Dissolution–precipitation reactions in hydrothermal experiments with quartz–feldspar aggregates

Batch and flow-through experiments were performed on quartz–feldspar granular aggregates at hydrothermal conditions (up to ≈150 °C, up to 5 MPa effective pressure, and near-neutral pH) for up to 141 days. The effect of dissolution–precipitation reactions on the surface morphology of the mineral grains was investigated. The starting materials as well as the solids and fluids resulting from the experiments were characterized using BET, energy dispersive X-ray spectroscopy, electron microprobe analysis, inductively coupled plasma-optical emission spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, and X-ray fluorescence spectroscopy. The electrical conductivity of fluid samples was used as a proxy for the evolution of the fluid composition in the experiments. The chemical analyses of the fluids in combination with hydrogeochemical simulations with PHREEQC suggested the precipitation of Al–Si-bearing solid phases. Electron microscopy confirmed the formation of secondary amorphous Al–Si-bearing solid phases. The microscopic observations are consistent with a process of stoichiometric dissolution of the mineral grains, transport of dissolved ions in the fluid phase, and spatially coupled precipitation of sub-μm sized amorphous particles on mineral surfaces. These findings shed light onto early stages of diagenesis of quartz–feldspar sands and indicate that amorphous phases may be precursors for the formation of crystalline phases, for example, clay minerals.     

Crystal clustering in magmas: Insights from HP–HT experiments

We have studied by high-resolution X-ray Computed Tomography the effect of crystal clustering on the Shape-Preferred Orientation (SPO) development in synthetic magmas experimentally deformed at 300 MPa and 475–550°C. A fully connected solid network that could potentially induce the onset of yield strength is not achieved in these suspensions containing 16 vol% of crystals. The alumina grain population exhibits a glomeroporphyritic texture made of isolated grains (59.6%) and clusters of touching grains (40.4%). The SPO of the sub-population of isolated grains exhibits foliation and lineation, which are closely parallel to the plane and direction of shear, respectively. The SPO of clustered grains has little influence overall shape fabric. The angular relationships between the average foliation and cluster elongation provide a good indicator of the shear sense. Finally, we highlight the strain partitioning between nearly non-deformed large clusters acting as rigid glomerocrysts and highly sheared zones in low concentrated suspensions.     

The solubility of calcite in water at 6–16 kbar and 500–800 °C

The solubility of calcite in H₂O was measured at 6–16 kbar, 500–800 °C, using a piston-cylinder apparatus. The solubility was determined by the weight loss of a single crystal and by direct analysis of the quench fluid. Calcite dissolves congruently in the pressure (P) and temperature (T) range of this study. At 10 kbar, calcite solubility increases with increasing temperature from 0.016±0.005 molal at 500 °C to 0.057±0.022 molal at 750 °C. The experiments reveal evidence for hydrous melting of calcite between 750 and 800 °C. Solubilities show only a slight increase with increasing P over the range investigated. Comparison with work at low P demonstrates that the P dependence of calcite solubility is large between 1 and 6 kbar, increasing at 500 °C from 1.8×10^–5 molal at 1 kbar to 6.4×10^–3 molal at 6 kbar. The experimental results are described by:

Zircon–quartz–calcite segregations in carbonate–alkaline metasomatic rocks of the western Baikal region and their petrogenetic implications

Fine-grained segregations up to 5 mm in size composed of graphic intergrowths of zircon, quartz, calcite and containing up to 0.8 wt % SrO have been found in albite–riebeckite and dolomite–biotite metasomatic rocks formed after alaskite granite. They contain magnetite, titanomagnetite (25.4 wt % TiO₂), cerite-(Ce,Nd), rutile (up to 1.2 wt % Nb₂O₅), as well as rare micrograins of monazite-(Ce), bastnaesite-(Ce), and barite (up to 5.7 wt % SrO). The fine-grained structure of mineral aggregates suggests a metacolloidal nature. It is assumed that the zircon–quartz–calcite assemblage was formed due to exchange decomposition reaction between the salt phase of hydrothermal solution with predominant Na₂CO₃, elevated Zr and, to a lesser extent, Fe, Ti, LREE, Nb contents and dissolved calcium and silica compounds of a Na₂SiO₃ type.     

The effect of added dissolved calcium on calcite dissolution kinetics in aqueous solutions at 25°C

The kinetics of calcite dissolution in solutions containing dissolved Ca²⁺ has been investigated at 25°C, using a rotating disc apparatus. In acid solutions no effect of Ca²⁺ in solution is observed. The rate is dependent on the transport of H⁺ to the surface. In neutral to alkaline solutions the dissolution reaction is controlled by mixed kinetics and the conventional empirical representation of the dissolution rate results through the interaction of chemical and transport gradients in the diffusion boundary layer. The chemical reaction rate is a function of the gradient between the equilibrium and the surface concentrations of calcium carbonate, whereas the transport reaction can be described in terms of a series of gradients between the surface and the bulk of dissolved calcium and carbonate species. The presence of dissolved Ca²⁺ decreases the rate of the transport reaction, making the dissolution process more transport-controlled. The chemical rate constant is independent of the Ca²⁺ concentration in solution. The chemical rate constant for Carrara marble dissolution is determined to ∼2·10⁻² cm s⁻¹ and the diffusion coefficient for the transport reaction to ∼7.6·10⁻⁶ cm² s⁻¹.In natural systems with high Ca²⁺ concentrations and in absence of inhibitors of the surface chemical reaction, the dissolution of calcite may approach a transport-controlled reaction, especially in environments with restricted flow.     

Research on the adsorptive kinetic experiments on humus and its spacial variations in the Changjiang (Yangtze) estuary

In this paper, based on the adsorptive kinetic experiments and interfacial chemistry experiments, the adsorption mechanism and the factors influencing the adsorption of humus by HS-12 resin have been studied. Humus in the water of the Changjiang estuary w…     

Dating the giant Zhuxi W–Cu deposit (Taqian–Fuchun Ore Belt) in South China using molybdenite Re–Os and muscovite Ar–Ar system

The recently discovered Zhuxi W–Cu ore deposit is located within the Taqian–Fuchun Ore Belt in the southeastern edge of the Yangtze Block, South China. Its inferred tungsten resources, based on new exploration data, are more than 280 Mt by 2016. At least three paragenetic stages of skarn formation and ore deposition have been recognized: prograde skarn stage; retrograde stage; and hydrothermal sulfide stage. Secondly, greisenization, marmorization and hornfels formation are also observed. Scheelite and chalcopyrite are the dominant metal minerals in the Zhuxi deposit and their formation was associated with the emplacement of granite stocks and porphyry dykes intruded into the surrounding Carboniferous carbonate sediments (Huanglong and Chuanshan formations) and the Neoproterozoic slate and phyllites. The scheelite was mostly precipitated during the retrograde stage, whereas the chalcopyrite was widely precipitated during the hydrothermal sulfide stage. A muscovite ⁴⁰Ar/³⁹Ar plateau age of about 150 Ma is interpreted as the time of tungsten mineralization and molybdenite Re–Os model ages ranging from 145.9 ± 2.0 Ma to 148.7 ± 2.2 Ma (for the subsequent hydrothermal sulfide stage of activity) as the time of the copper mineralization. Our new molybdenite Re–Os and muscovite ⁴⁰Ar/³⁹Ar dating results, along with previous zircon U–Pb age data, indicate that the hydrothermal activity from the retrograde stage to the last hydrothermal sulfide stage lasted up to 5 Myr, from 150.6 ± 1.5 to 145.9 ± 1 Ma, and is approximately coeval or slightly later than the emplacement of the associated granite porphyry and biotite granite. The new ages reported here confirm that the Zhuxi tungsten deposit represents one of the Mesozoic magmatic–hydrothermal mineralization events that took place in South China in a setting of lithospheric extension during the Late Jurassic (160–150 Ma). It is suggested that mantle material played a role in producing the Zhuxi W–Cu mineralization and associated magmatism.     

Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO₂+H₂O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove     

Crystallization temperature of anatectic melt: An example of biotite–muscovite granite in the Rikolatvi structure,Belomorian Mobile Belt

Zircon hosted in granite, which crystallized from local pools of anatectic melt among migmatites, in the Rikolatvi structure, Belomorian Mobile Belt, contains minute inclusions of various minerals, biotite and garnet among others. The compositions of the biotite and garnet in the microinclusions differ from those of the same minerals in the granite containing the zircon. The crystallization temperature of the anatectic melt was estimated by the biotite–garnet geothermometer and the composition of the biotite and garnet inclusions at ~800°C.     

Paragenesis of Cr-rich muscovite and chlorite in green-mica quartzites of Saigaon–Palasgaon area,Western Bastar Craton,India

Journal of Earth System Science - Green mica (fuchsite or chromian-muscovite) is reported worldwide in the Archaean metasedimentary rocks, especially quartzites. They are generally associated with...     

Neoarchean high-pressure margarite–phengitic muscovite–chlorite corona mantled corundum in quartz-free high-Mg,Al phlogopite–chlorite schists from the Bundelkhand craton,north central India

In quartz-free Fe, Na-poor and high-Mg, Al schists from the Bundelkhand craton in north central India, corundum porphyroblasts in finely interleaved phlogopite–chlorite aggregates with rare clinozoisite are mantled by fine-grained (<3 μm) intergrowths of outer collars (>200 μm wide) of phengitic-muscovite and chlorite (phlogopite + corundum + H₂O → phengitic-muscovite + chlorite), and <100 μm wide inner collars of margarite–muscovite (corundum + clinozoisite + phengitic muscovite → margarite + muscovite + H₂O). Wide-beam electron probe microanalyses indicate Mg in the bi-layered corona increases from corundum outwards, with a complementary decrease in Al and K. Si and Ca increase and then decrease to matrix values. The sharp chemical gradients across the highly structured bi-layered corona are inferred to suggest that the corona-forming reactions were promoted by local grain-boundary-controlled thermodynamic instability as opposed to element transport by advective diffusion. The P–T convergence of KMASH reactions and NCKMASH pseudosection phase relations computed using micro-domain compositions indicate the chlorite–phengitic muscovite outer collar formed at 18–20 kbar and ca. 630°C. The NCKMASH margarite–muscovite inner collar yielded lower metamorphic P–T conditions of 11 ± 3 kbar, ca. 630°C. U–Th–Pb chemical dating of metamorphic monazite and LA-ICPMS U–Pb isotope dating of re-equilibrated zircon yield ca. 2.78 Ga ages, which are interpreted to date corona formation and Neoarchean high-P metamorphism in the Bundelkhand craton, hitherto unknown in the Indian Precambrian. (220)     

Metastable phenomena on calcite {101̄4} surfaces growing from Sr2+–Ca2+–CO32− aqueous solutions

In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr²⁺–Ca²⁺–CO₃²⁻ aqueous solutions in contact with calcite {101̄4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation.     

Platiniferous gold–tourmaline aggregates in the gold–palladium belt of Minas Gerais,Brazil: implications for regional boron metasomatism

Mineralogy and Petrology - The platiniferous gold–palladium belt of Minas Gerais, Brazil, forms an approximately 240-km-long, roughly north–south-trending domain that includes numerous...     

Unravelling the fluid flow evolution and precipitation mechanisms recorded in calcite veins in relation to Pangea rifting–Newark Basin,USA

Calcite veins hosted in the Triassic Stockton, Lockatong and Passaic formations of the Newark Basin are investigated to reconstruct the fluid evolution. To constrain the parameters of calcite precipitation, a microthermometry study was carried, which reveals precipitation of calcite from a low to moderate saline H₂O-NaCl fluid (0.4 to 13.2 wt% NaCl equiv.) under low to moderate hydrothermal (137 °C to 232 °C) conditions. This fluid composition is interpreted to reflect mixing between a deep basement-derived heated diluted fluid and relatively low to moderate saline diagenetic formation waters hosted in the different Triassic formations. Carbon and strontium isotope analysis on the vein calcites suggests that these elements are derived from the pre-Triassic basement and the sedimentary cover through fluid-rock interactions. The aforementioned geochemical findings are supported by Rare Earth Elements and Yttrium (REY) systematics and oxygen isotope data.The Late Triassic extensional activity and gravity-driven fluid flow mechanism facilitated the infiltration of meteoric waters to deeper lithostratigraphic units (i.e., Precambrian-Paleozoic basement-Triassic Stockton Formation) where they became heated. In response to the extensional tectonics, the deep-seated hydrothermal basement-derived diluted fluids migrated upward along the tectonic-related fractures and the major faults to upper shallow crustal levels. Here, the heated, diluted meteoric waters were mixed with low, moderately saline, and relatively cooler formation waters, leading to calcite precipitation. The pH increase is suggested to be a contributing factor in the precipitation of calcite.     

Iron, calcite, and oxidative stress in coal dust-induced lung diseases

Backgrounds： Coal is and will remain a major energy resource worldwide with P.R. China and the U.S. the leading producers. It has long been known that coal mining causes health problems such as coal workers＇ pneumoconiosis （CWP） and chronic obstructive pulmonary disease （e.g., emphysema）. Yet, there are no accurate methods for predicting their occurrence. The goals of the present study are to determine whether bioavailable iron （BAI） is the active component in coal dust-induced lung diseases and to develop a model using BAI for the prediction of coal＇s pneumoconiotic potency. Methods： Thirty coal samples from Utah （UT）, West Virginia （WV） and Pennsylvania （PA） coalmine regions with a low, moderate, and high prevalence of CWP, respectively,     

Clay–clast aggregates in fault gouge: An unequivocal indicator of seismic faulting at shallow depths?

A common problem encountered in studies of gouge-bearing natural faults is the difficulty of ascertaining whether the observed gouge was sheared seismically or aseismically; this problem arises because of the scarcity of indicators of fault slip rates for gouge. Recently, clay–clast aggregates (CCAs; a CCA comprises a clastic core mantled by a rim of ultrafine particles) were proposed as a possible indicator of seismic slip in gouge, on the basis of shear experiments on gouge at seismic slip rates. To examine the processes and conditions of CCA formation, we conducted rotary shear experiments on quartz and quartz–bentonite gouges under normal stresses (0.3–3.0 MPa) and slip rates (0.0005–1.3 m s⁻¹), and in both room-humidity (room-dry) and water-saturated (wet) conditions. We found that CCAs could be produced in room-dry gouges even at the lowest slip rates, which are considerably slower than actual seismic slip rates. This finding demonstrates that thermal pressurization and fluidization at elevated temperature during seismic slip are not necessarily needed for the formation of CCAs, contrary to previous views. Given the occurrence of CCAs over a wide range of slip rates, we suggest that the presence of CCAs is not an unequivocal indicator of fault slip at seismic slip rates.     

Tremolite–calcite veins in the footwall of the Simplon Fault,Antigorio Valley,Lepontine Alps (Italy)

The lowermost units of the nappe pile of the Lepontine Alps crop out in the Antigorio valley in the footwall of the Simplon Fault. The whole orthogneiss section of the Antigorio Unit is exposed on both sides of the valley, sandwiched between the Mesozoic metasedimentary sequences of the Baceno unit below and the Tèggiolo unit above. The petrography and mineral composition of tremolite–calcite veins occurring in dolomite marble in both metasedimentary sequences were investigated. Tremolite–calcite (with lesser talc and minor phlogopite) veins have rhythmic banded texture. Banding is due to cyclic differences in modal abundances and fabric of tremolite and calcite. These veins are very similar to those occurring in dolomite rafts within the Bergell granite and it is inferred that they formed by the same “fracture-reaction-seal” mechanism. Veins formed by reaction of a silica-rich aqueous fluid with the host dolomite marble along fractures. According to thermo-barometric calculations, based on electron microprobe analyses, reaction occurred at temperatures between 450 and 490°C and minimum pressure of 2–3 kbar. Such temperature conditions occurred in this footwall region of the Simplon Fault Zone around 15 Ma, during exhumation and cooling of the nappe pile and a transition to brittle behaviour. Aqueous, silica-rich fluids concentrated along fractures, forming tremolite–calcite veins in the dolomite marbles and quartz veins in the orthogneiss.     

Molybdenite Re–Os and muscovite 40Ar/39Ar dating of quartz vein-type W–Sn polymetallic deposits in Northern Guangdong, South China

Northern Guangdong is an important part of Nanling tungsten–tin metallogenic belt, South China. The tungsten mineralization in this area consists of mainly quartz–wolframite vein-type mineralization, with W–Sn polymetallic deposits mostly distributed at the outer contact zone between concealed Late Jurassic granitic stocks and Cambrian–Ordovician low-metamorphosed sandstones and shales. Molybdenite Re–Os and muscovite ⁴⁰Ar/³⁹Ar isotopic dating of three typical tungsten vein-type deposits (Yaoling, Meiziwo, and Jubankeng) in northern Guangdong, show that two episodes of Late Jurassic W–Sn polymetallic mineralization occurred in this area: an early episode during the Late Jurassic (158–159?Ma) represented by the Yaoling, Hongling, and Meiziwo tungsten deposits, and a younger event during the Early Cretaceous (138?Ma) represented by the Jubankeng deposit. Analysis of available radiometric ages of several W–Sn deposits in the Nanling region indicate that these deposits formed at several intervals during the Mesozoic at 90–100, 134–140, 144–162, and 210–235?Ma, and that large-scale W–Sn mineralization in this region occurred mainly between 150 and 160?Ma.