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Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O ₂ budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic–Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O ₂. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen.

Bioleaching of metal sulfides is performed by a diverse group of microorganisms. The dissolution chemistry of metal sulfides follows two pathways, which are determined by the mineralogy and the acid solubility of the metal sulfides: the thiosulfate and the polysulfide pathways. Bacterial cells can effect this metal sulfide dissolution via iron(II) ion and sulfur compound oxidation. Thereby, iron(III) ions and protons, the metal sulfide-attacking agents, are available. Cells can be active either in planktonic state or in forming biofilms on the mineral surface; however, the latter is much more efficient in terms of bioleaching kinetics. In the case of Acidithiobacillus ferrooxidans , bacterial exopolymers contain iron(III) ions, each complexed by two uronic acid residues. The resulting positive charge allows an electrostatic attachment to the negatively charged pyrite. Thus, the first function of complexed iron(III) ions is the mediation of cell attachment, while their second function is oxidative dissolution of the metal sulfide, similar to the role of free iron(III) ions in non-contact leaching. In both cases, the electrons extracted from the metal sulfide reduce molecular oxygen via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner membranes. In this review, we summarize some recent discoveries relevant to leaching bacteria which contribute to a better understanding of these fascinating microorganisms. These include surface science, biochemistry of iron and sulfur metabolism, anaerobic metabolism, and biofilm formation. The study of microbial interactions among multispecies leaching consortia, including cell-to-cell communication mechanisms, must be considered in order to reveal more insights into the biology of bioleaching microorganisms and their potential biotechnological use.

The pyrite-type high-pressure form of FeOOH is predicted from first principles, and found experimentally to be stable under the conditions at the base of the mantle, with implications for transport of water within Earth’s deep interior. Hydroxide remains stable under pressure Hydroxide, FeOOH, was recently reported to decompose under the conditions of the middle region of the lower mantle to form FeO 2 and release H 2 . This would suggest the upward migration of hydrogen and large fluctuations in the oxygen distribution in the Earth system. In contrast, Masayuki Nishi et al . report the stability of FeOOH under deep-lower-mantle pressure and temperature conditions, based on first-principles calculations and in situ X-ray diffraction experiments. The authors predict that pyrite-type FeOOH would be much denser than the surrounding mantle and conclude that it might stabilize as a solid solution with other hydrous minerals in deeply subducted slabs. This could potentially lead to the incorporation of hydrogen into the outer core. Water transported into Earth’s interior by subduction strongly influences dynamics such as volcanism and plate tectonics 1 , 2 , 3 . Several recent studies have reported hydrous minerals to be stable at pressure and temperature conditions representative of Earth’s deep interior, implying that surface water may be transported as far as the core–mantle boundary 4 , 5 , 6 , 7 , 8 . However, the hydrous mineral goethite, α-FeOOH, was recently reported 9 to decompose under the conditions of the middle region of the lower mantle to form FeO 2 and release H 2 , suggesting the upward migration of hydrogen and large fluctuations in the oxygen distribution within the Earth system. Here we report the stability of FeOOH phases at the pressure and temperature conditions of the deep lower mantle, based on first-principles calculations and in situ X-ray diffraction experiments. In contrast to previous work suggesting the dehydrogenation of FeOOH into FeO 2 in the middle of the lower mantle 9 , we report the formation of a new FeOOH phase with the pyrite-type framework of FeO 6 octahedra, which is much denser than the surrounding mantle and is stable at the conditions of the base of the mantle. Pyrite-type FeOOH may stabilize as a solid solution with other hydrous minerals in deeply subducted slabs, and could form in subducted banded iron formations. Deep-seated pyrite-type FeOOH eventually dissociates into Fe 2 O 3 and releases H 2 O when subducted slabs are heated at the base of the mantle. This process may cause the incorporation of hydrogen into the outer core by the formation of iron hydride, FeH x , in the reducing environment of the core–mantle boundary.

In coal mining areas, the ambient atmospheric and aqueous oxidation of pyrite minerals (FeS 2 ) associated with coal as well as the other accompanying strata is significant in understanding the extent of acid mine drainage (AMD), the cause of severe environmental pollution. Therefore, in this paper, the oxidation kinetics of the coal-associated pyrite (CAPy) present in a coal sample (TpHM1) has been studied via aqueous leaching depyritization experiments at variety of temperatures and time intervals without the incorporation of any oxidizer. The outcomes obtained are juxtaposed with the standard pyrite mineral (SPM) oxidation at the same experimental conditions. Also, the coal and SPM slurry residues and filtrates obtained after aqueous leaching at 25 °C and 90 °C for 0 h and 24 h, respectively, were extensively analyzed through high-resolution transmission electron microscopy (HR-TEM), Powder X-ray diffraction (P-XRD), and X-ray-photoelectron spectroscopy (XPS) for evaluation of the mineralogical composition and proportions of iron and sulfur components during progression of the oxidation reaction. Both the reactions obey pseudo first-order kinetics during pyrite (FeS 2 ) oxidation but a significant difference in the experimentally found activation energies ( E a ) and rate constants ( k ) values of oxidation kinetics of both CAPy and SPM may be attributed to the varied geochemical compositions of the coal associated pyrite (CAPy). The rate constant for CAPy is much greater than that of SPM implying a higher E a around 10.838 kJ/mol for SPM as compared to 1.941 kJ/mol for CAPy. The CAPy in coal (TpHM1) is more susceptible to atmospheric oxidation than that of SPM, leading to the formation of acid mine drainage with lower pH. In this paper, the pH values on the basis of stoichiometric pyrite oxidation reaction were calculated and compared with the pH values obtained after aqueous leaching of CAPy to interpret the extent of acid formation and pyrite dissolution. Hence, with the assistance of the current study, further studies on the effects of mineral impurities, whereabouts of pyrite minerals in coal seams, the significance of compositional differences in the CAPy, the effect of metal oxides, and the role of alkalinity producing neutralizing agents of coal in the oxidative dissolution process of pyrite can be investigated.

Carbonates from approximately 2.3-2.1 billion years ago show markedly positive 6 13 C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ¹³C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth's most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ³⁴S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ³⁴S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ³⁴S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion.

The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial–interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial–interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial–interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.

The Iberian Pyrite Belt (IPB) contains the world’s largest massive sulfide deposit, and, due to extensive mining developed during the last 200 years, large amounts of mining waste have been abandoned in this area, with roasted pyrite ash being the focus of this study. Polymetallic mining is also classified as a NORM (naturally occurring radioactive material) activity, thus the main objective of this work was to develop a radiological and physicochemical characterization of this waste (mineral phases, elemental and radionuclide concentrations) in order to perform a valorization diagnosis of this material. The composition of this waste strongly depends on its origin (mine), and is mainly formed by iron oxides (hematite, Fe₂O₃) and heavy metals and metalloids such as As, Pb, Zn, and Cu, in levels 2–4 orders of magnitude higher than those of undisturbed soils, depending on each particular element. However, the average natural radionuclide levels are similar to those of unperturbed soils (around 30 Bqkg−1 of 238U-series, 50 Bqkg−1 of 232Th, and 70 Bqkg−1 for 40K), thus they are below the limits established by European Union regulations to require radiological control during their future valorization. As the main potential applications of roasted pyrite ash, the valorization diagnosis indicates that it can be used as a source of Fe (FeCl₃ or FeSO₄), or an additive in the manufacturing of cements, pigments, etc.

Pyrite (FeS 2 ) is the end-product of bacterial sulfur cycling in reduced sedimentary environments. Sulfate-reducing bacteria (SRB) are mostly considered for biogenic pyrite formation due to their significant contribution to sulfide production at ambient temperatures. However, most experiments using SRB for biogenic pyrite formation resulted in the formation of only metastable iron sulfide minerals such as mackinawite (FeS). In this study, we investigated the roles of elemental sulfur (S 0 ) and microbial sulfur reduction for pyrite formation. To this end, we cultivated the Fe(III)- and sulfur-reducing bacterium Geobacter sulfurreducens in the presence of the Fe(III) (oxyhydr)oxide mineral ferrihydrite and elemental sulfur at two different Fe/S ratios (4:1 and 1:4). While only mackinawite formed in Fe/S: 4:1 experiments, sulfidic conditions in the Fe/S: 1:4 experiments favored greigite (Fe 3 S 4 ) and pyrite formation via the polysulfide pathway. Morphological observations demonstrated that spherulitic pyrite particles formed at the surface of elemental sulfur, with clusters forming that preserved the original morphology of sulfur particles. Our results showed that sulfur-reducing bacteria could replace the role of SRB as a sulfide source and further showed that sulfur particles are likely hotspots for biogenic pyrite formation by creating polysulfide-rich microenvironments and by acting as templates for spatially heterogeneous pyrite precipitation in nature.

In the present work an intense bibliographic search is developed, with updated information on the microscopic fundamentals that govern the behavior of flotation operations of chalcopyrite, the main copper mineral in nature. In particular, the effect caused by the presence of pyrite, a non-valuable mineral, but challenging for the operation due to its ability to capture a portion of collector and float, decreasing the quality of the concentrate, is addressed. This manuscript discusses the main chemical and physical mechanisms involved in the phenomena of reagent adsorption on the mineral surface, the impact of pH and type of alkalizing agent, and the effect of pyrite depressants, some already used in the industry and others under investigation. Modern collector reagents are also described, for which, although not yet implemented on an industrial scale, promising results have been obtained in the laboratory, including better copper recovery and selectivity, and even some green reagents present biodegradable properties that generate a better environmental perspective for mineral processing.