Dolomite dissolution: An alternative diagenetic pathway for the formation of palygorskite clay

Palygorskite is a fibrous, magnesium‐bearing clay mineral commonly associated with Late Mesozoic and Early Cenozoic dolomites. The presence of palygorskite is thought to be indicative of warm, alkaline fluids rich in Si, Al and Mg. Palygorskite has been interpreted to form in peritidal diagenetic environments, either as a replacement of detrital smectite clay during a dissolution–precipitation reaction or solid‐state transformation, or as a direct precipitate from solution. Despite a lack of evidence, most diagenetic studies involving these two minerals posit that dolomite and palygorskite form concurrently. Here, petrological evidence is presented from the Umm er Radhuma Formation (Palaeocene–Eocene) in the subsurface of central Qatar for an alternative pathway for palygorskite formation. The Umm er Radhuma is comprised of dolomitized subtidal to peritidal carbonate cycles that are commonly capped by centimetre‐scale beds rich in palygorskite. Thin section, scanning electron microscopy and elemental analyses demonstrate that palygorskite fibres formed on both the outermost surfaces of dissolved euhedral dolomite crystals and within partially to completely dissolved dolomite crystal cores. These observations suggest that dolomite and palygorskite formed sequentially, and support a model by which the release of Mg²⁺ ions and the buffering of solution pH during dolomite dissolution promote the formation of palygorskite. This new diagenetic model explains the co‐occurrence of palygorskite and dolomite in the rock record, and provides valuable insight into the specific diagenetic conditions under which these minerals may form.     

近地表温压条件下白云岩溶解过程的实验研究

与溶解作用有关的次生孔隙是碳酸盐岩最主要的油气储集空间,从实验模拟角度研究碳酸盐溶解机制具有重要的理论与应用价值。本文在近地表的温度和压力条件下,进行了具相同成分和结构的白云岩在CO2和乙酸介质中的对照溶解实验,两种类型的具相同成分和不同结构的白云岩在CO2介质中添加和不添加硬石膏的对照溶解实验,以及方解石含量50%的岩石在CO2介质中添加和不添加硬石膏的对照溶解实验。实验结果表明:(1)近地表温压条件的酸性环境中,乙酸对碳酸盐矿物的溶解能力显著大于CO2流体,乙酸对白云石的溶解是接近化学计量的,而CO2流体则是非化学计量的,白云石中Ca优先溶出而Mg滞留;(2)溶解CaSO4的加入会显著改善近地表温压条件下CO2流体对白云石的溶解效果,使得白云石溶解接近化学计量组成,该过程是通过抑制Ca的溶出和加速Mg的溶出来实现的;(3)对于白云石含量大于90%的较纯的白云岩来说,溶解CaSO4的加入会使得白云岩溶出离子的Ca、Mg合量增加,因而总体上有利于白云岩溶解,与之相反,溶液中CaSO4的沉淀可能导致白云石的沉淀。实验结果可以帮助我们更深刻理解近地表环境白云岩的溶解过程,尤其是与膏盐伴生的白云岩的溶解及相应岩溶过程和次生孔隙的形成机制。      

Transient and quasi-steady-state dissolution of biotite at 22-25°C in high pH, sodium, nitrate, and aluminate solutions

Biotite dissolution under conditions of high pH and high aluminum, sodium, and nitrate concentrations analogous to those found in tank wastes at the Hanford Site was investigated using continuously stirred flow-through reactors at 22 to 25 °C. Experiments were designed to simulate tank leaks into the Hanford vadose zone where Fe(II) from biotite is the dominant reducing agent available to immobilize certain contaminants. Both non-steady-state and steady-state dissolution kinetics were quantified; interest in non-steady-state kinetics derives from the inherently transitory nature of tank leaks. Biotite was conditioned in pH 8 solutions to simulate the alkaline environment of the Hanford sediment, and then reacted in pH 10-14 solutions, some including 0.055 M Al(NO₃)₃ and/or 2 M or 6 M NaNO₃. Initial dissolution transients (intervals of rapid release rates that decay to slower steady-state rates) showed fast preferential release of K followed by near-stoichiometric release of Si, Al, and Mg, and slower release of Fe. Each increase in pH resulted in a second transient with the greatest amounts of Si, Al, and K released at pH 14, followed by pHs 13, 12, 11, and 10. Fe release also was highest at pH 14, but unchanging at pHs 10-13 within experimental error. Transient releases at high pH are attributed to dissolution of amphoteric secondary phases such as ferrihydrite that are inferred from saturation calculations and solid analyses to form during the conditioning interval. Transient release of Si was inhibited by the presence of 0.055 M Al(NO₃)₃; the effects of Al(NO₃)₃ and NaNO₃ on the release rates of Al, Fe, Mg, and K were variable and generally outweighed by the effect of pH. Quasi-steady-state release rates were slowest at pH 11-12 (10^−12.2 mol biotite m⁻² s⁻¹ for Si) and increased in either direction in pH away from this minimum (to 10^−11.5 at pHs 8 and 14 for Si). Fe release rates at high pH were sufficient to account for observed Cr(VI) reduction at Hanford. The net release rates of the major framework cations, from which the biotite dissolution rate is inferred, may reflect the precipitation of secondary phases or the alteration of biotite to vermiculite. The most extensive solid-phase alterations were observed in Na-enriched solutions.     

Dolomite effect on borosilicate glass alteration

Dolomite (CaMg(CO₃)₂) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.     

Reaction of montmorillonite with acid aqueous solutions: solute activity control by a secondary phase

Al, Ca, Mg and Na montmorillonites were reacted with acid aqueous solutions in order to test the assumption of equilibrium underlying solubility determinations of thermodynamic properties of montmorillonite. The value calculated for the equilibrium constant varied with pH over the pH range 1.5–4.2. Hence montmorillonite was not in a unique state of equilibrium with all solutions over this range. Therefore the derivation of thermodynamic properties of montmorillonite by the application of a single step dissolution equation to results of solubility studies in mildly acidic solutions is invalid. Indications of solute activity control by a secondary solid phase were given by: (1) the dependence of the solution concentrations of some, but not all, montmorillonite constituent elements upon each other; and (2) a lack of congruency in the dissolution of montmorillonite. These indications were confirmed by a principal components statistical analysis, which showed that the solution activities of Si, Al and H after long-term treatments of the mineral from undersaturation were always related by the same expression. This particular expression is equivalent to an equilibrium constant for the reversible dissolution of a secondary solid phase that is enriched in silicon by comparison with montmorillonite. An aluminous solid phase was also shown to be formed.     

A Report on a Biotite-Calcic Hornblende Geothermometer

This paper presents a biotite-calcic hornblende geothermometer which was empirically calibrated based on the gamet-biotite geothermometer and the gamet-plagioclase-hornblende-quartz geobarometer, in the ranges of 560-800℃ (T) and 0.26-1.4 GPa (P) using the data of metadolerite, amphibolite, metagabbro, and metapelite collected from the literature. Biotite was treated as symmetric Fe-Mg-AlVI-Ti quaternary solid solution, and calcic hornblende was simplified as symmetric Fe-Mg binary solid solution. The resulting thermometer may rebuild the input garnet-biotite temperatures well within an uncertainty of ±50℃. Errors of ±0.2 GPa for input pressure, along with analytical errors of ?% for the relevant mineral compositions, may lead to a random error of ±16℃ for this thermometer, so that the thermometer is almost independent of pressure estimates. The thermometer may clearly discriminate different rocks of lower amphibolite, upper amphibolite and granulite facies on a high confidence level. It is assume     

我国热带亚热带部分地区花岗岩和片麻岩中黑云母风化研究

综合应用Ｘ射线衍射、扫描电镜、透射电镜及偏光显微镜等技术手段研究了我国热带、亚热带部分地区花岗岩和片麻岩中黑云母的风化现象。结果表明，化学风化产物主要有黑云母／蛭石不规则间层矿物、水黑云母、蛭石、０．７ｎｍ埃洛石及铁的氢氧化物（氧化物）等。影响黑云母风化及次生产物形成的主要因素包括黑云母的晶体结构和化学成分、气候、风化壳母岩的矿物成分等。     

Irreversible water–rock mass transfer accompanying the generation of the neutral,Mg–HCO3 and high-pH,Ca–OH spring waters of the Genova province,Italy

In a recent survey of the spring waters of the Genova province, many neutral Mg–HCO₃ waters and some high-pH, Ca–OH waters were found in association with serpentinites. All the springs are of meteoric origin as indicated by the stable isotopes of water and dissolved N₂ and Ar. Interaction of these meteoric waters with serpentinites determines a progressive evolution in the chemistry of the aqueous phase from an immature Mg-rich, SO₄–Cl facies of low salinity to an intermediate Mg–HCO₃ facies (pH 7.0–8.5, P_CO210^−3.5–10^−2.5 bar, Eh 150–250 mV), and to a mature Ca–OH facies (pH 10–12, P_CO2 10^−9.4−10^−10.6 bar, Eh-390 to-516 mV). The irreversible water–rock mass transfer leading to these chemical changes in the aqueous phase was simulated through reaction path modeling, assuming bulk dissolution of a local serpentinite, and the precipitation of gibbsite, goethite, calcite, hydromagnesite, kaolinite, a montmorillonite solid mixture, a saponite solid mixture, sepiolite, and serpentine. The simulation was carried out in two steps, under open-system and closed-system conditions with respect to CO₂, respectively. The calculated concentrations agree with analytical data, indicating that the computed water-rock mass transfer is a realistic simulation of the natural process. Moreover, the simulation elucidates the role of calcite precipitation during closed-system serpentinite dissolution in depleting the aqueous solution of C species, allowing the concurrent increment in Ca and the acquisition of a Ca–OH composition. Calcium–OH waters, due to their high pH, tend to absorb CO₂, precipitating calcite. Therefore, these waters might be used to sequester anthropogenic CO₂, locally preventing environmental impact to the atmosphere.     

Effects of citrate on the dissolution and transformation of biotite,analyzed by chemical and atomic force microscopy

The aim of this study was to investigate the dissolution and transformation characteristics of phyllosilicate under low molecular weight organic acids in the farmland environment (pH 4.0–8.0). Changes of dissolution and morphology of biotite were evaluated using chemical extraction experiments and in situ/ex situ atomic force microscopy (AFM) with fluids of citric acid (CA) solution at pH 4.0, 6.0, and 8.0. Results of extracting experiments show that CA solutions contributed to the release rate of potassium (K), silicon (Si), and aluminum (Al) from biotite relative to a control aqueous solution. In situ AFM observations indicate that the dissolution of biotite from the biotite (0 0 1) surface occurred on the terrace, segment, and fringe of pits, while new etch pits did not readily form on biotite (0 0 1) surfaces in aqueous solutions. However, dissolution rates of terraces can be greatly accelerated with the help of citrate. In pH 4.0 CA solution, 70 min dissolution reactions of biotite (0 0 1) surfaces result in more etch pits than in pH 6.0 and 8.0 solutions. In addition, the transformation of biotite occurred simultaneously with the dissolution process. Secondary coating was observed on the biotite (0 0 1) surface after 140 h of immersion in a weak acid environment. Thus, the protons have a dominant role in the dissolution process of biotite with organic (carboxyl) acting as a catalyst under acidic condition. Based on the theory of interactions on a water–mineral interface in a weak acid environment, dissolution of biotite starts from defect/kink sites on the surface, one layer by one layer, and develops along the [h k 0] direction. A secondary coating that forms on the biotite (0 0 1) surface may restrain the formation and growth of etch pits, whereas this process may have a positive role on the stability of soil structure during long-term soil management.     

Corundum-bearing metasomatic rocks in the Central Pamirs

The Muzkol metamorphic complex in the Central Pamirs contains widespread occurrences of corundum mineralization, sometimes with gem-quality corundum. These occurrences are spatially related to zones of metasomatic alterations in calcite and dolomite marbles and crystalline schists. The calcite marbles contain corundum together with muscovite, scapolite, and biotite; the dolomite marbles contain corundum in association with biotite; and the schists bear this mineral coexisting with biotite and chlorite. All these rocks additionally contain tourmaline, apatite, rutile, and pyrite. The biotite is typically highly aluminous (up to 1.9 f.u. Al), and the scapolite is rich in the marialite end member (60–75 mol %). The crystallization parameters of corundum were estimated using mineral assemblages at T = 600–650°C, P = 4–6 kbar, X _{CO 2} = 0.2–0.5 at elevated alkalinity of the fluid. The Sr concentration in the calcite and dolomite marbles is low (345–460 and 62–110 ppm, respectively), as is typical of recrystallized sedimentary carbonates. The variations in the ⁸⁷Sr/⁸⁶Sr ratio in the calcite and dolomite marbles (0.70852–0.70999 and 0.70902–0.71021, respectively) were controlled by the introduction of radiogenic ⁸⁷Sr during the metasomatic transformations of the rocks. The isotopic-geochemical characteristics obtained for the rocks and the results of numerical simulations of the fluid-rock interactions indicate that the corundum-bearing metasomatic rocks developed after originally sedimentary Phanerozoic carbonate rocks, with the desilication of the terrigenous material contained in them. This process was a manifestation of regional alkaline metasomatism during the closing stages of Alpine metamorphism. In the course of transformations in the carbonate reservoir, the juvenile fluid flow became undersaturated with respect to silica, which was a necessary prerequisite for the formation of corundum.     

Optimization of the garnet-biotite geothermometer: Part II. Calibration equations and accuracy of the estimation

Calibrations of the garnet-biotite geothermometer are considered with allowance for the effect of the nonideality of the coexisting garnet and biotite upon K _D . The calibrations based on the model of an asymmetric subregular Prp-Alm-Grs-Sps solid solution with W _i−j ^Grt (after Ganguly et al. (1996) and Holdaway (2000) and taking into account the experimental data published by Perchuk et al. (1983)) are the most accurate. The same may be said about the equations additionally taking into consideration the model of the symmetric regular Phl-Ann-Ms-(Ti-Bt) solution with W _i−j ^Bt after Holdaway et al., (1997), Kaneko and Miano (2004), and the data published by Ferry and Spear (1978) and Perchuk et al. (1983). These equations well reproduce the temperature at which the Prp + Ann = Alm + Phl equilibrium is reached in experiments, and they are the least sensitive to the variation of the Ca and Mn contents in garnet and Al^VI and Ti in biotite. The uncertainty of the temperature interval is 30–46°C (2σ).     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.     

Mineralogy of New Caledonian metamorphic rocks

Variations in chemistry and related physical properties of sheet silicates in the Ouégoa district with metamorphic grade are investigated. Weakly metamorphosed rocks prior to the crystallization of lawsonite contain phengite (d ₀₀₆=3.317–3.323 Å), chlorite and occasionally paragonite while interstratified basaltic sills contain chlorite, minor phengite and stilpnomelane. Pyrophyllite crystallizes before lawsonite in some metamorphosed acid tuffs and is also stable in the lawsonite zone. Paragonite, phengite and chlorite appear to be stable through the sequence from weakly metamorphosed rocks into high-grade “eclogitic” schists and gneisses. Optical, chemical and some X-ray diffraction data is given for representative sheet silicates. Electron probe analyses of 55 phengites, 21 paragonites, 57 chlorites, 12 vermiculites, 2 stilpnomelanes, and 2 chloritoids are presented in graphical form. All K-micas analysed are consistently phengitic (3.29–3.55 Si^iv ions per formula unit) and show limited solid solution with paragonite (4 to 13% Pa). The K∶Na ratio of the phengite is strongly dependant on the assemblage in which it occurs; the amount of phengite component and its Fe∶Mg ratio depends on bulk-rock composition. Phengites from acid volcanics have the highest Fe∶Mg ratio, highest phengite component and β refractive indices. Phengites from basic volcanics and metasediments of the epidote zone have the lowest Fe∶Mg ratio. Phengites from lawsonite-zone metasediments have intermediate Fe∶Mg ratios. The phengites show a small decrease in phengite component with increasing metamorphic grade. d ₀₀₆ for phengites varied from 3.302 to 3.323 Å but at least in the lawsonite and epidote zones appears to reflect composition and had little systematic variation with metamorphic grade; phengites from very low-grade rocks showed the longest values of d ₀₀₆. Paragonite shows almost no phengite-type substitution and only limited solid solution (4–12%) with muscovite. All paragonites (6) and most phengites (20) which have been examined are 2M₁ polymorphs; one Fe²⁺-phengite appears to be a 1M polymorph. The chemistry of chlorites closely reflects parent-rock chemistry. Chlorites from metasediments have distinctly higher Fe/(Fe+Mg) ratios than chlorites from basic igneous rocks; chlorites from the lawsonite and lawsonite-epidote transitional zone metasediments have the highest Fe/(Fe+Mg) ratios. In metabasalts Fe/(Fe+Mg) ratios appear to reflect individual variations in bulk-rock chemistry and show no direct correlation with metamorphic grade. There is little difference in Al/(Si+Al) ratio between chlorites from sediments and basic igneous rocks although in both lithologies the chlorites from the epidote zone appear to be slightly more aluminous. Fe-rich chlorites of the lawsonite zone metasediments have been altered by a process involving leaching of Fe and Mg and introduction of alkalies to a brown pleochroic Fe-vermiculite. Chemical and physical data for this vermiculite are given. The decrease in Fe/(Fe+Mg) ratio in chlorites and phengites on passing from the lawsonite to the epidote zone can be correlated with the crystallization of Fe-rich epidote and almandine in the epidote zone. Elemental partitioning between coexisting minerals has shown Ti to be partitioned into phengite, while Fe and Mn are strongly partitioned into chlorite. When either stilpnomelane or chloritoid coexists with phengite or chlorite, Fe and Mn are slightly enriched in the stilpnomelane or chloritoid relative to the chlorite.     

Iron isotope fractionation during proton- and ligand-promoted dissolution of primary phyllosilicates

We studied stable iron isotope fractionation during dissolution of a biotite and chlorite enriched mineral fraction from granite by HCl and 5 mM oxalic acid in a pH range of 4-5.9. Batch experiments covered a time period from 2 h to 100 days and were performed at initial potassium concentrations of 0, 0.5, and 5 mM to induce different levels of biotite exfoliation. All experiments were kept anoxic to investigate solely the dissolution step without the influence of oxidation and precipitation of secondary Fe oxyhydroxides. Oxalic acid increased the release of Fe by a factor of ∼15 compared with the HCl experiments. Addition of 0.5 mM K to initial solutions in proton-promoted dissolution decreased the release of Fe by 30-65% depending on the dissolution stage. In ligand-controlled dissolution, K reduced the Fe release only to a minor extent. All solutions of the early dissolution stages were enriched in light Fe isotopes by up to −1.4‰ in δ⁵⁶Fe compared with the isotopic composition of biotite and chlorite mineral separates, which we explained by a kinetic isotope effect. In proton-promoted dissolution, early released fractions of K-enriched experiments were significantly lighter (−0.7‰ to −0.9‰) than in the initially K-free experiments. The evolution of Fe isotope ratios in solution was modeled by a linear combination of kinetic isotope effects during two independent dissolution processes attacking different crystallographic sites. In ligand-controlled dissolution, K did not influence the kinetic isotope effect and the Fe isotope composition in solution in the late dissolution stages remained slightly lighter than the bulk composition of the biotite/chlorite enriched mineral fraction. This study demonstrates that the initial Fe weathering flux should be enriched in light Fe isotopes and that Fe isotope data in combination with dissolution kinetics and stoichiometry provide new insights into dissolution mechanisms.     

Assessment of natural and anthropogenic influences on regional groundwater chemistry in a highly industrialized and urbanized region: a case study of the Vaal River Basin,South Africa

The Vaal River Basin is an economically significant area situated in the interior of South Africa (SA), where mining, industrial, domestic and agricultural activities are very intense. The purpose of the study was to assess the influence of geology and anthropogenic activities on groundwater chemistry, and identify the predominant hydrochemical processes in the basin. Data from seventy groundwater sites were retrieved from the national database, and attention was paid to fifteen water quality parameters. Groundwater samples were clustered into seven hydrochemically distinct groups using Hierarchical Cluster Analysis (HCA), and three samples treated independently. A Piper plot revealed two major water types, Ca–Mg–HCO₃ and Ca–Mg–SO₄-Cl, which were linked to dissolution of the underlying geology and mine pollution. The Ca?+?Mg vs HCO₃?+?SO₄ plot indicated that reverse ion exchange is an active process than cation exchange in the area. Principal component analysis (PCA) was used to identify the main natural and anthropogenic processes causing variation in groundwater chemistry. Four principal components were extracted using PCA that explains 82% of the total variance in the chemical parameters. The PCA results can be categorized by four components: (1) evaporites and silicates weathering enrichment of Na, K, Cl, SO₄ and F, and anthropogenic Cl; (2) dissolution of dolomite, limestone and gypsum; (3) agricultural fertilizers (4) wastewater treatment. This study reveals that both natural and anthropogenic activities are the cause of groundwater variation in the basin.     

Precipitation of aluminum and magnesium secondary minerals from uranium mill raffinate (pH 1.0–10.5) and their controls on aqueous contaminants

Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)₃, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)₃. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)₃ and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations.     

Mineral Surface after Reaction with Aqueous Solution at High Temperatures and Pressures

This work presents new experimental results on surface chemistry of reacting minerals and interface kinetics between mineral and aqueous solutions. These experiments were carried out using a flow reactor (packed bed reactor) of an open system as well as a continuous stirred tank reactor, CSTR. The authors measured reaction rates of such minerals as zeolite, albite and carbonate (rhodochrosite, dolomite) in various solutions, and tested corresponding mineral surface by using SEM, XPS, SIMS, etc. This paper mainly presents the experimental results of zeolite dissolution in water and in low pH solutions at room temperature, and dolomite dissolution at elevated temperatures. The results show that the release rates of Si, Al and Na of zeolite are different in most cases. The incongruent dissolution of zeolite is related to surface chemical modifications. The Na, Al and Si release rates for dissolution of albite and zeolite in water and various solutions were measured as a function of temperature, flow veloci     

Scales of equilibrium and disequilibrium during cleavage formation in chlorite and biotite-grade phyllites, SE Vermont

Detailed electron microprobe analyses of phyllosilicates in crenulated phyllites from south‐eastern Vermont show that grain‐scale zoning is common, and sympathetic zoning in adjacent minerals is nearly universal. We interpret this to reflect a pressure‐solution mechanism for cleavage development, where precipitation from a very small fluid reservoir fractionated that fluid. Multiple analyses along single muscovite, biotite and chlorite grains (30–200 μm in length) show zoning patterns indicating Tschermakitic substitutions in muscovite and both Tschermakitic and di/trioctahedral substitutions in biotite and chlorite. Using cross‐cutting relationships and mineral chemistry it is shown that these patterns persist in cleavages produced at metamorphic conditions of chlorite‐grade, chlorite‐grade overprinted by biotite‐grade and biotite‐grade. Zoning patterns are comparable in all three settings, requiring a similar cleavage‐forming mechanism independent of metamorphic grade. Moreover, the use of ⁴⁰Ar/³⁹Ar geochronology demonstrates this is true regardless of age. Furthermore, samples with chlorite‐grade cleavages overprinted by biotite porphyroblasts suggest the closure temperatures for the diffusion of Al, Si, Mg and Fe ions are greater than the temperature of the biotite isograd (>～400 °C). Parallel and smoothly fanning tie lines produced by coexisting muscovite–chlorite, and muscovite–biotite pairs on compositional diagrams demonstrate effectively instantaneous chemical equilibrium and probably indicate simultaneous crystallization. These results do not support theories suggesting cleavages form in fluid‐dominated systems. If crenulation cleavages formed in systems in which the chemical potentials of all major components are fixed by an external reservoir, then the compositions of individual grains defining these cleavages would be uniform. On the contrary, the fine‐scale chemical zoning observed probably reflects a grain‐scale process consistent with a pressure‐solution mechanism in which the aqueous activities of major components are defined by local dissolution and precipitation. Thus the role of fluids was probably limited to one of catalysing pressure‐solution and fluids apparently did not drive cleavage development.     

The effect of oxalate on the dissolution rates of oligoclase and tremolite

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22°C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si.Large transient “spikes” of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; we suggest adsorption on feldspar surfaces away from sites of active dissolution as a possibility. Solutions in the reactors are undersaturated with respect to both gibbsite and kaolinite, so neither the spikes nor the incongruent dissolution can be explained by formation of a secondary precipitate.The rate of dissolution of tremolite is independent of pH over the pH range 2–5, and decreases at higher pH. The rate of dissolution of oligoclase in our experiments was independent of pH over the pH range 4–9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.     

Dissolution Characteristic Study on Dustfall in Citric

In this paper, the dissolution characteristics of Xining dustfall in citric acid solution was studied to evaluate the physical chemical change in acid conditions. pH along with conductivity was tested with time. FTIR, SEM and ICP analysis were applied to analyze the residuum and filtrate after 2 days’ dissolution experiment. It was shown in the pH/conductivity variation, solution’s pH rise sharply in the front 4 hours, then decrease slowly. After 4 hours, both the pH and conductivity become stable. Based on combined analysis of XRD and FTIR spectrum of dustfall before and after dissolution, that calcite and dolomite in dustfall are dissolved completely in the 0.05M citric acid solution in two days. Besides, amount of metal cations were extracted from the dustfall during the dissolution, including Ca2+,K+,Mg2+,Fe3+,Al3+,Si. In general, after the dissolution of dustall in citric acid, some minerals are dissolved and amount of metal elements are extracted. Carbonate minerals almost dissolved completely, also the structure of silicate minerals changed as the extraction of elements.