in Mississippi Valley-Type systems from sulfide deposition to oxidative weathering: A perspective from Fule Pb-Zn(-Ge) deposit, South China

Abstract Germanium (Ge) is a critical raw material for emerging high-tech and green industries, resulting in considerable recent interest in understanding its distribution and geochemical behavior in ore deposits. In this contribution, the distribution of Ge and related trace elements in the Fule Pb-Zn(-Ge) deposit, South China, is investigated to reveal the distribution of Ge in the hydrothermal ores and during sulfide weathering, using multiple microanalytical techniques, including scanning electron microscopy, electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In the Fule MVT deposit, sphalerite (ZnS) is the most significant Ge-carrier relative to other sulfides, though the five recognized textural types of sphalerite display progressive depletion in Ge from the first sphalerite generation to the late one. In the early stage, sphalerite with fine-grained chalcopyrite inclusions has the highest Ge concentrations, probably accounting for a significant proportion of the total Ge. We interpret that high Ge concentrations in the early sphalerite may be attributable to high Cu activity in the mineralizing fluids. During oxidative weathering, Ge was redistributed from its original host, sphalerite, to the weathering product willemite (Zn2SiO4) rather than smithsonite (ZnCO3), with high levels of Ge (up to 448 μg/g) present in the willemite. The formation of abundant willemite largely prevents the dispersion of Ge during weathering. In principle, willemite-hosted Ge should be fully recoverable, and the Zn-silicate ores may, therefore, be a potential target to meet future demand. This study provides new information on how Ge behaves from sulfide- to weathering-stage in MVT systems, which directly impacts Ge mobility and deportment changes and the development of metal-lurgical strategies for Ge recovery.

Improving the re-use potential of reactive waste rock using sieving: a laboratory geochemical study

Stockpiles containing sulfide minerals are subject to oxidation reactions when exposed to atmospheric conditions, which can result in the formation of acid mine drainage (AMD). Reactive waste rock has limited re-use potential due to the contamination risk associated with the generated drainage water. The re-use of reactive waste rock could lead to a significant reduction in the volume of waste rock as it mitigates the environmental impact of mine waste deposition. Acid mine drainage generation rate depends on sulfide weathering kinetics which are controlled by many parameters such as the mineralogy and the particle size. Fine fractions of waste rock have higher specific surface areas and degree of liberation of sulfides, resulting in greater reactivity than the coarse fractions. The objective of this research was therefore to evaluate the potential of re-use by controlling particle size using the sieving method. Two different potentially acid-generating waste rocks were divided into six fractions and subjected to both static and kinetic tests. Prediction of the geochemical behavior using static test did not consider the liberation of the minerals, and the long-term prediction was therefore overestimated. Results of the kinetic columns showed there was less oxidation of the sulfide minerals in the coarse fractions than in the fine fractions. Additionally, the distribution of sulfidic minerals and neutralizing minerals with particle size is influencing the potential of the re-use of the reactive waste rock.

Mines to moana: Hydrochemical legacies in a historically mined watershed

This study investigates contemporary freshwater contamination originating from old mine workings in the Thames-Coromandel region of Te Ika-a-Māui (North Island), Aotearoa New Zealand. We employed a multi-method approach, including stable H and O isotope determinations of surface water, geochemical modelling, and diffusive gradients in thin films (DGT) deployments. Atypically, spring-summer (Sept–Nov) surface water stable oxygen isotope ratios (δ18O) were negatively displaced from meteoric values (ca. −0.28 ± 0.13 ‰), indicating a remarkable degree of low-temperature water-rock interaction, likely enhanced by dry antecedent conditions. Isotope ratios in tributaries showed less alteration than the main stem, suggesting greater meteoric inputs and shorter residence times in areas of high topographic relief. Conversely, in the main stem, isotope ratios revealed higher mineral weathering, accompanied by elevated dissolved metal concentrations, consistent with dominant inputs from shallow groundwater. Weathering of primary sulfides contributed pronounced acidity in one tributary (pH ca. 3.8), but overall, carbonate buffering ameliorated acid mine drainage across the catchment (pH ca. 7–8). Nevertheless, our results confirm exceedances of ecological guideline values (>80% protection threshold) for several toxic metals including Al, Zn, Cd and Pb; with implications for fresh and coastal water quality in Tikapa Moana-o-Hauraki, the Firth of Thames.

A distinctive rare earth element signature for pyrite oxidation and glacial weathering

The application of rare earth elements (REE) and neodymium (Nd) isotopes to authigenic Fe-(oxyhydr)oxide phases leached from marine sediments can be used for reconstructing past ocean circulation and chemical weathering patterns on nearby continental landmasses. To explore the behaviour of REE during chemical weathering in glacial environments, we analyzed the authigenic fraction of glacimarine sediments from the continental shelf off northern Svalbard (Arctic Ocean), where the evolution of ice sheet dynamics since the last deglaciation is well constrained. Our results show that leached authigenic fractions in Svalbard sediments exhibit shale-normalized REE patterns characterized by anomalously high mid-REE enrichment relative to both light- and heavy-REE, as expressed by concavity index values (CI > 2.5) that significantly depart from typical REE signatures for leached fractions in marine and river sediments worldwide. Using a compilation of literature data, we provide compelling evidence that the occurrence of pronounced mid-REE enrichment in authigenic fractions of Svalbard marine sediments links to terrestrial oxidation of pyrite following glacial weathering. While future investigation will be required to further understand the detailed mechanism accounting for the observed REE decoupling and its link to pyrite oxidation, we propose that preferential dissolution of mid-REE-enriched rock-bearing minerals such as apatite following glacial erosion, sulfide weathering and subsequent release of sulfuric acid could release a distinctive REE signature in glacial surface environments. Our findings suggest that the use of authigenic REE in the sedimentary record could provide a means for tracing glacial weathering and associated biogeochemical sulfur and iron cycling across geological times.

Toxic element characterization against a typical high geology background: Pollution enrichment, source tracking, spatial distribution, and ecological risk assessment

The geological environment determines the initial content of various elements in soil, while the late input of toxic elements produced through weathering and leaching is a persistent threat to food security and human health. In this study, we selected the Lou Shao Basin, a black rock system background, and combined geostatistical analysis and multivariate statistics to quantify the specific contribution of weathering of the black rock system, and to analyze the source traces, spatial distributions, and ecological risks of the soil toxicity of elements. The results show that the soils in the study area are acidic, which is related to the weathering of sulfides in the black rock system. The concentrations of most elements in the soil were determined to exceed the soil background values, and the Cd, Se and N contents, exceeded more than five times, especially Se, Mo nearly as high as 13 times. Strong positive correlation between Se, Cu, V and P, low correlation between N and Se, Cu, V, P, Ni and Cd.72.52%, 43%, 77.79%, 82%, 77%, and 44.1% of Cd, Se, Ni, Cu, B, and Mo came from the black rock system, respectively, which were greatly affected by geogenic weathering; V, Zn, Pb, and As are mainly from biomass burning sources; N and P are mainly from agricultural surface sources. Comparison found that the Cd and Se elements in the rocks in the study area were 16.78 times and 1.36 times higher than the world shale average, respectively, and need to pay attention to the weathering process of the two, and the spatial distribution of the 12 elements in soils showed a striped and centralized block distribution pattern, specifically around the distribution of carbonate and metamorphic rocks and other high-geology blocks. The ecological risk results showed that Cd was the main element causing high ecological risk, followed by Se and N, which were at moderate to high ecological risk levels, and Se and N showed similar ecological risk patterns, which may be related to the fact that selenium can promote the uptake and transformation of nitrogen. The present results add to the endogenous sources of toxic elements, quantify the source contributions of toxic elements in soils with high geologic backgrounds, fill this knowledge gap, and provide new insights for pollution control and ecological protection in areas with high geochemical backgrounds.

Spatial distribution and health risk assessment of toxic metal(oid)s in soils of coal mining areas of the Salt Range, Punjab, Pakistan

Long-term coal mining operations have been linked to increases in HM concentrations in subterranean soils, which degrades soil quality. The clusters of coal mines and mine tailings considerably increase metal(loid)s concentrations in the surrounding soils and air of the Eastern (ESR), Central (CSR), and Trans-Indus Salt Range (TSR). The present study was conducted in this scenario to ascertain the occurrence and dispersion of toxic metals from mine tailings to different environmental components and their pollution load in soils and possible risk. The geochemical characterization of the soil, coal waste, and dust particulate matter revealed that waste samples are highly enriched in As, Cd, Pb, Fe, and Zn. In terms of soil quality standards, geo-accumulation index (Igeo), enrichment factor (EF), and contamination factor (CF), Fe, Mn, and Zn are extremely contaminated. However, As, Cd, Co, and Cr show moderate contamination. These harmful soil contaminants, primarily originate from coal-associated tailings. Further, the principal component analysis, multiple linear regression (PCA-MLR), and agglomerative hierarchical clustering (AHC) signify that mineralization and weathering of sulfide and carbonate minerals within the coal wastes and lithological units of the present study area cause the release of environmentally sensitive trace elements, which upon dispersion, leaching, and atmospheric deposition enters the air and soils of the present study area. We propose that higher HI index of Co (4), Fe (35), Mn (11), and Zn (13) values can be a significant human health concern.

Efficient Thermoelectric Conversion of Sulfide Chimneys in Submarine Volcanic Systems

AbstractSubmarine volcanos are the most active areas in the deep sea, but the environmental consequences of frequent volcanic activity on the geophysical fields and biogeochemical processes near hydrothermal chimneys have not been fully understood yet. In particular, how continuous high‐flux thermal energy, the most typical form of energy in active submarine volcanic systems, affects electron transport and geoelectric field remains unknown. This study provides the first evidence that thermal energy can be efficiently converted to electrical energy at an extremely small spatial scale of the submarine black chimneys. The Seebeck coefficient of sulfide chimneys can reach more than 200 μV/K, with high electrical conductivity of 104 S/m and low thermal conductivity of 1.0 W/(m·K) within 300–700 K. A maximal potential gradient of 300 mV/cm under a temperature difference of 300–700 K can be generated by the thermoelectric conversion of sulfide chimneys, with a maximum energy converting efficiency up to 1%. The thermoelectric conversion effect of a global‐scale submarine volcanos could enable electroactive bacteria to fix appromaxiately 105–106 tons of carbon per year. In addition, the thermal‐electrochemical experiments indicated sulfides underwent rapid oxidation under thermoelectric effects, which may help explain the intense oxidative weathering of sulfides in some anoxic deep‐sea hydrothermal zones.

Erosional modulation of the balance between alkalinity and acid generation from rock weathering

The balance between alkalinity generation by carbonate and silicate weathering and sulfuric acid generation by sulfide weathering controls the effect of weathering on atmospheric pCO2 over geologic timescales. How this balance varies across environmental gradients remains poorly constrained. Here, we analyze this balance across an erosional gradient of two orders of magnitude in the Three Rivers (Yangtze, Mekong, and Salween Rivers) Headwater Region (TRHR), eastern Qinghai-Tibet Plateau (QTP). By employing major element chemistry and multiple isotopes (δ34SSO4, δ18OSO4, and δ18OH2O) coupled with forward and inverse approaches, we unmix contributions of silicates, carbonates, evaporites, and sulfides to the total weathering budget. Across the TRHR, riverine SO42– is derived mainly from a mixture of an evaporite source with uniform values of δ34SSO4 and δ18OSO4, and a sulfide source that contributes highly variable values of δ34S (−12.2 ‰ to +4.1 ‰) and δ18O (−17.7 ‰ to −1.6 ‰). Contributions of sulfide oxidation to riverine SO42– vary from 16 % to 94 %, and sulfuric acid consumes 6 % to 63 % of the alkalinity produced by weathering. The fractions of weathering alkalinity derived from carbonate weathering range from 36 % to 98 % relative to silicate weathering. The combination of silicate, carbonate, and sulfide weathering suggests that the instantaneous weathering fluxes of most sampled catchments in the TRHR act as a sink of atmospheric CO2 over timescales shorter than marine carbonate burial (∼104 years), but as a carbon source over timescales longer than carbonate burial and shorter than sulfide burial (∼107 years). The spatial variability of the balance between alkalinity and acid generation, and, thus, the relationship between chemical weathering and atmospheric pCO2, are largely dependent on lithology. However, within comparable lithologic settings, sulfide and carbonate weathering rates rise with increasing erosion, whereas silicate weathering rates remain constant. Consequently, plateau weathering shifts from a sink to a source of atmospheric CO2 with increasing erosion. These findings suggest that sulfide weathering is more sensitive to erosion than carbonate and silicate weathering, and that it could play an important role in the long-term carbon cycle during mountain building.

Iron sulfide weathering by oxyhalogen species: Implications for iron sulfate and (oxyhydr)oxides formation on Mars

Sulfate salts are abundant, widespread, and temporally distributed on the surface of Mars. Several processes, including sulfide weathering, have been proposed to explain the formation and accumulation of oxidized iron(III) hydroxysulfate (e.g., jarosite) in Martian sediments. Oxidative weathering of iron sulfide minerals (like pyrite and pyrrhotite) could explain the presence of sulfate as well as the relative absence of sulfide minerals in Martian sediments. However, the effectiveness of oxyhalogen compounds, plausible oxidants present on Mars, to weather iron sulfides remain unknown. Here we investigate the oxidative weathering of iron sulfide minerals, pyrite and pyrrhotite, by chlorate and bromate in Mars-relevant fluids. Our results demonstrate that both oxyhalogen species readily oxidize iron sulfides and produce an alteration assemblage comprised of elemental sulfur, Fe(III) (oxyhydr)oxide (magnetite, goethite, and lepidocrocite), and Fe(III) hydroxysulfates (jarosite and schwertmannite). The mineral products depend strongly on the type of sulfide, oxidant, and initial solution pH. Owing to their abundance and highly reactive nature, oxyhalogen brines could be important Fe(III) hydroxysulfate-forming reagents on early and modern Mars and substantially impact the survivability of sulfide minerals at the Martian surface. Additionally, sulfide bearing units might serve as indicators of minimal post-depositional alteration. Oxyhalogens may be responsible for the loss of magmatic sulfides in surface materials given the prevalence of oxyhalogen brines and the reactivity of the sulfides.

Supergene Hydrous Sulfates in the Tuolugou Co-Au Deposit, Northern Qinghai–Tibet Plateau: Implications for Genetic Mechanism and Exploration

Supergene hydrous sulfate minerals form through the oxygenation and weathering of primary sulfides. In the Qinghai–Tibet Plateau region, with an alpine and dry environment, hydrous sulfate minerals oxidized from pyrite-bearing ore bodies provide important clues regarding the mineralization and environment. The Tuolugou sedimentary-exhalative (SEDEX) Co-Au deposit is located in the East Kunlun metallogenic belt of the northern Qinghai–Tibet Plateau in China. In the mining district, pyrite is the prevalent Co-hosting sulfide mineral, and is partially exposed on the surface to weathering and oxidation. Herein, we document the mineral assemblages in the supergene oxidation zone in the Tuolugou deposit, probe the genesis of supergene assemblage, and explore the implications for exploration. Three zones can be recognized in the oxidation zone of the Tuolugou deposit, including the outer zone (natrojarosite), intermediate zone (rozenite and aplowite), and inner zone (roemerite and melanterite). The mechanism of oxidation under aerobic and anaerobic conditions, as well as zoning with different oxidation degrees, are described in detail. Hydrous sulfates such as natrojarosite can be used as possible indicators of the exploration of albitite-related SEDEX deposit in this region.

Isotope diffusion and re-equilibration of copper and evaporation of mercury during weathering of tetrahedrite in an oxidation zone

To understand the mobility of heavy metals during oxidative weathering of sulfides, we investigated weathering processes of tetrahedrite [(Cu,Fe,Zn,Hg)12(Sb,As)4S13] in an oxidation zone with abundant siderite (FeCO3) and baryte (BaSO4) at Rudňany (Slovakia). The focus of this work lied in the isotopic (δ65Cu, δ202Hg, δ34S) variations of the minerals during weathering and the interpretation of such changes. In the studied oxidation zone, Hg-rich tetrahedrite converts in situ to pockets of powdery cinnabar (HgS) and an X-ray amorphous mixture rich in Sb, Fe, and Cu that slowly re-crystallizes to Cu-rich tripuhyite (FeSbO4). Copper is mobile and precipitates as malachite [Cu2(OH)2(CO3)], azurite [Cu3(OH)2(CO3)2], or less abundant clinoclase [Cu3(AsO4)(OH)3]. The isotopic composition (δ65Cu) of tetrahedrite correlates well with the degree of weathering and varies between 0.0 ‰ and −4.0 ‰. This correlation is caused by isotopic changes during dissolution and subsequent rapid equilibration of δ65Cu values in the tetrahedrite relics. Simple diffusion models showed that equilibration of Cu isotopic values in the tetrahedrite relics proceeds rapidly, on the order of hundreds or thousands of years. Abundant secondary iron oxides draw light Cu isotopes from the aqueous solutions and shift the isotopic composition of malachite and azurite to higher δ65Cu values as the distance to the primary tetrahedrite increases. Clinoclase and tripuhyite have lower δ65Cu values and are spatially restricted near to the weathering tetrahedrite. The Hg and S isotopic composition of tetrahedrite is δ202Hg = −1.27 ‰, δ34S = −1.89 ‰, that of the powdery secondary cinnabar is δ202Hg = +0.07 ‰, δ34S = −5.50 ‰. The Hg isotopic difference can be explained by partial reduction of Hg(II) to Hg(0) by siderite and the following evaporation of Hg(0). The S isotopic changes indicate no involvement of biotic reactions in the oxidation zone, probably because of its hostility owing to high concentrations of toxic elements. This work shows that the Cu isotopic composition of the primary sulfides minerals changes during weathering through self-diffusion of Cu in those minerals. This finding is important for the use of Cu isotopes as tracers of geochemical cycling of metals in the environment. Another important finding is the Hg in the oxidation zones evaporates and contributes to the global cycling of this element through atmospheric emission.

Chromium isotopes in an acidic fluvial system: Implications for modern and ancient Cr isotope records

Chromium is an important redox-active element, with significant Cr isotope fractionations driven by redox transformations in the natural environment and quantified through laboratory experiments. Recent work has demonstrated that non-redox-driven transformations can also produce small variations in Cr isotopes, but the role of these processes in controlling environmental Cr isotope variations remains unclear. The highly acidic but biologically diverse acid rock drainage system in Río Tinto, Spain (and affiliated rivers) provides a unique opportunity to examine how non-redox-related processes can substantially affect the isotopic composition of Cr in a natural system. Our results suggest that under conditions where Cr redox transformations are obviated, Cr cycling is largely controlled by formation of Fe-oxyhydroxides and Fe-hydroxysulfates, Cr adsorption, and Cr speciation, with little apparent Cr isotope fractionation between source materials, waters, and sediments. Moderate Cr isotope shifts, however, may be the result of non-redox processes, including adsorption to organic ligands and potentially biological uptake. These results add to a growing body of evidence for the importance of non-redox transformations in contributing to environmental Cr isotope variations, with implications for the use of chromium isotopes in studies of sedimentary Cr isotope records. In particular, this study is a validation of the potential for sulfide weathering in the Proterozoic to deliver relatively unfractionated Cr isotopes to the ocean, despite rising and sustained high oxygen levels.

Ktenasit a jeho minerální asociace z ložiska Zlaté Hory - východ (Česká republika)

The rare Cu-Zn sulphate, ktenasite, was found in the association with schulenbergite, serpierite, gypsum and brochantite at abandoned stope of the Modrá štola adit, the ore deposit Zlaté Hory - East, Czech Republic. Ktenasite occurs there as two different (color, morphology) types, the first is olive green to dark green columnar crystals up to 4 mm in length which forms radially arranged groups or rich crystalline coatings. The second type is represented by blue to greenish blue crystalline coatings or hemispherical or fan-shaped aggregates formed by thin tabular crystals. The X-ray powder diffraction data, Raman spectra and chemical composition of both types are almost identical. Ktenasite is monoclinic, space group P21/c, the unit-cell parameters refined from X-ray powder diffraction data are: a 5.610(2), b 6.123(2), c 23.827(9) Å, β 95.27(3)o and V 815.0(4) Å3. Its chemical analyses correspond to the empirical formula Zn1.00(Cu3.13Zn0.96Mg0.07Al0.01)Σ4.17(SO4)1.98(PO4)0.01(SiO4)0.01(OH)6.32·6H2O. Schulenbergite most often occurs only as an admixture in blue-green crystalline aggregates of ktenasite, sometimes together with serpierite. More rarely, its blue tabular crystals with a pearly luster up to 0.4 mm in size were also observed. Schulenbergite is trigonal, space group R-3, the unit-cell parameters refined from X-ray powder diffraction data are: a 8.187(3), c 7.012(4) Å and V 410.5(3) Å3. Its chemical analyses correspond to the empirical formula (Cu4.96Zn2.34)7.30(SO4)1.92(SiO4)0.05(PO4)0.02 (OH)10.47·6H2O. Serpierite is relatively abundant in the studied mineral association, usually forms light blue fine crystalline coatings, its fan-shaped aggregates up to 4 mm in size formed by elongated tabular crystals have also been found more rarely. Its chemical analyses correspond to the empirical formula (Ca1.14Mn0.03Mg0.02)Σ1.19(Cu3.08Zn0.73)Σ3.81(SO4)1.99 (PO4)0.02(OH)5.97·3H2O. Abundant brochantite forms bright green crystalline coatings and tiny dark green to black-green crystals. Its chemical analyses correspond to the empirical formula (Cu3.80Zn0.17Al0.02)Σ3.99(SO4)0.99(PO4)0.01(OH)6.00. The origin of studied mineral association is connected with sub-recent weathering of primary sulphides (pyrite, pyrrhotite, sphalerite and chalcopyrite) in the conditions of abandoned mine space.

Hydrotermální a supergenní mineralizace křemen-kalcitové žíly z kamenolomu Smrčník, Lipová-lázně u Jeseníku (Česká republika)

An extraordinary rich supergene mineral association (about 20 determined mineral species) has been discovered in an active marble quarry Smrčník located at NW slope of the hill Smrčník (799 m a.s.l.), 2 km NW of the village Lipová-Lázně, 7 km WNW of Jeseník, Rychlebské hory Mountains, Czech Republic. The origin of supergene minerals is connected with weathering of primary sulphides (galena, chalcopyrite, sphalerite) in quartz-calcite hydrotermal vein in the conditions of supergene zone in-situ. The most common supergene mineral is cerussite, quite abundant are anglesite, phosphohedyphane, hemimorphite, malachite, chrysocolla, fornacite and vauquelinite. Other determined minerals are rare: aurichalcite, caledonite, cesàrolite, conichalcite, descloizite, duftite, leadhillite, linarite, mottramite, plumbojarosite, rosasite and wulfenite. The detailed descriptions, X-ray powder diffraction data, refined unit-cell parameters and quantitative chemical composition of individual studied mineral phases are presented.

Lithological and glacial controls on sulfide weathering and the associated CO2 budgets in the Tibetan Plateau: New constraints from small catchments

The Tibetan Plateau, a region that hosts low to middle-latitude glaciers and a high density of metasedimentary rocks, is a hotspot of continental weathering and carbon cycling. However, quantitative estimations of sulfide oxidation and how it affects CO2 budgets from the plateau weathering are lacking. Here we use chemical and isotopic datasets from the studied small catchments in the Tibetan Plateau to estimate that 69.1% to 77.0% of stream SO42– originates from sulfide oxidation. Thus, more than 80% of the CO2 consumed by silicate weathering is counterbalanced by transient CO2 release from H2SO4-driven carbonate dissolution in the study area. In addition, the sulfide oxidation rate for glacial catchments is 5 times that of nonglacial catchments. The CO2 release rate from acid generated by sulfide oxidation in metasedimentary catchments is approximately 3 times that of granitic catchments. We propose that sulfide oxidation has greatly modified the CO2 budget of chemical weathering of the Tibetan Plateau. This study reveals new constraints on the CO2 budget in the Tibetan Plateau weathering, and will provide important insights into the carbon cycle during the plateau uplifting in Cenozoic.

Enhanced sulfide oxidation by monsoon rainfall in a small typical karstic catchment of Southwest China

CO2 is released to the atmosphere via sulfuric acid weathering of carbonate rocks, affecting the flux of CO2 drawdown via silicate weathering. Precisely quantifying the proportion of oxidative weathering of sulfide minerals to riverine sulfate is critical to improving the estimation of the global carbon budge. Sulfur and oxygen isotopic compositions of sulfate and major ion concentrations in river water samples collected monthly at 12 sampling sites from a small typical karstic catchment of Southwest China were analyzed, in order to quantify the relative contribution of sulfide oxidation to riverine sulfate and elucidate the factors affecting its changes. Results show that the sulfate concentration and δ34Ssulfate and δ18Osulfate values at most sampling sites have obvious seasonal changes, with low values in the monsoon season and high values in the non-monsoon season, suggesting that the relative contributions of different sulfur sources to riverine sulfate are seasonally variable throughout of the year. Results from the Beyesian isotope mixing model show that overall, the fraction of sulfide-derived sulfate to riverine sulfate ranges from 44.3 ± 13.7% to 53.3 ± 10.5%, although it has a wide range for different sampling sites. In addition, the relative contribution of sulfide weathering displays a seasonal variation and is higher in the monsoon season, which is mainly attributed to the influence of high rainfall in wet season. This study indicates that an increase in rainfall intensity under climate change may lead to a raised sulfide oxidation rate in the karstic catchment, which is important for assessment of global carbonate and silicate weathering in future.

Application of nano remediation of mine polluted in acid mine drainage water using machine learning model

Acid mine drainage (AMD) is the term used to describe drainage from coal mines with high sulfur-bearing rocks. The oxidative weathering of metal sulfides leads to AMD. The acidic environment corrodes more harmful compounds in the soil, which is spread throughout the working area. One such significant metal is copper, which is extracted in massive quantities from ores rich in sulfide. A copper-extraction resin might be created by combining diatomaceous earth (DE) particles with polyethyleneimine (PEI), which is shown to have great selectivity and affinity for copper. In this effort, PEI-DE particles’ copper absorption level was examined by using synthetic and actual acid mine drainage samples at varied pH values. The findings of the copper uptake particles have been examined through the Support Vector Machine (SVM) model. Using the n-fold 14 cross-validation approach, the quantities of parameters and C are estimated to be 0.001 and 0.01, respectively. The SVM analysis was correct, and the findings indicated that copper could bind to the material efficiently and preferentially at pH 4. Subsequent water elution studies at a pH value of 1 confirmed the pH-reliant interaction between dissolved Cu and PEI by demonstrating full release of the adsorbed Cu. In this research, the copper absorption of PEI-DE particles from synthetic and genuine AMD specimens was studied based on several pH conditions. The findings suggest that copper may attach to the material effectively and preferentially at pH 4. Studies of filtering water at pH1 later confirmed that all of the adsorbed Cu was released. This shows that the interaction between PEI and dissolved Cu depends on PH.

Potential autotrophic carbon-fixer and Fe(II)-oxidizer Alcanivorax sp. MM125-6 isolated from Wocan hydrothermal field.

The genus Alcanivorax is common in various marine environments, including in hydrothermal fields. They were previously recognized as obligate hydrocarbonoclastic bacteria, but their potential for autotrophic carbon fixation and Fe(II)-oxidation remains largely elusive. In this study, an in situ enrichment experiment was performed using a hydrothermal massive sulfide slab deployed 300 m away from the Wocan hydrothermal vent. Furthermore, the biofilms on the surface of the slab were used as an inoculum, with hydrothermal massive sulfide powder from the same vent as an energy source, to enrich the potential iron oxidizer in the laboratory. Three dominant bacterial families, Alcanivoraceae, Pseudomonadaceae, and Rhizobiaceae, were enriched in the medium with hydrothermal massive sulfides. Subsequently, strain Alcanivorax sp. MM125-6 was isolated from the enrichment culture. It belongs to the genus Alcanivorax and is closely related to Alcanivorax profundimaris ST75FaO-1T (98.9% sequence similarity) indicated by a phylogenetic analysis based on 16S rRNA gene sequences. Autotrophic growth experiments on strain MM125-6 revealed that the cell concentrations were increased from an initial 7.5 × 105 cells/ml to 3.13 × 108 cells/ml after 10 days, and that the δ13CVPDB in the cell biomass was also increased from 234.25‰ on day 2 to gradually 345.66 ‰ on day 10. The gradient tube incubation showed that bands of iron oxides and cells formed approximately 1 and 1.5 cm, respectively, below the air-agarose medium interface. In addition, the SEM-EDS data demonstrated that it can also secrete acidic exopolysaccharides and adhere to the surface of sulfide minerals to oxidize Fe(II) with NaHCO3 as the sole carbon source, which accelerates hydrothermal massive sulfide dissolution. These results support the conclusion that strain MM125-6 is capable of autotrophic carbon fixation and Fe(II) oxidization chemoautotrophically. This study expands our understanding of the metabolic versatility of the Alcanivorax genus as well as their important role(s) in coupling hydrothermal massive sulfide weathering and iron and carbon cycles in hydrothermal fields.