Acid Mine Drainage Systems Research Articles

Cleaner flotation separation of chalcopyrite from pyrite at low alkalinity: Based on calcium hypochlorite oxidative modification in acid mine drainage system

Efficient and clean flotation separation of copper-sulfur has attracted soaring interest in the beneficiation of sulfide ore. The objective of this work was to examine the influence of calcium hypochlorite (Ca(ClO)2) oxidative modification on the flotation separation of chalcopyrite from pyrite in acid mine drainage (AMD) system. A maximum recovery difference of 69.70 % between both minerals was observed under the recommended conditions (initial pH = 8.5 ± 0.2, [Ca(ClO)2] = 100 mg/L, [EX] = 32 mg/L, and the volume ratio of AMD to pure water = 1:1). A high-grade concentrate with 77.35 % Cu recovery and 29.01 % Cu grade was obtained, demonstrated by mixed-mineral micro-flotation experiments. Analysis of Cu and Fe ions influence indicated that low concentrations of Fe3+ and Cu2+ favored the selective separation of pyrite and chalcopyrite. Moreover, analysis of the pulp ion concentrations showed that Ca(ClO)2 promoted the dissolution of iron ions on the pyrite surface compared to chalcopyrite, thereby enhancing pyrite oxidation. The Ca(ClO)2 interacted more intensively with the pyrite surface, forming a passivated layer that impeded the adsorption of collector, as demonstrated by Zeta potential and contact angle results. The generation of hydrophilic products caused by oxidation on the pyrite surface, such as CaSO4, CaOH+, Fe(Ⅲ)–OOH, and/or Fe2(SO4)3 was confirmed by XPS analysis, further reducing the floatability of pyrite. Furthermore, local electrochemical impedance spectroscopy and scanning electron microscopy analyses further afforded favorable evidence for selective inhibition of pyrite by Ca(ClO)2 in the AMD system. This study provides a new approach to achieve cleaner separation of pyrite and chalcopyrite and offers new perspectives for AMD treatment solutions.

Biochar-induced alterations in Acidithiobacillus ferrooxidans activity and its impact on Cd(II) and As(III) adsorption from acid mine drainage

Due to continuing mining activities, Cd(II) and As(III) contamination in acid mine drainage (AMD) has become a major environmental challenge. Currently, there is increasing focus on the use of biochar to mitigate AMD pollution. However, the impact of biochar on the process of Fe(II) oxidation by Acidithiobacillus ferrooxidans (A. ferrooxidans) in AMD systems has not been determined. In this study, we investigated the effects of introducing biochar and biochar-leachate on Fe(II) biooxidation by A. ferrooxidans and on the removal of Cd(II) and As(III) from an AMD system. The results showed that the biochar-leachate had a promoting effect on Fe(II) biooxidation by A. ferrooxidans. Conversely, biochar inhibited this process, and the inhibition increased with increasing biochar dose. Under both conditions (c(A. ferrooxidans) = 1.4 × 107 copies mL–1, m(FeSO4·7H2O):m(biochar) = 20:1; c(A. ferrooxidans) = 7.0 × 107 copies mL–1, m(FeSO4·7H2O):m(biochar) = 5:1), the biooxidation capacity of A. ferrooxidans was severely inhibited, with Fe(II) oxidation efficiency reaching a value of only ~ 20% after 84 h. The results confirmed that this inhibition might have occurred because a large fraction of the A. ferrooxidans present in the system adsorbed to the biochar, which weakened bacterial activity. In addition, mineral characterization analysis showed that the introduction of biochar changed the A. ferrooxidans biooxidation products from schwertmannite to jarosite, and the specific surface area increased after the minerals combined with biochar. Coprecipitation experiments of As(III) and Cd(II) showed that Cd(II) was adsorbed by the biochar over the first 12 h of reaction, with a removal efficiency of ~ 26%. As(III) was adsorbed by the generated schwertmannite over 24 h, with a removal efficiency of ~ 100%. These findings have positive implications for the removal of As(III) and Cd(II) from AMD.Graphical

An innovative method to degrade xanthate from flotation tailings wastewater in acid mine drainage (AMD) system: Performance, degradation mechanism and pathways

This study objective is to degrade xanthate from flotation tailings wastewater by using a coagulation-flocculation co-Fenton oxidation process in an acid mine drainage (AMD)-H2O2 system. More than 98% sodium butyl xanthate (SBX) removal rate was achieved by the method under optimal conditions. The acids and Fe2+ in AMD were sufficient to initiate a Fenton reaction at the aid of H2O2. Furthermore, iron ions were reduced to an extremely low level (0.19 mg/L) by participating in an oxidation process. Meanwhile, the Cu2+ ions in AMD facilitated the coagulation-flocculation process. Comparison experiments confirmed that the method was superior to the AMD alone (54.26%) and H2O2 alone (32.23%) in terms of performance in degrading SBX. The kinetic results showed that SBX degradation followed a pseudo first-order kinetic model. Additionally, the electron paramagnetic resonance (EPR) and quenching results suggested that hydroxyl radicals (•OH) were the main active species in AMD-H2O2 system. Degradation products were analyzed, and two possible pathways of SBX degradation were proposed. One pathway displayed that the SBX was first transformed into butyl xanthate peroxide (BPX), CO32− and S2O32−, and then further decomposed into CO2, H2O and SO42− under the ongoing •OH attack. Another pathway showed that precipitates consisting of butyl copper xanthate and iron oxide species were generated during the SBX degradation. This study provides a novel perspective on the innovative application of AMD in Fenton oxidation and provides a strong basis for the green and sustainable treatment of xanthate wastewater in tailings.

Direct immobilization of Se(IV) from acidic Se(IV)-rich wastewater via ferric selenite Co-precipitation

The attenuation of acidic Se(IV)-rich wastewater, including those associated with acid mine drainage (AMD) and nonferrous metallurgical wastewater (NMW), presents a serious environmental challenge. This study investigates the effects of diverse factors from pH values to Se(IV)/Fe(III) molar ratios, initial Se(IV) concentrations, and alkali neutralization agents on the direct co-precipitation of ferric selenites in AMD and NMW systems involving different orders of Fe(III) and alkali addition. Our results show that amorphous sulfate-substituted ferric (hydrogen) selenite and Se(IV)-bearing ferrihydrite-schwertmannite are the major Se(IV)-attenuation solids except that gypsum is an additional phase in the NMW system with Ca(OH)2 neutralization. Produced ferric selenites achieve 98–99.8% of Se(IV) immobilization under optimal conditions of pH 4.5, Se(IV)/Fe(III) molar ratios of 0.0625–0.5, and initial Se(IV) concentrations of 0.15–1.3 mmol·L-1. Moreover, completing FeSO4+ and FeHSeO32+/FeSeO3+ complexes as well as different ferric selenite co-precipitates are shown to collectively control aqueous Se(IV) remaining. Specifically, three distinct trends of aqueous Se(IV) concentrations separately correspond to changes in the four factors. The co-precipitation in the NMW system via pH adjustment followed by Fe(III) addition is more efficient for Se(IV) fixation than that in the AMD system because of minimal complexation, concurrent Fe(III) hydrolysis, and enhanced ferric selenite co-precipitation in the former.

Flotation separation of chalcopyrite and pyrite via Fenton oxidation modification in a low alkaline acid mine drainage (AMD) system

The selective flotation separation of pyrite and chalcopyrite, and the comprehensive utilization of AMD play a vital role in the cleaner production of copper sulfide ore. In this paper, flotation separation of chalcopyrite and pyrite via Fenton oxidation modification in a low alkaline acid mine drainage (AMD) system was investigated. The results of micro-flotation experiment displayed that the maximum recovery difference between chalcopyrite and pyrite was 74.6% at recommended test conditions. The artificial mixed-mineral flotation experiment further confirmed the desirable flotation separation of minerals. Zeta potential, FTIR spectra analysis, contact angle measurement and adsorption amount analysis results confirmed that the hydrophilic species caused by Fenton oxidation could seriously hinder the interaction between pyrite surfaces and EX collector. Whereas, the Fenton oxidation had feeble influence on the floatability of chalcopyrite. The XPS study indicated that Fenton oxidation significantly increased the contents of SO42- on pyrite surfaces, and the concentration of SO42- increased from 5.9% to 37.65%. Meanwhile, this modification promoted the deep transformation of Fe chemical states mainly from Fe(Ⅱ)-S to Fe(III)–OOH and Fe2(SO4)3. As a result, the contents of Fe(III)–OOH and Fe2(SO4)3 reached 50.04% and 29.19%, respectively. For chalcopyrite, a small amount of oxide/hydroxide species were formed during this processing, and the chalcopyrite can interact with EX collector effectively. Thus, flotation separation of chalcopyrite and pyrite via Fenton oxidation modification in a low alkaline AMD system mainly attributes to the significant differences in the number and species of hydrophilic species.

Thermal Transformation of Natural Schwertmannite in the Presence of Chromium

Schwertmannite is a metastable mineral playing a crucial role in the immobilization of metal(oid)s in acid mine drainage (AMD) systems. High temperatures associated with wildfires could lead to a sudden schwertmannite transformation, changing the mobility of metal(oid)s. The objective of the present study was to examine the thermal transformation from schwertmannite to hematite, and the subsequent effect on the chromium partitioning. The immobilization of arsenate after thermal transformation and its implications on chromium mobility was also evaluated. Natural schwertmannite, with increasing contents of chromium, was thermally treated between 200 to 800 °C. Transformation products were characterized by solid-phase techniques and selective chemical extractions. Results indicated a transformation to hematite at temperatures above 400 °C. The presence of chromium barely affected the temperature at which the transformation occurred, although partitioning of chromium in the mineral changed with temperature. As the temperature increased from 25 °C to 400 °C, chromium was less mobile and less outcompeted by arsenic adsorption, suggesting a larger contribution of inner-sphere complexes with increasing temperature. At temperatures above 600 °C, non-mobile forms strongly associated with neo-formed hematite were found. Finally, neo-formation of hematite led to a decrease in arsenic adsorption, implying a potentially enhanced arsenic mobility in AMD systems upon wildfires.

Metagenomic Mining for Esterases in the Microbial Community of Los Rueldos Acid Mine Drainage Formation.

Acid mine drainage (AMD) systems are extremely acidic and are metal-rich formations inhabited by relatively low-complexity communities of acidophiles whose enzymes remain mostly uncharacterized. Indeed, enzymes from only a few AMD sites have been studied. The low number of available cultured representatives and genome sequences of acidophiles inhabiting AMDs makes it difficult to assess the potential of these environments for enzyme bioprospecting. In this study, using naïve and in silico metagenomic approaches, we retrieved 16 esterases from the α/β-hydrolase fold superfamily with the closest match from uncultured acidophilic Acidobacteria, Actinobacteria (Acidithrix, Acidimicrobium, and Ferrimicrobium), Acidiphilium, and other Proteobacteria inhabiting the Los Rueldos site, which is a unique AMD formation in northwestern Spain with a pH of ∼2. Within this set, only two polypeptides showed high homology (99.4%), while for the rest, the pairwise identities ranged between 4 and 44.9%, suggesting that the diversity of active polypeptides was dominated not by a particular type of protein or highly similar clusters of proteins, but by diverse non-redundant sequences. The enzymes exhibited amino acid sequence identities ranging from 39 to 99% relative to homologous proteins in public databases, including those from other AMDs, thus indicating the potential novelty of proteins associated with a specialized acidophilic community. Ten of the 16 hydrolases were successfully expressed in Escherichia coli. The pH for optimal activity ranged from 7.0 to 9.0, with the enzymes retaining 33–68% of their activities at pH 5.5, which was consistent with the relative frequencies of acid residues (from 54 to 67%). The enzymes were the most active at 30–65°C, retaining 20–61% of their activity under the thermal conditions characterizing Los Rueldos (13.8 ± 0.6°C). The analysis of the substrate specificity revealed the capacity of six hydrolases to efficiently degrade (up to 1,652 ± 75 U/g at pH 8.0 and 30°C) acrylic- and terephthalic-like [including bis(2-hydroxyethyl)-terephthalate, BHET] esters, and these enzymes could potentially be of use for developing plastic degradation strategies yet to be explored. Our assessment uncovers the novelty and potential biotechnological interest of enzymes present in the microbial populations that inhibit the Los Rueldos AMD system.

Adsorption of octahedral mono-molybdate and poly-molybdate onto hematite: A multi-technique approach

Molybdenum (Mo) is a key trace element and a contaminant in many environments including mine tailings and acid mine drainage systems. Under oxic conditions Mo exists in a number of forms, including mono-molybdate (Mo(VI)O42-) and various poly-molybdate species (e.g. Mo(VI)7O246-) depending on the geochemical conditions (e.g. pH). The mobility and bioavailability of Mo is often controlled by sorption to mineral surfaces, including iron (oxyhydr)oxides e.g. hematite (Fe2O3). This study uses adsorption isotherms, PHREEQC geochemical modeling, Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and X-ray Absorption Spectroscopy (XAS) to holistically characterise the molecular scale adsorption of molybdate to hematite as a function of pH (3−12) and Mo(VI) concentration (0.01 × 10−4 - 2 × 10−3 M). PHREEQC and ATR-FTIR indicated both pH and Mo concentration are important variables when forming mono- vs. poly- molybdate and suggest low pH (≤ 4) and high Mo(VI) concentration (≥ 5 × 10−4 M) contribute to the formation of a poly-molybdate surface species on the hematite surface. XAS found Mo adsorbed to hematite via an inner-sphere corner-sharing bidentate binuclear complex with an octahedral mono-molybdate structure at a Mo concentration of 0.6 × 10−4 M across the pH range, and at a Mo(VI) concentration of 5 × 10−4 M and pH over 5. This is the first direct observation of octahedrally coordinated Mo(VI) adsorption species on hematite, and this information has broad implications for the mobility and transport of Mo as a contaminant in the environment.

Molecular structures of dissolved and colloidal AsV–FeIII complexes and their roles in the mobilization of AsV under strongly acidic conditions

The effect of high concentration of iron (FeIII) on the speciation and mobility of arsenic (As) under strongly acidic conditions remains unclear. This work studied the redistribution and speciation of AsV and FeIII at Fe/As molar ratio of 1–14 and pH 1.5–2.0 in the dissolved, colloidal, and solid phases. Results showed that the elevated FeIII induced the decomposition of the precipitated poorly crystalline ferric arsenate by forming dissolved (< 3 kDa) and colloidal (3 kDa–0.1 µm) As–Fe complexes. The fraction of particulate As (> 0.1 µm) decreased from 70–90% to less than 20% when the Fe/As molar ratio increased from 1 to 14. The particle size of the bulk samples decreased significantly with the increase of FeIII concentration. The FTIR results suggested that AsV in dissolved/colloidal As–Fe complexes dominantly occurred as HAsO42− species. The EXAFS results indicated that each HAsO42− coordinated with approximately two Fe atoms in dissolved/colloidal As–Fe complexes at Fe/As ≥ 2. The findings suggest that high aqueous FeIII concentration can promote the mobility of As by forming dissolved/colloidal Fe–As complexes in acidic waters, potentially accelerating As transport from source to downstream in acid mine drainage systems.

Dissolution and solubility of rhomboclase and arsenic-substituted rhomboclase phases at pH 2–10 and 25–45 °C

The synthetic rhomboclase (Rbc) and arsenic-substituted rhomboclase phases (As-Rbc) were colorless well-formed rhombic thin tabular crystals. For their dissolution at initial pH 2–10 and 25–45 °C, the constituents were preferentially dissolved in the order of H5O2+ ≫ AsO4 > SO4 > Fe for ~1 h, H5O2+ ≫ AsO4 > Fe > SO4 from ~1 h to 720 h and finally H5O2+ ≫ AsO4 > SO4 = Fe, suggesting an initial nonstoichiometric dissolution of As-Rbc to form Fe-rich outlayers and a final stoichiometric dissolution. The PHREEQC simulation indicated that the dissolved iron, sulfate and arsenate were present mainly as FeSO4+/Fe(SO4)2-/Fe3+, HSO4−/FeSO4+ and H3AsO40/H2AsO4−, respectively. The SEM observation showed that the tops and edges of the crystals were dissolved and that the crystal surfaces were then gradually smoothed/rounded until all the edges and corners disappeared. For the dissolution at pH 2 and 25 °C for 720–2880 h, the ion-activity products [log IAP], which equal the solubility products [log Ksp] at equilibrium, and the Gibbs free energies of formation [ΔGf°] were estimated to be −8.80 ± 0.01 and −2706.44 ± 1.90 kJ/mol for the Rbc [(H5O2)1.434Fe0.855(SO4)2·2H2O], respectively. For the As-Rbc [(H5O2)y (Fe)z [(AsO4)x (SO4)1-x]2·2H2O], the log IAP and ΔGf° values varied from −10.03 ± 0.03 to −8.89 ± 0.01 and from −2680.51 ± 2.05 kJ/mol to −2548.71 ± 1.94 kJ/mol, respectively. There was a strong negative correlation between the log IAP and the AsO4/(AsO4+SO4) molar ratio of As-Rbc. The results of this study provide new interesting thermodynamic data for the most acidic sulfates Rbc and As-Rbc; these data can be applied in the geochemical modeling and prediction of acid mine drainage systems.

Response of soil protozoa to acid mine drainage in a contaminated terrace

Acid mine drainage (AMD) system represents one of the most unfavorable habitats for microorganisms due to its low pH and high concentrations of metals. Compared to bacteria and fungi, our understanding regarding the response of soil protozoa to such extremely acidic environments remains limited. This study characterized the structures of protozoan communities inhabiting a terrace heavily contaminated by AMD. The sharp environmental gradient of this terrace was generated by annual flooding from an AMD lake located below, which provided a natural setting to unravel the environment-protozoa interactions. Previously unrecognized protozoa, such as Apicomplexa and Euglenozoa, dominated the extremely acidic soils, rather than the commonly recognized members (e.g., Ciliophora and Cercozoa). pH was the most important factor regulating the abundance of protozoan taxa. Metagenomic analysis of protozoan metabolic potential showed that many functional genes encoding for the alleviation of acid stress and various metabolic pathways were enriched, which may facilitate the survival and adaptation of protozoa to acidic environments. In addition, numerous co-occurrences between protozoa and bacterial or fungal taxa were observed, suggesting shared environmental preferences or potential bio-interactions among them. Future studies are required to confirm the ecological roles of these previously unrecognized protozoa as being important soil microorganisms.

Implication of biofilms in the sustainability of acid mine drainage and metal dispersion near coal tailings

In this study, the ecology of biofilms collected from sediments and efflorescent crusts (EFC) along an acid mine drainage (AMD) system was determined using 16S bacterial metagenomics. The dissolution of coal tailing and EFC by bacteria hosted in biofilms was investigated. Results revealed the predominance of acidophilic bacteria such as Acidithiobacillus ferrooxidans, Leptospirilum ferrooxidans, Acidithrix, Leptospirilum sp, Acidimicrobiaceae, Sulfobacillus, Acidiphilium, and Acidithiobacillus sp. in the biofilms, some of which have been reported to oxidize sulfide minerals and contribute to AMD formation. The experimental results further highlighted the ability of the bacteria in biofilms to leach out metals such as Co, Fe, and Zn, while decreasing the pH of the solution. The bioleaching of EFC was very fast, and increased diversity of the bacterial inoculum contributed to accelerating the leaching rate. Compared to abiotic leaching, the dissolution of minerals by acidophilic bacteria increased the percentage of free hydrated metal speciated forms over the inorganic complex speciated forms, suggesting the potential of biofilms to enhance the dispersion of metals in aquatic systems.

The adsorption of As(V) on poorly crystalline Fe oxyhydroxides, revisited: Effect of the reaction media and the drying treatment

Arsenic (As) adsorbed on Fe oxyhydroxides (adsorbent) is widely occurring in many environmental settings such as in acid mine drainage systems or in the hydrometallurgical operations to form Fe-As coprecipitates. However, the influence of the reaction media and the drying treatment on the microstructure of the directly formed adsorbents at various pHs was still not fully understood. In this work, As adsorption behaviors on various forms of Fe oxyhydroxides were systematically investigated by using XRD, FTIR, Raman, XANES, and HRTEM. The results revealed that at weak acidic pH, more As could adsorbed on the suspension adsorbent formed in sulfate and chloride media than that in nitrate media, possibly due to the microstructure alteration of the adsorbent in the presence of sulfate and chloride. Besides, the increasing crystallinity of the Fe oxyhydroxides and the aggregation effect after drying were the major reasons why less As could be hold by the dried adsorbents than that of the corresponding suspension adsorbents. These findings could shed more light on the nature of the Fe oxyhydroxides which may be helpful for more precisely predicting the fate of some toxic metal(loid)s in the environment.

The role of iron in the rare earth elements and uranium scavenging by Fe–Al-precipitates in acid mine drainage

The scavenging of soluble metals by iron (Fe) and aluminium (Al) oxyhydroxides is a natural process that occurs in acid mine drainage (AMD). This phenomenon is relevant to the immobilization, transport, and recovery of important natural resources such as rare earth elements (REE) and uranium (U). Furthermore, understanding the players and the reactions that govern the scavenging of REE and U by Fe and Al oxyhydroxides in aqueous systems is fundamental for natural and engineering sciences and for environmental management. In this scenario, the current work investigated the role of iron in the co-precipitation of REE and U when treating effluents by pH neutralization in an AMD system located in Brazil. The research employed water sampling, co-precipitation batch experiments, sequential extraction, X-ray diffraction and 57Fe Mössbauer spectroscopy. The results revealed that the presence and the amount of Fe in the initial solution can influence the REE removal efficiency positively. The effect of the addition of Fe over the REE removal efficiency was irrelevant when the pH of the AMD was raised to values equal to 7–8. The scavenging of U was not influenced by the addition of Fe to the AMD. The sequential extraction results showed that precipitates containing higher amounts of Fe tend to be less labile. The 57Fe Mössbauer spectra revealed that the REE can occupy iron sites in the structure of the amorphous precipitates. The findings of the current study can be extrapolated to other AMD systems and contribute to the development of novel REE recovery and hydrometallurgical techniques.

Secondary Sulfates from the Monte Arsiccio Mine (Apuan Alps, Tuscany, Italy): Trace-Element Budget and Role in the Formation of Acid Mine Drainage

A suite of sulfate minerals from the Monte Arsiccio mine (Apuan Alps, Northern Tuscany, Italy), previously identified by using both X-ray diffraction and micro-Raman spectroscopy, was studied through inductively coupled plasma mass spectrometry (ICP-MS), in order to determine their trace-element content. Several elements (Tl, Rb, As, Sb, Co, Ni, Cu, Zn, and Cr) were found above the detection limits. Among them, some are important from an environmental perspective and may reach relatively high concentrations (e.g., Tl = 1370–2988 μg/g; As = 505–1680 μg/g). Thus, these sulfates may act as transient sinks for some of these potentially toxic elements, as well as for sulfate ions and acidity. Indeed, dissolution experiments revealed the ability of these secondary minerals to produce a significant pH decrease of the solutions, as well as the release of Fe, Al, and K as major ions. This work discusses the relation between the budget of trace elements and the crystal chemistry of sulfate minerals and provides new insights about the environmental role played by the sulfate dissolution in controlling the quality of water in acid mine drainage systems.

Thermoplasmata and Nitrososphaeria as dominant archaeal members in acid mine drainage sediment of Malanjkhand Copper Project, India.

Acid mine drainage (AMD) harbors all three life forms inspite of its toxic and hazardous nature. In comparison to bacterial diversity, an in-depth understanding of the archaeal diversity in AMD and their ecological significance remain less explored. Archaeal populations are known to play significant roles in various biogeochemical cycles within the AMD ecosystem, and it is imperative to have a deeper understanding of archaeal diversity and their functional potential in AMD system. The present study is aimed to understand the archaeal diversity of an AMD sediment of Malanjkhand Copper Project, India through archaea specific V6 region of 16S rRNA gene amplicon sequencing. Geochemical data confirmed the acidic, toxic, heavy metal-rich nature of the sample. Archaea specific V6-16S rRNA gene amplicon data showed a predominance of Thermoplasmata (BSLdp215, uncultured Thermoplasmata, and Thermoplasmataceae) and Nitrososphaeria (Nitrosotaleaceae) members constituting ~ 95% of the archaeal community. Uncultured members of Bathyarchaeia, Group 1.1c, Hydrothermarchaeota, and Methanomassiliicoccales along with Methanobacteriaceae, Methanocellaceae, Haloferaceae, Methanosaetaceae, and Methanoregulaceae constituted the part of rare taxa. Analysis of sequence reads indicated that apart from their close ecological relevance, members of the Thermoplasmata present in Malanjkhand AMD were mostly involved in chemoheterotrophy, Fe/S redox cycling, and with heavy metal resistance, while the Nitrososphaeria members were responsible for ammonia oxidation and fixation of HCO3- through 3-hydroxypropionate/4-hydroxybutyrate cycle at low pH and oligotrophic environment which subsequently played an important role in nitrification process in AMD sediment. Overall, the present study elucidated the biogeochemical significance of archaeal populations inhabiting the toxic AMD environment.

Selective radionuclide co-sorption onto natural minerals in environmental and anthropogenic conditions

Anthropogenic activities can redistribute the constituents of naturally occurring radioactive materials (NORM), posing potential hazards to populations and ecosystems. In the present study, the co-sorption of several RN from the U decay chain– 238U, 230Th, 226Ra, 210Pb and 210Po, onto common minerals associated with mining activities (chalcopyrite, bornite, pyrite and barite) was investigated, in order to identify the various factors that control long-term NORM mobility and retentivity in environmental acid-mine drainage systems and hydrometallurgical processing. The results show selective RN co-sorption to the various natural minerals, suggesting that mineral-specific mechanisms govern the variability in NORM mobility and retentivity. Both 226Ra and 210Po underwent significant sorption onto the natural minerals investigated in this study. The order of co-sorption in sulfate media for chalcopyrite and bornite was 210Po>226Ra>206Pb>210Pb>238U/230Th. Conversely, both pyrite and barite showed increased affinity for 226Ra; the order of co-sorption in sulfate media was 226Ra>210Po>206Pb/210Pb>238U/230Th for pyrite and 226Ra>206Pb/210Pb>230Th/238U/210Po for barite. Similar orders of co-sorption were observed in the nitrate media: for chalcopyrite and bornite the order was 210Po>226Ra/206Pb/210Pb/238U/230Th compared to 226Ra>210Po/206Pb/210Pb/238U/230Th for pyrite and barite. The behavior of 210Po was found to the anomalous: in both sulfate and nitrate solutions, 210Po had little affinity for barite compared to the sulfides. Thermodynamic modeling indicated the formation of a reduced PoS(s) phase at the surface of sulfide minerals, leading to the suggestion that 210Po likely undergoes reductive precipitation on the surface of sulfide minerals. The high sorption of both 206Pb and 210Pb observed in the sulfate systems were likely as a result of co-precipitation as insoluble anglesite compared to nitrate where they mainly remained in solution. Overall, barite showed the highest affinity for 226Ra, given its propensity to sorb 226Ra (similar ionic size). Both 238U and 230Th were highly mobile in acidic sulfate and nitrate solutions. The results highlighted here identify the various constraints on the natural variability and fractionation of NORM in the environment, as well as the mineral-specific mechanisms that control co-sorption of RN. This information provides a framework for predicting RN transport within soils and ground waters with variable geochemical conditions and in metallurgical extraction processes, in order to develop effective strategies towards NORM mitigation.

Acid Mine Drainage as Energizing Microbial Niches for the Formation of Iron Stromatolites: The Tintillo River in Southwest Spain.

The Iberian Pyrite Belt in southwest Spain hosts some of the largest and diverse extreme acidic environments with textural variation across rapidly changing biogeochemical gradients at multiple scales. After almost three decades of studies, mostly focused on molecular evolution and metagenomics, there is an increasing awareness of the multidisciplinary potential of these types of settings, especially for astrobiology. Since modern automatized exploration on extraterrestrial surfaces is essentially based on the morphological recognition of biosignatures, a macroscopic characterization of such sedimentary extreme environments and how they look is crucial to identify life properties, but it is a perspective that most molecular approaches frequently miss. Although acid mine drainage (AMD) systems are toxic and contaminated, they offer at the same time the bioengineering tools for natural remediation strategies. This work presents a biosedimentological characterization of the clastic iron stromatolites in the Tintillo river. They occur as laminated terraced iron formations that are the most distinctive sedimentary facies at the Tintillo river, which is polluted by AMD. Iron stromatolites originate from fluvial abiotic factors that interact with biological zonation. The authigenic precipitation of schwertmannite and jarosite results from microbial-mineral interactions between mineral and organic matrices. The Tintillo iron stromatolites are composed of bacterial filaments and diatoms as Nitzschia aurariae, Pinnularia aljustrelica, Stauroneis kriegeri, and Fragilaria sp. Furthermore, the active biosorption and bioleaching of sulfur are suggested by the black and white coloration of microbial filaments inside stromatolites. AMD systems are hazardous due to physical, chemical, and biological agents, but they also provide biogeochemical sources with which to infer past geochemical conditions on Earth and inform exploration efforts on extraterrestrial surfaces in the future.

Sulfates from the Pyrite Ore Deposits of the Apuan Alps (Tuscany, Italy): A Review

The occurrence of sulfate minerals associated with the pyrite ores of the southern Apuan Alps has been known since the 19th century but modern mineralogical studies started only in the last decade. Sulfate assemblages were identified in all the pyrite ore deposits from the studied area but the more impressive associations were discovered in the Fornovolasco and Monte Arsiccio mines. Their study allowed to improve the knowledge of the sulfate crystal-chemistry and to achieve a better understanding of the acid mine drainage (AMD) systems associated with pyrite oxidation. More than 20 different mineral species were identified and, among them, four sulfates (volaschioite, giacovazzoite, magnanelliite, and scordariite) have their type localities in the pyrite ore deposits of the Apuan Alps. A review of the mineralogical results of a ten-year-long study is given here.

Insights into the Metabolism and Evolution of the Genus Acidiphilium, a Typical Acidophile in Acid Mine Drainage.

Here, we report three new Acidiphilium genomes, reclassified existing Acidiphilium species, and performed the first comparative genomic analysis on Acidiphilium in an attempt to address the metabolic potential, ecological functions, and evolutionary history of the genus Acidiphilium In the genomes of Acidiphilium, we found an abundant repertoire of horizontally transferred genes (HTGs) contributing to environmental adaption and metabolic expansion, including genes conferring photosynthesis (puf, puh), CO2 assimilation (rbc), capacity for methane metabolism (mmo, mdh, frm), nitrogen source utilization (nar, cyn, hmp), sulfur compound utilization (sox, psr, sqr), and multiple metal and osmotic stress resistance capacities (czc, cop, ect). Additionally, the predicted donors of horizontal gene transfer were present in a cooccurrence network of Acidiphilium Genome-scale positive selection analysis revealed that 15 genes contained adaptive mutations, most of which were multifunctional and played critical roles in the survival of extreme conditions. We proposed that Acidiphilium originated in mild conditions and adapted to extreme environments such as acidic mineral sites after the acquisition of many essential functions.IMPORTANCE Extremophiles, organisms that thrive in extreme environments, are key models for research on biological adaption. They can provide hints for the origin and evolution of life, as well as improve the understanding of biogeochemical cycling of elements. Extremely acidophilic bacteria such as Acidiphilium are widespread in acid mine drainage (AMD) systems, but the metabolic potential, ecological functions, and evolutionary history of this genus are still ambiguous. Here, we sequenced the genomes of three new Acidiphilium strains and performed comparative genomic analysis on this extremely acidophilic bacterial genus. We found in the genomes of Acidiphilium an abundant repertoire of horizontally transferred genes (HTGs) contributing to environmental adaption and metabolic ability expansion, as indicated by phylogenetic reconstruction and gene context comparison. This study has advanced our understanding of microbial evolution and biogeochemical cycling in extreme niches.