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Granite-related wolframite-quartz veins are the world's most important tungsten mineralization and production resource. Recent progress in revealing their hydrothermal processes has been greatly facilitated by the use of infrared microscopy and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis of both quartz- and wolframite-hosted fluid inclusions. However, owing to the paucity of detailed petrography, previous fluid inclusion studies on coexisting wolframite and quartz are associated with a certain degree of ambiguity. To better understand the fluid processes forming these two minerals, free-grown crystals of intergrown wolframite and quartz from the giant Yaogangxian W deposit in South China were studied using integrated in situ analytical methods including cathodoluminescence (CL) imaging, infrared microthermometry, Raman microspectroscopy, and fluid inclusion LA-ICP-MS analysis. Detailed crystal-scale petrography with critical help from CL imaging shows repetition of quartz, wolframite, and muscovite in the depositional sequence, which comprises a paragenesis far more complex than previous comparable studies. The reconstruction of fluid history in coexisting wolframite and quartz recognizes at least four successive fluid inclusion generations, two of which were entrapped concurrently with wolframite deposition. Fluctuations of fluid temperature and salinity during precipitation of coexisting wolframite and quartz are reflected by our microthermometry results, according to which wolframite-hosted fluid inclusions do not display higher homogenization temperature or salinity than those in quartz. However, LA-ICP-MS analysis shows that both primary fluid inclusions in wolframite and quartz-hosted fluid inclusions associated intimately with wolframite deposition are characterized by strong enrichment in Sr and depletion in B and As compared to quartz-hosted fluid inclusions that are not associated with wolframite deposition. The chemical similarity between the two fluid inclusion generations associated with wolframite deposition implies episodic tungsten mineralization derived from fluids exhibiting distinct chemical signatures. Multiple chemical criteria including incompatible elements and Br/Cl ratios of fluid inclusions in both minerals suggest a magmatic-sourced fluid with the possible addition of sedimentary and meteoric water. Combined with microthermometry and Raman results, fluid chemical evolution in terms of B, As, S, Sr, W, Mn, Fe, and carbonic volatiles collectively imply fluid phase separation and mixing with sedimentary fluid may have played important roles in wolframite deposition, whereas fluid cooling and addition of Fe and Mn do not appear to be the major driving factor. This study also shows that fluid inclusions in both wolframite and coexisting quartz may contain a substantial amount of carbonic volatiles (CO2 ± CH4) and H3BO3. Ignoring the occurrence of these components can result in significant overestimation of apparent salinity and miscalculation of LA-ICP-MS elemental concentrations. We suggest that these effects should be considered critically to avoid misinterpretation of fluid inclusion data, especially for granite-related tungsten-tin deposits.

The Neoproterozoic sulfur isotope (δ34S) record is characterized by anomalously high δ34Spyrite values. Many δ34Spyrite values are higher than the contemporaneous δ34Ssulfate (i.e., δ34Spyrite > δ34Ssulfate), showing reversed fractionation. This phenomenon has been reported from the Neoproterozoic post-glacial strata globally and is called \"Neoproterozoic superheavy pyrite.\" The commonly assumed biogenic genesis of superheavy pyrite conflicts with current understanding of the marine sulfur cycle. Various models have been proposed to interpret this phenomenon, including extremely low concentrations of sulfate in seawaters or pore waters, or the existence of a geographically isolated and geochemically stratified ocean. Implicit and fundamental in all these published models is the assumption of a biogenic origin for pyrite genesis, which hypothesizes that the superheavy pyrite is syngenetic (in the water column) or early diagenetic (in shallow marine sediments) in origin and formed via microbial sulfate reduction (MSR). In this study, the Cryogenian Datangpo Formation in South China, which preserves some of the highest δ34Spyrite values up to +70 ppm, is studied by secondary ion mass spectrometry (SIMS) at unprecedented spatial resolutions (2 µm). Based on textures and the new sulfur isotope results, we propose that the Datangpo superheavy pyrite formed via thermochemical sulfate reduction (TSR) in hydrothermal fluids during late burial diagenesis and, therefore, lacks a biogeochemical connection to the Neoproterozoic sulfur cycle. Our study demonstrates that SEM-SIMS is an effective approach to assess the genesis of sedimentary pyrite using combined SEM petrography and micrometer-scale δ34S measurements by SIMS. The possibility that pervasive TSR has overprinted the primary δ34Spyrite signals during late diagenesis in other localities may necessitate the reappraisal of some of the δ34Spyrite profiles associated with superheavy pyrite throughout Earth's history.

Pozzolanic reaction of volcanic ash with hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old Roman harbor concrete. Pliny the Elder, however, in first century CE emphasized rock-like cementitious processes involving volcanic ash (pulvis) \"that as soon as it comes into contact with the waves of the sea and is submerged becomes a single stone mass (fierem unum lapidem), impregnable to the waves and every day stronger\" (Naturalis Historia 35.166). Pozzolanic crystallization of Al-tobermorite, a rare, hydrothermal, calcium-silicate-hydrate mineral with cation exchange capabilities, has been previously recognized in relict lime clasts of the concrete. Synchrotron-based X-ray microdiffraction maps of cementitious microstructures in Baianus Sinus and Portus Neronis submarine breakwaters and a Portus Cosanus subaerial pier now reveal that Al-tobermorite also occurs in the leached perimeters of feldspar fragments, zeolitized pumice vesicles, and in situ phillipsite fabrics in relict pores. Production of alkaline pore fluids through dissolution-precipitation, cation-exchange and/or carbonation reactions with Campi Flegrei ash components, similar to processes in altered trachytic and basaltic tuffs, created multiple pathways to post-pozzolanic phillipsite and Al-tobermorite crystallization at ambient seawater and surface temperatures. Long-term chemical resilience of the concrete evidently relied on water-rock interactions, as Pliny the Elder inferred. Raman spectroscopic analyses of Baianus Sinus Al-tobermorite in diverse microstructural environments indicate a cross-linked structure with Al3+ substitution for Si4+ in Q3 tetrahedral sites, and suggest coupled [Al3++Na+] substitution and potential for cation exchange. The mineral fabrics provide a geoarchaeological prototype for developing cementitious processes through low-temperature rock-fluid interactions, subsequent to an initial phase of reaction with lime that defines the activity of natural pozzolans. These processes have relevance to carbonation reactions in storage reservoirs for CO2 in pyroclastic rocks, production of alkali-activated mineral cements in maritime concretes, and regenerative cementitious resilience in waste encapsulations using natural volcanic pozzolans.

Bone is a natural nanocomposite. Its mineral component is nanocrystalline calcium phosphate apatite, whose synthetic biomimetic analogs can be prepared by wet chemistry. The initially formed crystals, whether biological or synthetic, exhibit very peculiar physicochemical features. In particular, they are nanocrystalline, nonstoichiometric, and hydrated. The surface of the nanocrystals is covered by a non-apatitic hydrated layer containing mobile ions, which may explain their exceptional surface reactivity. For their precipitation in vivo or in vitro, for their evolution in solution, for the 3D organization of the nanocrystals, and for their consolidation to obtain bulk ceramic materials, water appears to be a central component that has not received much attention. In this mini-review, we explore these key roles of water on the basis of physicochemical and thermodynamic data obtained by complementary tools including FTIR, XRD, ion titrations, oxide melt solution calorimetry, and cryo-FEG-SEM. We also report new data obtained by DSC, aiming to explore the types of water molecules associated with the nanocrystals. These data support the existence of two main types of water molecules associated with the nanocrystals, with different characteristics and probably different roles and functions. These findings improve our understanding of the behavior of bioinspired apatite-based systems for biomedicine and also of biomineralization processes taking place in vivo, at present and in the geologic past. This paper is thus intended to give an overview of the specificities of apatite nanocrystals and their close relationship with water.

Ash fall layers and vitroclastic-carrying sediments distributed throughout the entire Permian stratigraphic range of the Parana Basin (Brazil and Uruguay) occur in the Tubarao Supergroup (Rio Bonito Formation) and the Passa Dois Group (Irati, Estrada Nova/Teresina, Corumbatai, and Rio do Rasto Formations), which constitute the Gondwana 1 Supersequence. U-Pb zircon ages, acquired by SHRIMP and isotope-dissolution thermal ionization mass spectrometer (ID-TIMS) from tuffs within the Mangrullo and Yaguari Formations of Uruguay, are compatible with a correlation with the Irati and parts of the Teresina and Rio do Rasto Formations, respectively, of Brazil. U-Pb zircon ages suggest maximum depositional ages for the samples: (1) Rio Bonito Formation: ages ranging from 295.8±3.1 to 304.0±5.6 Ma (Asselian, lowermost Permian), consistent with the age range of the Protohaploxypinus goraiensis subzone; (2) Irati Formation: ages ranging from 279.9±4.8 to 280.0±3.0 Ma (Artinskian, Middle Permian), consistent with the occurrence of species of the Lueckisporites virkkiae zone; (3) Rio do Rasto Formation: ages ranging from 266.7±5.4 to 274.6±6.3 Ma (Wordian to Roadian, Middle Permian). All the SHRIMP U-Pb zircon ages are consistent with their superimposition order in the stratigraphy, the latest revisions to the Permian timescale (International Commission of Stratigraphy, 2018 version), and the most recent appraisals of biostratigraphic data. The ID-TIMS U-Pb zircon ages from the Corumbatai Formation suggest that U-Pb ages may be >10% younger than interpreted biostratigraphic ages.

Biomineralization is an evolutionarily ancient phenomenon and one of the fundamental biological processes by which living organisms produce minerals with multifunctional properties. Among the more general biomineralization processes, those involving silica (biosilicification), calcium-based biominerals (calcification), and iron-based biominerals (biomagnetism) have been described in a wide pattern of living organisms, from single cells to higher plants, animals, and even humans. After 25 yr of extensive studies of biosilicification, diverse biomacromolucules have been proposed and confirmed as active players in this special field of biomineralization. Despite these discoveries, biosilicification is still a paradigm and a cause of scientific controversy. This review has the ambitious goal of providing thorough and comprehensive coverage of biosilicification as a multifaceted topic with intriguing hypotheses and numerous challenging open questions. The structural diversity, chemistry, and biochemistry of biosilica in viruses, bacteria, plants, diatoms, and sponges are analyzed and discussed here. Special attention is paid to prospects and trends in applications of biosilica for technology, materials science and biomedicine.

Arsenic and antimony are highly toxic to humans, animals, and plants. Incorporation in alunite, jarosite, and beudantite group minerals can immobilize these elements and restrict their bioavailability in acidic, oxidizing environments. This paper reviews research on the magnitude and mechanisms of incorporation of As and Sb in, and release from, alunite, jarosite, and beudantite group minerals in mostly abiotic systems. Arsenate-for-sulfate substitution is observed for all three mineral groups, with the magnitude of incorporation being beudantite (3-8.5 wt% As) > alunite (3.6 wt% As) > natroalunite (2.8 wt%) > jarosite (1.6 wt% As) > natroalunite (1.5 wt% As) > hydroniumalunite (0.034 wt% As). Arsenate substitution is limited by the charge differences between sulfate (-2) and arsenate (-3), deficiencies in B-cations in octahedral sites and for hydroniumalunite, difficulty in substituting protonated H2O-for-OH- groups. Substitution of arsenate causes increases in the c-axis for alunite and natroalunite, and in the c- and a-axes for jarosite. The degree of uptake depends on, but limited by, the AsO4/TO4 ratio. Aerobic and abiotic As release from alunite and natroalunite is limited, especially between pH 5 and 8. Release of As is also very limited in As-bearing jarosite, natrojarosite, and ammoniumjarosite at pH 8 due to the formation of secondary maghemite, goethite, hematite, and Fe arsenates that resorb the liberated As. Abiotic reductive dissolution of As-bearing jarosite at pH 4, 5.5, and 7 is likewise restricted by the formation of secondary green rust sulfate, goethite, and lepidocrocite that take up the As. Similar processes have been observed for the aerobic dissolution of Pb-As-jarosite (beudantite analog), with secondary Fe oxyhydroxides resorbing the released As at pH 8. Higher amounts of As are released, however, during microbial-driven jarosite dissolution. Natural jarosite has been found to contain up to 5.9 wt% Sb5+ substituting for Fe3+ in the B-site of the mineral structure. Sb(V) is not released from jarosite at pH 4 during abiotic reductive dissolution, but at pH 5.5 and 7, up to 75% of the mobilized Sb can be structurally incorporated into secondary green rust sulfate, lepidocrocite, or goethite. Further research is needed on the co-incorporation of As, Sb, and other ions in, and the uptake and release of Sb from, alunite, jarosite, and beudantite group minerals, the influence of microbes on these processes and the long-term (>1 yr) stability of these minerals.

Magnesian calcites are important components of sediments and biominerals. Although Raman spectra of calcite, dolomite, and magnesite are well known, those of magnesian calcites deserve further investigation. Nineteen syntheses of magnesian calcites covering the range 0-50 mol% MgCO3 have been carried out at high pressure and temperature (1-1.5 GPa, 1000-1100 °C). The crystalline run products have been characterized by µ-Raman spectroscopy. For all lattice and internal modes (L, T, ν1, ν4, 2ν2) but ν3, wavenumbers align closer to the calcite- dolomite line than the calcite-magnesite line. The compositional dependence is strong and regression curves with high correlation coefficients have been determined. Full-width at half maximum (FWHM) plot along parabolas that depart from the calcite-dolomite or calcite-magnesite lines. The limited data dispersion of both shifts and FWHM allow using Raman spectral properties of magnesian calcites to determine the Mg content of abiotic calcites. A comparison with Raman data from the literature obtained on synthetic magnesian amorphous calcium carbonate (Mg ACC) shows that the wavenumber position of the ACC ν1 mode is systematically shifted toward lower values, and that their FWHM are higher than those of their crystalline counterparts. The FWHM parameters of crystalline and amorphous materials do not overlap, which allows a clear-cut distinction between crystalline and amorphous materials. In synthetic magnesian calcites, the shift and FWHM of Raman bands as a function of magnesium can be interpreted in terms of changes of metal-O bond lengths resulting from the replacement of calcium by magnesium. The facts that the wavenumber of magnesian calcites are close to the calcite-dolomite line (not calcite-magnesite), that the FWHM of the T, L, and ν4 modes reach a maximum around 30 ±5 mol% MgCO3, and that a peak specific to dolomite at 880 cm-1 is observed in high-magnesian calcites indicate that dolomite-like ordering is present above ∼10 mol% MgCO3. Mg atom clustering in cation layers combined with ordering in successive cation basal layers may account for the progressive ordering observed in synthetic magnesian calcites.

Dusty olivine (olivine containing multiple sub-micrometer inclusions of metallic iron) in chondritic meteorites is considered an ideal carrier of paleomagnetic remanence, capable of maintaining a faithful record of pre-accretionary magnetization acquired during chondrule formation. Here we show how the magnetic architecture of a single dusty olivine grain from the Semarkona LL3.0 ordinary chondrite meteorite can be fully characterized in three dimensions, using a combination of focused ion beam nanotomography (FIB-nT), electron tomography, and finite-element micromagnetic modeling. We present a three-dimensional (3D) volume reconstruction of a dusty olivine grain, obtained by selective milling through a region of interest in a series of sequential 20 nm slices, which are then imaged using scanning electron microscopy. The data provide a quantitative description of the iron particle ensemble, including the distribution of particle sizes, shapes, interparticle spacings and orientations. Iron particles are predominantly oblate ellipsoids with average radii 242 ± 94 × 199 ± 80 × 123 ± 58 nm. Using analytical TEM we observe that the particles nucleate on sub-grain boundaries and are loosely arranged in a series of sheets parallel to (001) of the olivine host. This is in agreement with the orientation data collected using the FIB-nT and highlights how the underlying texture of the dusty olivine is crystallographically constrained by the olivine host. The shortest dimension of the particles is oriented normal to the sheets and their longest dimension is preferentially aligned within the sheets. Individual particle geometries are converted to a finite-element mesh and used to perform micromagnetic simulations. The majority of particles adopt a single vortex state, with \"bulk\" spins that rotate around a central vortex core. We observed no particles that are in a true single domain state. The results of the micromagnetic simulations challenge some preconceived ideas about the remanence-carrying properties of vortex states. There is often not a simple predictive relationship between the major, intermediate, and minor axes of the particles and the remanence vector imparted in different fields. Although the orientation of the vortex core is determined largely by the ellipsoidal geometry (i.e., parallel to the major axis for prolate ellipsoids and parallel to the minor axis for oblate ellipsoids), the core and remanence vectors can sometimes lie at very large (tens of degrees) angles to the principal axes. The subtle details of the morphology can control the overall remanence state, leading in some cases to a dominant contribution from the bulk spins to the net remanence, with profound implications for predicting the anisotropy of the sample. The particles have very high switching fields (several hundred millitesla), demonstrating their high stability and suitability for paleointensity studies.

Here we present a study on the quenchability of hydrous mafic melts. We show via hydrothermal experiments that the ability to quench a mafic hydrous melt to a homogeneous glass at cooling rates relevant to natural samples has a limit of no more than 9 ± 1 wt% of dissolved H2O in the melt. We performed supra-liquidus experiments on a mafic starting composition at 1-1.5 GPa spanning H2O-undersaturated to H2O-saturated conditions (from ∼1 to ∼21 wt%). After dissolving H2O and equilibrating, the hydrous mafic melt experiments were quenched. Quenching rates of 20 to 90 K/s at the glass transition temperature were achieved, and some experiments were allowed to decompress from thermal contraction while others were held at an isobaric condition during quench. We found that quenching of a hydrous melt to a homogeneous glass at quench rates comparable to natural conditions is possible at water contents up to 6 wt%. Melts containing 6-9 wt% of H2O are partially quenched to a glass, and always contain significant fractions of quench crystals and glass alteration/devitrification products. Experiments with water contents greater than 9 wt% have no optically clear glass after quench and result in fine-grained mixtures of alteration/devitrification products (minerals and amorphous materials). Our limit of 9 ± 1 wt% agrees well with the maximum of dissolved H2O contents found in natural glassy melt inclusions (8.5 wt% H2O). Other techniques for estimating pre-eruptive dissolved H2O content using petrologic and geochemical modeling have been used to argue that some arc magmas are as hydrous as 16 wt% H2O. Thus, our results raise the question of whether the observed record of glassy melt inclusions has an upper limit that is partially controlled by the quenching process. This potentially leads to underestimating the maximum amount of H2O recycled at arcs when results from glassy melt inclusions are predominantly used to estimate water fluxes from the mantle.