Overlooked pyrite-mediated heterogeneous Fenton processes: Mechanisms of surface hydroxyl radical generation and associated decontamination performance.

Pyrite-based Fenton-like processes have been extensively studied for wastewater decontamination; however, most relevant studies placed excessive emphasis on the homogeneous Fenton reaction mediated by aqueous Fe2+, resulting in the proposed technologies facing issues such as additional acid requirements for pH adjustment and excessive iron sludge production. Herein, through in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), custom dual-chamber reactor experiments, and a series of control experiments, significant hydroxyl radical generation was identified during the pyrite/H2O2 process, while the dominant reactive iron species was verified to the structural Fe sites on the pyrite surface, rather than structural Fe(II) in secondary iron minerals and surface adsorbed Fe2+. Consequently, even with significant suppression of the homogeneous Fenton pathway, the pyrite/H2O2 process exhibited significant degradation efficiency for sulfamethoxazole (SMX) at pH 4. Moreover, the pyrite/H2O2 process was found to selectively remove 50 µM of pollutants with high affinity for pyrite (bisphenol A, carbamazepine, nitrobenzene, and SMX), even in the presence of 50-100 mM methanol. Compared to the typical iron-based reductive catalyst (zero-valent iron, ZVI), pyrite mediated a Fenton process with greater potential for practical applications at pH 4, achieving a 43.75-fold reduction in iron sludge production and almost doubling the H2O2 utilization efficiency. Additionally, in contrast to ZVI, minimal iron oxide formed on the pyrite surface during the oxidation process. Thus, after seven cycles of degradation experiments, the decontamination efficiency of the pyrite/H2O2 process remained stable. These findings are crucial for understanding the complex environmental behavior of pyrite in both natural and engineering processes and provide a new perspective for the efficient utilization of pyrite resources as well.

Acidithiobacillus species mediated mineral weathering promotes lead immobilization in ferric-silica microstructures at sulfidic tailings.

Immobilization and stabilization of heavy metals (HMs) in sulfidic and metallic tailings are critical to long-term pollution control and sustainable ecological rehabilitation. This study aims to unravel immobilization mechanisms of Pb (Ⅱ) in the neoformed hardpan structure resulting from Acidithiobacillus spp. accelerated bioweathering of sulfides in the presence of silicates. It was found that the bioweathered mineral composite exhibited an elevated Pb (Ⅱ) adsorption capacity compared to that of natural weathered mineral composite. A suit of microspectroscopic techniques such as synchrotron-based X-ray Absorption Spectroscopy (XAS), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR) and Field-Emission Scanning Electron Microscope (FE-SEM) indicated that secondary Fe-bearing minerals, functional groups, and surface properties in the neoformed hardpan were key factors contributing to Pb (Ⅱ) adsorption and immobilization in ferric-silica microstructures. The underlying mechanisms might involve surface adsorption-complexation, dissolution-precipitation, electrostatic attraction, and ion exchange. Microbial communities within the muscovite groups undergoing bioweathering processes demonstrated distinctive survival strategies and community composition under the prevailing geochemical conditions. This proof of concept regarding Pb (Ⅱ) immobilization in microbial transformed mineral composite would provide the basis for scaling up trials for developing field-feasible methodology to management HMs pollution in sulfidic and metallic tailings in near future.

Arsenic redistribution associated with Fe(II)-induced jarosite transformation in the presence of polygalacturonic acid.

Jarosite exists widely in acid-sulfate soil and acid mine drainage polluted areas and acts as an important host mineral for As(V). As a metastable Fe(III)-oxyhydoxysulfate mineral, its dissolution and transformation have a significant impact on the biogeochemical cycle of As. Under reducing conditions, the trajectory and degree of abiotic Fe(II)-induced jarosite transformation may be greatly influenced by coexisting dissolved organic matter (DOM), and in turn influencing the fate of As. Here, we explored the impact of polygalacturonic acid (PGA) (0-200 mg·L-1) on As(V)-coprecipitated jarosite transformation in the presence of Fe(II) (1 mM) at pH 5.5, and investigated the repartitioning of As between aqueous and solid phase. The results demonstrated that in the system without both PGA and Fe(II), jarosite gradually dissolved, and lepidocrocite was the main transformation product by 30 d; in Fe(II)-only system, lepidocrocite appeared by 1 d and also was the mainly final product; in PGA-only systems, PGA retarded jarosite dissolution and transformation, jarosite might be directly converted into goethite; in Fe(II)-PGA systems, the presence of PGA retarded Fe(II)-induced jarosite dissolution and transformation but did not alter the pathway of mineral transformation, the final product mainly still was lepidocrocite. The retarding effect on jarosite dissolution enhanced with the increase of PGA content. The impact of PGA on Fe(II)-induced jarosite transformation mainly was related to the complexation of carboxyl groups of PGA with Fe(II). The dissolution and transformation of jarosite drove pre-incorporated As transferred into the phosphate-extractable phase, the presence of PGA retarded jarosite dissolution and maintained pre-incorporated As stable in jarosite. The released As promoted by PGA was retarded again and almost no As was released into the solution by the end of reactions in all systems. In systems with Fe(II), no As(III) was detected and As(V) was still the dominant redox species.

Competitive adsorption of heavy metals onto xanthate-modified sludge hydrochar and its solidification as secondary minerals.

In this study, a sulfur-modified magnetic hydrochar was synthesized by grafting thiol-containing groups onto the sludge-derived hydrochar. The modified hydrochar exhibited effective adsorption of Cu2+, Pb2+, Zn2+, and Cd2+ over a wide pH range and in the presence of coexisting ions, and showed almost no secondary leaching in three acidic solutions. In the mult-metal ion system, the modified hydrochar exhibited maximum adsorption capacities were 39.38, 105.74, 26.53, and 38.11 mg g-1 for Cu2+, Pb2+, Zn2+, and Cd2+, respectively. However, the binding capacity and adsorption amount of modified hydrochar for metal ions were lower in the mult-metal ion system compared to the unit-metal ion system. Notably, Pb2+ showed a strong inhibitory effect on the adsorption of other heavy metal ions by modified hydrochar due to strong competition for xanthate functional groups. The Pb2+ occupied the xanthate and native functional groups (-OH, -NH2, and Fe-O etc.), leaving only a small amount of adsorption sites for Cu2+, Zn2+ and Cd2+. Simulation results further supported these findings, indicating that Pb2+ had the highest density profiles near the four functional groups, and the density profiles of the four heavy metals near the xanthate functional groups were greater compared to the other three functional groups. Furthermore, the SEM-EDS, TOF-SIMI, and XPS results indicated that modified hydrochar achieved excellent mineral binding mainly through electrostatic interaction, ion exchange, and chelation. Overall, these results highlight the sulfur-modified magnetic hydrochar as a highly efficient adsorbent for heavy metals in environmental applications.

Divergent redistribution behavior of divalent metal cations associated with Fe(II)-mediated jarosite phase transformation.

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).

Geochemistry and 14C dating of guano deposits in the Karaftu Cave, Kurdistan, Iran: implication for paleoenvironment.

Karaftu Cave in the northwest of Divandareh includes four floors plus an underground area. The bat hall and its underground area are covered with guano deposits. 14C dating indicates the onset of guano deposition is about 14,260±50 BP years, and its average accumulation rate is about 4.1 mm/yr for depths of 360 to 205 cm. Bacterial and fungal metabolisms decay guano, release acids, and disperse large amounts of microorganisms inside the cave. Interactions between acids and guano caused leaching, dissolution, change in the distribution, and abundance of elements, which leads to the formation of secondary minerals in guano. These variations in minerals and elements also depend on the local climatic conditions. Distribution of elements in the Ce/Ce* versus Pr/Pr* diagram and the correlation coefficient between Ce and Mn display three different paleoclimate conditions (dry, wet, and dry) during the accumulation of the guano. Also, dolomite, phosphate, and iron oxide minerals have been formed during the passage of water through bedrock beneath the guano. This water is unsuitable for drinking and harmful to the organisms in the region. Effect of these acids on the substrate also leads to the collapse of the cave floor, generation of a new underground, fall in the groundwater level, change in the groundwater drainage system, drying of springs around the cave, loss of green cover, and a negative impact on the ecosystem in the region. To keep the cave environment clean and remove these problems, it is better to harvest guano and use it as fertilizer.

Divergent repartitioning of antimony and arsenic during jarosite transformation: A comparative study under aerobic and anaerobic conditions.

Jarosite is the host mineral of Sb(V) and As(V) in mining environments. However, the repartitioning of Sb and As during its transformation is poorly understood. Additionally, the mutual effect between the redistribution behavior of As and Sb during jarosite conversion remains unclear. Here, we investigated the transformation of Sb(V)-, As(V)- and Sb(V)-As(V)-jarosite at pH 5.5 under aerobic and anaerobic conditions without a reductant. The results indicated that co-precipitated Sb(V) promotes jarosite dissolution, and the final products were mainly goethite and hematite. In contrast, the co-precipitated As(V) retarded jarosite dissolution and altered the transformation pathway, mainly forming lepidocrocite, which might be attributed to the formation of As-Fe complexes on the jarosite surface. The inhibiting or promoting effect increased with the increase in co-precipitated As or Sb concentration. In the treatment with Sb(V)-As(V)-jarosite, the inhibition effect of co-precipitated As(V) on mineral dissolution was predominant, but the end-products were mainly goethite and hematite. Compared with the aerobic system, the dissolution and transformation of jarosite in treatments in the anaerobic system occurred faster, although without a reductant, which was possibly associated with the reduced CO2 content in the reaction solutions after degassing. In all treatments, the release of Sb(aq) and As(aq) into the solution was negligible during jarosite transformation. The transformation processes drove As into the surface-bound exchangeable and poorly crystalline phases, while Sb was typically redistributed in the poorly crystalline phase. During the transformation of Sb(V)-As(V)-jarosite, the co-existence of As significantly increased the proportion of Sb distributed on the solid surface and in the poorly crystalline phase. These findings are valuable for predicting the long-term fate of Sb and As in mining environments.

Geochemical and mineralogical investigation of cemented crusts in the tailings cover at Long Lake Gold Mine, Sudbury, Canada.

In mine tailings, precipitation of secondary minerals may cement the tailings material and form cemented crusts or hardpans. Hardpans typically form beneath the surface of reactive tailings. However, at the former Long Lake Gold Mine near Sudbury, Ontario, cemented crusts formed in a clean sand cover above the tailings. We applied mineralogical and geochemical techniques to investigate the formation of these cemented crusts. Representative samples were collected from the sand cover and vertical cores from the underlying tailings. Elevated concentrations of arsenic (As), iron (Fe), and sulfur (S) in the sand cover indicate the upward transport of sulfide-mineral oxidation products. The shallow porewater of the tailings is acidic (pH 4 - 6) and contains elevated concentrations of As (up to 346 mg/L), Fe (up to 1844 mg/L), and SO4 (up to 12,000 mg/L). Mineralogical observations indicate that primary sulfide minerals in the near-surface tailings display moderate to strong oxidation, and secondary Fe-arsenate and jarosite minerals are formed both in the near-surface tailings and the sand cover. Upward migration of sulfide-mineral oxidation products leads to the formation of cemented crusts, which with continuing erosion, represent a long-term source of pollution to the surrounding environment.

Anaerobic syntrophic system composed of phosphate solubilizing bacteria and dissimilatory iron reducing bacteria induces cadmium immobilization via secondary mineralization.

Secondary mineralization is a promising method for remediating cadmium (Cd) pollution in sediments, but the poor stability of Cd-containing secondary minerals is a bottleneck that limits the development of this approach. The existence of phosphate can enhance the formation of stable secondary minerals and points a new direction for Cd immobilization. In this research, a novel syntrophic system composed of phosphate solubilizing bacteria (PSB) and dissimilatory iron reducing bacteria (DIRB) was established and the effect and mechanism of Cd immobilization in the system were also explored. The results showed that under the conditions of DIRB:PSB (V:V)= 3:1, syntrophic bacteria dosage of 5% and glucose dosage of 5 g/L, Cd incorporated in the secondary minerals could account for about 60% of the total Cd. In the pH range of 5-9, alkaline environment was conducive to the immobilization of Cd and the percentage of combined Cd was up to 58%, while the combined Cd in secondary minerals decreased from 62% to 56% with the increase of initial Cd concentration from 0.1 to 0.3 mmol/L. In addition, XRD, XPS, Mössbauer and other characterization results showed that secondary minerals, such as Cd exchange hydroxyapatite (Cd-HAP) and kryzhanovskite (Fe3(PO4)2(OH)3) were formed in this new system. The established syntrophic system of PSB and DIRB is thus a prospective bioremediation technology for Cd immobilization in sediments and can avoid the potential risk might be caused by the addition of phosphorus-containing materials.

Aging and reactivity assessment of nanoscale zerovalent iron in groundwater systems.

In this study, changes in the reactivity of nanoscale zerovalent iron (NZVI) in five different groundwater (GW) systems under anoxic and oxic conditions were examined over a wide range of aging time (0 - 60 d). p-nitrophenol (p-NP) was used as a redox-sensitive probe, whereas nalidixic acid (NA), a typical antibiotic found in the natural environment, was used as a sorbing compound. Investigation of the p-NP reduction in pure water systems showed that NZVI lost 41% and 98% of its reductive activity under anoxic and oxic conditions after 60 d, while enhancement of its reactivity was observed after short-term aging in GW (1 - 5 d), followed by a further decline. This behavior has been ascribed to the formation of secondary Fe(II)-bearing phases, including magnetite and green rust, resulting from NZVI aging in GW. Adsorption experiments revealed that GW-anoxic-aged NZVI samples exhibited a good affinity toward NA, and a greater NA adsorption (∼27 µmol g - 1) than that of pristine NZVI (∼2 µmol g - 1) at alkaline pH values. Surface complexation modeling showed that the enhanced adsorption of NA onto secondary minerals can be attributed to the Fe(II)-NA surface complexation. This considerable change in the reductive ability and the adsorption capacity of NZVI arising from groundwater corrosion calls for greater attention to be paid in assessment studies, where NZVI is injected for long-term remediation in groundwater.

Characteristics and Environmental Response of White Secondary Mineral Precipitate in the Acid Mine Drainage From Jinduicheng Mine, Shaanxi, China.

The study focuses on the white secondary mineral precipitate and its environmental response formed in acid mine drainage (AMD) at Jinduicheng Mine (Shaanxi, China). The mineral composition of white precipitate was characterized by Scanning electron microscopy-energy dispersive spectrometer (SEM-EDS), X-ray photoelectron spectroscopy (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Inductively coupled plasma-atomic emission spectrometer (ICP-AES), chemical quantitative calculation and PHREEQC software. The white precipitate was a kind of amorphous crystal with the characteristics of a fine powder, and its main elements were O, Al, S, F, OH- and SO42- groups. Moreover, by comparing the mole number of chemical elements, the main mineral composition of the white precipitate was closest to basaluminite. The geochemical simulation result of the PHREEQC software verified that the white precipitate was basaluminite. According to the analysis of water quality characteristics of water samples, basaluminite can reduce the ions content in the AMD and enrich Cu, Ni, Mo, Cr and F ions, showing an excellent self-purification capacity of the water body. These results are helpful to improve the understanding of secondary mineral and its environmental response, and are of great significance for the environmental protection and sustainable development of mining area.

Conductive property of secondary minerals triggered Cr(VI) bioreduction by dissimilatory iron reducing bacteria.

Although secondary minerals have great potential for heavy metal removal, their impact on chromium biogeochemistry in subsurface environments associated with dissimilatory iron reducing bacteria (DIRB) remains poorly characterized. Here, we have investigated the mechanisms of biogenic secondary minerals on the rate of Cr(VI) bioreduction with shewanella oneidensis MR-1. Batch results showed that the biogenic secondary minerals, schwertmannite and jarosite, appreciably increased the Cr(VI) bioreduction rate. UV-vis diffuse reflection spectra showed that schwertmannite and jarosite are semiconductive minerals, which can be activated by MR-1, followed by transferred conduction electrons toward Cr(VI). Cyclic voltammetry and Tafel analysis suggested that the resistance of secondary minerals is a dominant factor controlling Cr(VI) bioreduction. In addition, Cr(VI) adsorption on secondary minerals through ligand exchange promoted Cr(VI) bioreduction by decreasing the electron transfer distance between MR-1 and chromate. Fe(III)/Fe(II) cycling in schwertmannite and jarosite also contributed to Cr(VI) bioreduction as reflected by X-ray photoelectron spectroscopy and Fourier transform infrared spectrometer. Complementary characterizations further verified the contributions of Fe(III)/Fe(II) cycling, Cr(VI) adsorption, and conduction band electron transfer to enhanced Cr(VI) bioreduction. This study provides new insights on the understanding of Cr(VI) bioreduction by semiconductor minerals containing sulfate in subsurface environments.

Acidophilic Iron- and Sulfur-Oxidizing Bacteria, Acidithiobacillus ferrooxidans, Drives Alkaline pH Neutralization and Mineral Weathering in Fe Ore Tailings.

The neutralization of strongly alkaline pH conditions and acceleration of mineral weathering in alkaline Fe ore tailings have been identified as key prerequisites for eco-engineering tailings-soil formation for sustainable mine site rehabilitation. Acidithiobacillus ferrooxidans has great potential in neutralizing alkaline pH and accelerating primary mineral weathering in the tailings but little information is available. This study aimed to investigate the colonization of A. ferrooxidans in alkaline Fe ore tailings and its role in elemental sulfur (S0) oxidation, tailings neutralization, and Fe-bearing mineral weathering through a microcosm experiment. The effects of biological S0 oxidation on the weathering of alkaline Fe ore tailings were examined via various microspectroscopic analyses. It is found that (1) the A. ferrooxidans inoculum combined with the S0 amendment rapidly neutralized the alkaline Fe ore tailings; (2) A. ferrooxidans activities induced Fe-bearing primary mineral (e.g., biotite) weathering and secondary mineral (e.g., ferrihydrite and jarosite) formation; and (3) the association between bacterial cells and tailings minerals were likely facilitated by extracellular polymeric substances (EPS). The behavior and biogeochemical functionality of A. ferrooxidans in the tailings provide a fundamental basis for developing microbial-based technologies toward eco-engineering soil formation in Fe ore tailings.

Role of secondary minerals in the acid generating potential of weathered mine tailings: Crystal-chemistry characterization and closed mine site management involvement.

Mine tailings exposed to water and oxygen generate acid mine drainage (AMD) when the neutralizing minerals are insufficient to buffer the acid produced by sulfide oxidation. Mineral reactivity, such as sulfide oxidation and carbonate dissolution, leads to several changes within mine tailings in terms of their physical, mineralogical, and geochemical properties, which may lead to the release of metal(oid)s (e.g., As, Cu, Zn, Fe, S) into the environment. Fresh and oxidized tailings were sampled at two vertical profiles in a tailings storage facility (TSF). The TSF contains tailings from gold ore processing at a mine that has been closed for more than 25 years. Oxidized tailings have formed by in-situ oxidation of fresh tailings over more than 20 years. The collected samples were analyzed for: i) chemical composition by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), and total S/C; and ii) mineralogical composition by X-ray diffraction (XRD), Mineral Liberation Analyzer (MLA), Mossbauer spectroscopy, and Fe L-edge X-ray absorption near-edge spectroscopy (XANES). Mineralogically, the fresh tailings included more than 22 wt% carbonates and more than 10 wt% sulfides. In contrast, the oxidized tailings were composed mainly of secondary minerals such as iron oxy-hydroxides and gypsum. Geochemically, the fresh tailings exhibited a circumneutral behavior during weathering cell experiments and contaminants such as As were negligibly released (<0.3 mg/L). The latter is explained by formation of secondary iron oxy-hydroxides, which are known for the capacity to uptake several contaminants from the leachate. Long term oxidation of fresh tailings will lead to highly oxidized tailings similar to those collected in situ. The oxidized tailings exhibited an acidic behavior despite sulfide depletion due to latent acidity. The geochemical behavior was strongly controlled by the reactivity of secondary minerals (e.g., dissolution of gypsum and iron oxy-hydroxides). Quantitatively, the oxidized tailings released 163 mg/kg Fe, around 12,000 mg/kg S, and around 6 mg/kg Zn.

Mineralogical dataset of natural zeolites from Lessini Mounts, Northern Italy: Analcime, natrolite, phillipsite and harmotome chemical composition.

This dataset article contains mineralogical and chemical data of some natural zeolites such as analcime, natrolite, phillipsite and harmotome. These minerals were found as secondary phases within vesicles and veins in the basaltic rocks of the Lessini Mounts, Northern Italy. Methods for obtaining the datasets include optical microscopy, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Analcime forms well-developed, transparent to milky crystals with a typical icositetrahedron habit. The average composition of analcime is calculated as Na13.79Ca0.01K0.03Ba0.03[Al14.28Si33.82O96] 16H2O, with all of the extra-framework sites occupied by sodium. Natrolite usually forms hemispherical aggregates with glassy, colourless to white thin prismatic crystals, which generally radiate from a central point. The average chemical composition of natrolite is Na14.28Ca0.14K0.01[Al15.60Si24.59O80] 16H2O. Crystals of phillipsite-harmotome serie occur in a variety of forms and display a highly variable chemical composition, from almost pure compositions to intermediate values. Phillipsite is more common and its average chemical composition is Ca1.40Na0.29K1.08Ba0.27[Al4.68Si11.28O32] 12H2O, while harmotome is rare and has an average chemical composition of Ca0.97Na0.20K0.36Ba0.91[Al4.60Si11.46O32] 12H2O. The obtained dataset can be used for various purposes: it can be used by other authors to compare morphological features and chemical compositions of similar zeolites crystals discovered in other parts of the world, it can be compared with those obtained from similar geologic environments encouraging studies on hydrothermal processes, and it could represent the starting point for a potential exploration of zeolites from an industrial point of view.

Acid mine drainage formation and arsenic mobility under strongly acidic conditions: Importance of soluble phases, iron oxyhydroxides/oxides and nature of oxidation layer on pyrite.

Acid mine drainage (AMD) formation and toxic arsenic (As) pollution are serious environmental problems encountered worldwide. In this study, we investigated the crucial roles played by common secondary mineral phases formed during the natural weathering of pyrite-bearing wastes-soluble salts (melanterite, FeSO4·7H2O) and metal oxides (hematite, Fe2O3)-on AMD formation and As mobility under acidic conditions (pH 1.5-4) prevalent in historic tailings storage facilities, pyrite-bearing rock dumps and AMD-contaminated soils and sediments. Our results using a pyrite-rich natural geological material containing arsenopyrite (FeAsS) showed that melanterite and hematite both directly-by supplying H+ and/or oxidants (Fe3+)-and indirectly-via changes in the nature of oxidation layer formed on pyrite-influenced pyrite oxidation dynamics. Based on SEM-EDS, DRIFT spectroscopy and XPS results, the oxidation layer on pyrite was mainly composed of ferric arsenate and K-Jarosite when melanterite was abundant with/without hematite but changed to Fe-oxyhydroxide/oxide and scorodite when melanterite was low and hematite was present. This study also observed the formation of a mechanically 'strong' coating on pyrite that suppressed the mineral's oxidation. Finally, As mobility under acidic conditions was limited by its precipitation as ferric arsenate, scorodite, or a Fe/Al arsenate phase, including its strong adsorption to Fe-oxyhydroxides/oxides.

Fate of oxalic-acid-intervened arsenic during Fe(II)-induced transformation of As(V)-bearing jarosite.

Jarosite is a metastable Fe(III)-oxyhydroxysulfate mineral that can act as an excellent scavenger for arsenic (As) in acid sulfate soils (ASSs) and in areas polluted by acid mine drainage (AMD). The Fe(II)-induced transformation of jarosite can influence the As mobility in reducing soil and sediment systems. Although organic acids are prevalent in these environments, their influence on the behavior of As during the Fe(II)-induced transformation of jarosite is yet to be fully understood. In this study, we investigated the effects of oxalic acid on the partitioning of As into dissolved, adsorbed, poorly crystalline, and residual phases during the Fe(II)-induced transformation of As(V)-bearing jarosite at pH 5.5 and 1 mM Fe(II) concentration. The results demonstrated that jarosite frequently transformed to lepidocrocite in treatments without oxalic acid or with low oxalic acid (0.1 mM), and As was typically redistributed in the surface-bound exchangeable and residual phases. While a high concentration of oxalic acid (1 mM) retarded the transformation of jarosite and produced goethite as the primary end product, it also changed the Fe(II)-induced transformation pathway and drove most As into the residual phase (approximately 92%). The results indicated that oxalic acid exerts a significant influence on the partitioning and speciation of As during the above-mentioned transformation. X-ray photo electron spectroscopy analysis of the reaction products also revealed that As(V) may be still the dominant redox species. Overall, this study provides critical information for understanding the fate of As during the transformation of secondary minerals under complex influencing factors, thereby assisting in more accurately predicting the geochemical cycling of As in natural systems.

Coupled dynamics of As-containing ferrihydrite transformation and As desorption/re-adsorption in presence of sulfide.

This study investigated the coupled dynamics of the redox transformation of arsenic-containing ferrihydrite, and arsenate desorption and re-adsorption in presence of sulfide. Batch experiments, various microscopic and spectroscopic analyses collectively revealed that electrons from sulfide competitively transferred to ferrihydrite and no arsenate was reduced. The reductive dissolution of ferrihydrite by sulfide led to the quick formation of FeS that competitively decreased the availability of sulfide for its subsequent reduction of ferrihydrite. The quick formation of FeS was followed by a relatively slow transformation of ferrihydrite to magnetite and other Fe(II)-Fe(III) minerals that were primarily bound to the residual ferrihydrite surfaces. As a result of the preservation of As-containing ferrihydrite and surface covering by the secondary minerals, the majority (> 90%)of sorbed arsenate resided in the solid phase, and <10% of arsenate participated in the desorption process during the ferrihydrite dissolution and transformation. The desorption of arsenate was fast, and followed by the kinetic re-adsorption. The rate and extent of the re-adsorption was consistent with the dynamic transformation of the secondary minerals and their sorption affinity toward As. The results have a strong implication to understanding of As concentration changes during the redox transformation of As-containing minerals in groundwater systems.

Reductive dissolution of jarosite by a sulfate reducing bacterial community: Secondary mineralization and microflora development.

Jarosite is an iron-hydroxysulfate mineral commonly found in acid mine drainage (AMD). Given its strong adsorption capacity and its ability to co-precipitation with heavy metals, jarosite is considered a potent scavenger of contaminants in AMD-impacted environments. Sulfate-reducing bacteria (SRB) play an important role in the reductive dissolution of jarosite; however, the mechanism involved has yet to be elucidated. In this study, an indigenous SRB community enriched from the Dabaoshan mine area (Guangdong, China) was employed to explore the mechanism of the microbial reduction of jarosite. Different cultures, with or without dissolved sulfate and the physical separation of jarosite from bacteria by dialysis bags, were examined. Results indicate that the reduction of jarosite by SRB occurred via an indirect mechanism. In systems with dissolved sulfate, lactate was incompletely oxidized to acetate coupled with the reduction of SO42- to S2-, which subsequently reduced the Fe3+ in jarosite, forming secondary minerals including vivianite, mackinawite and pyrite. In systems without dissolved sulfate, jarosite dissolution occurred prior to reduction, and similar secondary minerals formed as well. Extracellular polymeric substances secreted by SRB appeared to facilitate the release of sulfate from jarosite. Structural sulfate in the solid phase of jarosite may not be available for SRB respiration. Although direct contact between SRB and jarosite is not necessary for mineral reduction, wrapping jarosite into dialysis bags suppressed the reduction to a certain extent. Microbial community composition differed in direct contact treatments and physical separation treatments. Physical separation of the SRB community from jarosite mineral supported the growth of Citrobacter, while Desulfosporosinus dominated in direct contact treatments.

Microbial sulfate reduction decreases arsenic mobilization in flooded paddy soils with high potential for microbial Fe reduction.

Arsenic (As) tends to mobilize in flooded paddy soil due to the reductive dissolution of the iron (oxyhydr)oxides to which As sorbs, resulting in elevated As accumulation in rice that poses a potential risk to the food safety and human health. Microbial sulfate reduction is an important biogeochemical process in paddy soils, but its impact on As mobilization remains poorly understood. In this study, we incubated eight As-contaminated paddy soils under flooded conditions to investigate the effect of sulfate addition on As mobility. Porewater Fe and As concentrations and As species were determined. Among the eight soils, an addition of 50 mg S kg-1 as sodium sulfate decreased porewater arsenite only in two soils, which also showed a high mobilization of Fe2+. Further experiments showed that the addition of sulfate to these two soils stimulated microbial sulfate reduction but decreased porewater concentrations of both arsenite and Fe2+. Additionally, the supply of sulfate increased the fractions of As associated with acid volatile sulfides in the solid phase and decreased As uptake by rice in pot experiments under similar conditions. The effect of sulfate addition on porewater As was diminished by the addition of molybdate, an inhibitor of sulfate reducing bacteria. These results suggest the formation of secondary FeS minerals which co-precipitate or sorb arsenite as a likely mechanism of As immobilization, which was also supported by thermodynamic modeling of the pore water. Thus, sulfate additions can immobilize As and reduce its availability to rice plants in paddy soils containing a high potential for microbial Fe reduction, providing an efficient way to mitigate the As transfer to the food chain.