Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Jadeite, albite and nepheline as inclusions in spinel of chromitite from Hess Deep, equatorial Pacific: their genesis and implications for serpentinite diapir formation

Polymineralic inclusions which consist of a few grains of diopside, enstatite, jadeite, nepheline, albite, pargasite, phlogopites and olivine were found in chromian spinel in a chromitite pod and in troctolite from Hess Deep, equatorial Pacific. The inclusion mineral suite in chromitite is characterized by Na-Al silicates, such as jadeite, nepheline and albite. Jadeite and nepheline commonly coexist with enstatite, and tend to occur as interstitial grains between subhedral enstatite (or other minerals) and host spinel. Albite, diopside and enstatite occur as equant inclusions. The mafic minerals in the inclusions have similar chemistry to those found in the troctolite and dunite. The modes of occurrence and mineral chemistry of the inclusions are controlled by magmatic precipitation, and subsequent reequilibration due to decrease of temperature in the uppermost mantle. The mafic minerals in spinel inclusions were crystallized from a melt enriched in Cr and some incompatible components formed by melt-mantle interaction process mixed to various extent with subsequently supplied more primary melt. Albite and nepheline could also be formed at the magmatic stage. Jadeite was formed by a subsolidus reaction of albite and nepheline at low temperatures (250–300 °C) at slightly less than 3 kbar. This requires a remarkable temperature decrease, at least locally, of the uppermost mantle and crust. The Hess Deep rocks were formed in the uppermost mantle beneath a spreading-ridge axis at more than 1000 °C, and were transposed outwards from the axis by corner flow. At the off-ridge conditions, the rocks were cooled and serpentinized by circulation of sea water at the mantle depth to form jadeite in chromitite. The serpentinized portion could have risen as a kind of serpentinite diapir through the thin crust up to the ocean floor. Received: 24 January 1997 / Accepted: 6 November 1997     

Experimental studies of the distribution of rare earths as trace elements among silicate minerals and liquids and water

The distribution of the REE between synthetic diopside, forsterite, enstatite, and gaseous water and between natural plagioclase, 2 rhyolite obsidian melts and gaseous water have been measured. Values for distribution coefficients (D) for the REE between the minerals and aqueous fluid vary significantly over the temperature range of 550°C to 850°C, but little variation was found for the values of D between the silicate liquids and aqueous fluid over a temperature range of 100°C. By assuming that the values of D for the silicate liquids are independent of major element composition and temperature, it is possible to calculate values of D for REE between silicate minerals and silicate liquid. The values obtained for diopside, forsterite, enstatite and plagioclase compare favorably with those obtained for the natural materials clinopyroxene, olivine, orthopyroxene and plagioclase (except for Eu). The values of D for diopside were found to increase and those for forsterite and enstatite to decrease with increasing temperatuie. Values of temperature of equilibration for natural minerals obtained by extrapolation of graphs for experimental data of In D against 1/T for the systems diopside-silicate liquid, forsterite-silicate liquid, and forsterite-diopside fall within a reasonable range, suggesting the possibility of geothermometry using REE concentrations of minerals.     

Experimental study of incongruent evaporation kinetics of enstatite in vacuum and in hydrogen gas

Variations in bulk Mg/Si ratios in the various groups of chondritic meteorites indicate that Mg/Si fractionation occurred in the primitive solar nebula. Enstatite (MgSiO₃) evaporates incongruently forming forsterite (Mg₂SiO₄) as an evaporation residue; therefore, evaporation of enstatite produces Mg/Si variations in solid (Mg-rich) and gas (Si-rich) and must be considered as a probable process responsible for Mg/Si fractionation recorded in chondrites. To understand the evaporation kinetics of enstatite, incongruent evaporation experiments on enstatite single crystals have been carried out in vacuum and in hydrogen gas at temperatures of 1300 to 1500°C. A polycrystalline forsterite layer is formed on the surface of enstatite by preferential evaporation of the SiO₂ component, both in vacuum and in hydrogen gas. The thickness of the forsterite layer in vacuum increases with time in the early stage of evaporation and later the thickness of the forsterite layer remains constant (several microns). This is due to the change in the rate limiting process from surface reaction plus nucleation and growth to diffusion in the surface forsterite layer. The activation energy of the diffusion-controlled evaporation rate constant of enstatite is 457 (±58) kJ/mol. A thinner forsterite layer is formed on the surface of enstatite in hydrogen gas than in vacuum. Evaporation of enstatite in hydrogen gas is also considered to be controlled by diffusion of ions through the forsterite layer. The thin forsterite layer formed in hydrogen gas is ascribed to the enhanced evaporation rate of forsterite in the presence of hydrogen gas.The results are applied to incongruent evaporation under the solar nebular conditions. The steady thickness of the forsterite of nebular pressure-temperature conditions is estimated to be submicron because of the enhanced evaporation rate of forsterite under hydrogen-rich nebular conditions if evaporated gases are taken away immediately and no back reaction occurs (an open system). Because enstatite grains in the solar nebula would be comparable to the estimated steady thickness of forsterite, evaporation of such enstatite grains under kinetic conditions could play an important role in producing variations in Mg/Si ratios between solid and gas in the solar nebula.     

Stability of the assemblage albite plus forsterite at high temperatures and pressures with petrologic implications

The maximum limits of the assemblage albiteforsterite have been determined experimentally at high pressures and temperatures. At subsolidus temperatures, albite plus forsterite is replaced at high pressures by jadeitic clinopyroxene and enstatitic orthopyroxene. The boundary for this reaction lies within experimental uncertainity of that for jadeite=albite+nepheline. Melting of albite+forsterite at high pressures produces enstatite+liquid, which is different from the low-pressure eutectic behavior. Melting rates are very slow and several hundred hours are required to establish equilibrium near the solidus. The subsolidus boundary for albite plus forsterite lies near that for sanidine plus forsterite, but with a shallower slope which more closely matches that of anorthite plus forsterite. Both albite plus forsterite and anorthite plus forsterite are replaced at high pressures by an assemblage containing clinopyroxene plus orthopyroxene, unlike sanidine plus forsterite, which is replaced by a feldspathoid plus orthopyroxene. The presence of sodium enlarges the depth region over which plagioclase lherzolite can stably exist; it may also stabilize alkali feldspar plus olivine in crustal rocks.     

Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

Far from equilibrium enstatite dissolution rates both open to atmospheric CO₂ and CO₂ purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO₂ conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO₂ was purged by performing the experiments in a N₂ atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO₃²⁻ above pH 10.33. It is argued that CO₃²⁻ forms a >Mg₂-CO₃ complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO₂-purged enstatite dissolution in moles per cm² per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.     

Symplectites in upper mantle peridotites: Development and implications for the growth of subsolidus garnet,pyroxene and spinel

Silicate-oxide symplectites in complex mineral intergrowths are relatively common in upper mantle xenoliths and in xenoliths in the Jagersfontein Kimberlite, South Africa.Harzburgites of olivine and high-Al (1.9–3.6 wt%), Ca (0.6–0.9 wt%) and Cr (0.3–0.9 wt%) enstatite contain symplectites of spinel and diopside, or spinel, diopside and lower-Al (0.8–2.2 wt%), Ca (0.1–0.4 wt%) and Cr (0.02–0.8 wt%) enstatite. From textures and mineral chemistries these symplectites are interpreted to have formed by mineral unmixing and migration from Al–Ca–Cr discrete enstatite to adjoining mineral interfaces.Garnet harzburgites are composed of large (0.5–1 cm) olivine, equally large discrete low-Al (0.6–1.1 wt%), Ca (0.1–0.5 wt%), and Cr (0.1–0.3 wt%) enstatite and smaller interstitial garnet, diopside, and high-Cr and low-Al spinel. Symplectites are composed of either spinel+diopside+garnet, or garnet+spinel. Spinel diopside garnet symplectites have cores of spinel+diopside, resembling symplectites inharzburgites, but surrounded by rims of garnet or garnet+undigested globular spinel. From textures and chemistries we suggest that the spinel+diopside cores formed from Ca-Al-Cr-rich orthopyroxene initially as a nonstoichiometric homogeneous single phase clinopyroxene enriched in Fe, Cr and Al. This was followed by decomposition of the clinopyroxene to diopside+spinel, and subsequent garnet formation in a prograde reaction with olivine or enstatite. In bothharzburgites andgarnet harzburgites the metastable cellular structures may also have formed by the simultaneous precipitation of pyroxene and spinel. In all cases there is a strongly preferred embayment of symplectite bodies into olivine. Olivine appears to have activated adjacent     

Raman identification of calcite grains in the Chelyabinsk meteorite

Samples of the Chelyabinsk meteorite fallen in February 15, 2013, near Chelyabinsk, Russia, are analyzed by Raman spectroscopy. Olivines (forsterite), orthopyoxenes (enstatite), plagioclases (albite), iron oxides and sulfides, as well as calcite and, possibly, parisite were identified among mineral phases. Results were verified using scanning electron microscope with an energy-dispersive system (SEM-EDX). Data were compared with available materials on calcites from ordinary meteorites.     

Long-term interaction of wollastonite with acid mine water and effects on arsenic and metal removal

This paper reports the results of a laboratory experiment conducted to investigate the effects of wollastonite dissolution on removal of potentially toxic trace elements from stream waters affected by acid mine drainage (AMD). Nearly pure wollastonite was treated with natural acid mine water (pH 2.1) for different lengths of time (15, 30, 50 and 80 days). The compositional and textural characterization of the solid reaction products suggests that wollastonite was incongruently dissolved leaving a residual amorphous silica-rich phase that preserved the prismatic morphology of the parent wollastonite. The release of Ca into solution resulted in a pH increase from 2.1 to 3.5, and subsequent precipitation of gypsum as well as poorly crystallized Fe–Al oxy-hydroxides and oxy-hydroxysulfates whose components derived from the AMD solution. A geochemical modeling approach of the wollastonite–AMD interaction using the PHREEQC code indicated supersaturation with respect to schwertmannite (saturation index = 10.7–15.7), jarosite (SI = 8.7–10.2), alunite (SI = 5.1), goethite (SI = 4.7) and jurbanite (SI = 2.2). These secondary phases developed a thin coating on the reacted wollastonite surface, readily cracked and flaked off upon drying, that acted as a sink for trace elements, especially As, Cu and Zn, as indicated by their enrichment relative to the starting wollastonite. At such low pH values, adsorption of As oxyanions on the positively charged solid particles and coprecipitation of metals (mainly Cu and Zn) with the newly formed Fe oxy-hydroxides and oxy-hydroxysulfates seem to be the dominant processes controlling the removal of trace elements.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO₃ solution, suspension density = 0.4 g/L [U(VI)]_i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (p_CO2 = 10^−3.45 atm).     

Calorimetry of silicate melts at 1773 K: measurement of enthalpies of fusion and of mixing in the systems diopside-anorthite-albite and anorthite-forsterite

Transposed-temperature-drop calorimetry, using a Setaram HT 1500 calorimeter, was used to study directly the melting at 1773 K of mixtures of crystalline albite, anorthite, and diopside and of anorthite and forsterite. The enthalpy of albite at 1000–1773 K, starting with both crystalline and glassy samples, was also measured. The results confirm previously measured enthalpies of fusion of albite, diopside and anorthite (Stebbins et al. 1982, 1983; Richet and Bottinga 1984,1986). The new results use thermochemical cycles which completely avoid the glassy state by transforming crystals directly to melts. The enthalpy of fusion of forsterite is estimated to be 89±12 kJ/mol at 1773 K and 114±20 kJ/mol at its melting point of 2163 K. The data allow semiquantitative evaluation of heats of mixing in the molten silicates. Along the Ab-An join, enthalpies of mixing in the liquid at 773 K are the same or somewhat more negative than those in the glass at 986 K, whereas along Ab-Di and An-Di, enthalpies of mixing in the liquid are distinctly more positive than in the glass. These differences correlate with excess heat capacities in the liquids suggested by Stebbins et al. (1984).     

Gel synthesis of magnesium silicates: A 29Si magic angle spinning NMR study

The formation of the magnesium silicate minerals forsterite, enstatite, and roedderite by heating of amorphous “protosilicate” gels precipitated from aqueous solution has been studied by ²⁹Si MAS nmr. Gentle drying of the hydrogels at 110° C gives materials with broad nmr signals that do not differ appreciably with preparation conditions, but the minerals formed by heating at 750° C or higher are greatly dependent on the precipitation and washing conditions of the original gel. The rare mineral roedderite, best known from studies of unequilibrated enstatite chondrite meteorites, becomes a major species along with forsterite when the hydrogels are washed with sodium hydroxide solution before drying and heating to 750° C.     

Formation conditions of aluminum-rich chondrules

We have studied the formation conditions of Al-rich chondrules by doing isothermal and dynamic crystallization experiments at one atmosphere on four different chondrule analogue compositions within the pure CaO-MgO-Al₂O₃-SiO₂ system. For the dynamic crystallization experiments, we cooled from both liquidus and subliquidus peak temperatures (T_max), at cooling rates from 5-1000 °C/h. The starting compositions include two with anorthite and two with forsterite as the dominant liquidus phases, all at or near spinel-saturation. One of each pair evolves towards diopside crystallization, and the others cordierite or enstatite crystallization, giving a total of four completely different crystallization sequences analogous to the four basic varieties of Al-rich chondrule recently proposed. Bulk composition is the main controlling factor, both in terms of mineralogy and texture. The textures of the anorthite-rich compositions are more sensitive to T_max than they are to cooling rate, whereas the textures of the forsterite-rich compositions are more sensitive to cooling rate. Comparisons of natural Al-rich chondrules having similar compositions to our synthetic analogues indicate that the natural objects reflect a range of peak heating temperatures, ∼1400-1500 °C, and cooling rates of 10-500 °C/h for porphyritic chondrules and possibly higher (1000 °C/h) for barred chondrules. These conditions are consistent with the conditions inferred for ferromagnesian chondrules but differ from those inferred for some calcium-aluminum-rich inclusions.     

Activities of olivine and plagioclase components in silicate melts and their application to geothermometry

The activity of a given mineral component in a silicate melt can be calculated from the compositions of coexisting melt and crystals, provided that 1) the component is an independently variable component of the crystal, and 2) appropriate thermodynamic data for the component are known. This approach is used to calibrate the compositional dependence of the activities of forsterite, fayalite, anorthite, and albite from experimental data on natural mafic-to-intermediate melts. The natural logarithms of the activities of forsterite and anorthite can be closely approximated as second-degree polynomial functions of the melt composition (r ²=0.99 and 0.97, respectively); corresponding fits for fayalite and albite are significantly poorer (r ²=0.81 and 0.87, respectively). The shapes of the fitted activity surfaces yield information about speciation in silicate melts. The activity models for forsterite and anorthite provide excellent geothermometers with standard deviations of temperature residuals of approximately 10° C. These geothermometers, when combined with the activity models for fayalite and albite, can be used to predict the temperature at which olivine or plagioclase will crystallize from a melt, along with the composition of the crystals.     

Kinetics and mechanism of natural fluorapatite dissolution at 25 °C and pH from 3 to 12

The dissolution rates of natural fluorapatite (FAP), Ca₁₀(PO₄)₆F₂, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ? pH ? 7, FAP dissolution rates are pH independent at 7 ? pH ? 10, and FAP dissolution rates again decrease with increasing pH at pH ? 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10.Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using

     

Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment

Arsenic sulfide (AsS (am), As₂S₃ (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH∼2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As₂S₃ (am), orpiment, AsS (am), and realgar, respectively.Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ∼1.14 to 13 times and that pH values decrease by ∼0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase.Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As₂S₃ (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH∼8 and temperature 25 to 40°C, and pyrite activation energies are ∼52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As₂S₃ (am). Low activation energies of As₂S₃ (am) indicate that diffusion may be rate controlling.Limestone is commonly mixed with sulfide minerals in a mining environment to prevent acid water formation. However, the oxidation rates of arsenic sulfides increase as solution pH rises and result in a greater release of As. Furthermore, the lifetimes of carbonate minerals (i.e., calcite, aragonite, and dolomite) are much shorter than those of arsenic sulfide and silicate minerals. Thus, within a geologic frame time, carbonate minerals may not be present to act as a pH buffer for acid mine waters. Additionally, the presence of silicate minerals such as pyroxenes (wollastonite, jadeite, and spodumene) and Ca-feldspars (labradorite, anorthite, and nepheline) may not be important for buffering acid solutions because these minerals dissolve faster than and have shorter lifetimes than sulfide minerals. However, other silicate minerals such as Na and K-feldspars (albite, sanidine, and microcline), quartz, pyroxenes (augite, enstatite, diopsite, and MnSiO₃) that have much longer lifetimes than arsenic sulfide minerals may be present in a system. The results of our modeling of arsenic sulfide mineral oxidation show that these minerals potentially can release significant concentrations of dissolved As to natural waters, and the factors and mechanisms involved in arsenic sulfide oxidation warrant further study.     

Diffusion-controlled growth of albite and pyroxene reaction rims

The growth rates of albite and pyroxene (enstatite + diopside + spinel) reaction rims were measured at 1000°C and ˜700 MPa and found to be parabolic indicating diffusion-controlled growth. The parabolic rate constants for the pyroxene (+ spinel) rims in samples with 0.5 wt% H₂O added or initially vacuum dried at 25°C and 250°C are 1.68 ± 0.09, 0.54 ± 0.05 and 0.25 ± 0.06 μm²/h, respectively. The values for albite rim growth in samples initially dried at 60°C and with 0.1 wt% H₂O added are 0.25 ± 0.04 and 0.33 ± 0.03 μm²/h, respectively. The latter values were used to derive the product of the grain boundary diffusion coefficient D′_A, where A = SiO₂, NaAlO₂, or NaAlSi₋₁, and the grain boundary thickness δ in albite. The calculated D′_SIO2δ in the albite aggregate for the situations of two different water contents are about 9.9 × 10⁻²³ and 1.4 × 10⁻²² m³ s⁻¹, respectively. Both the rate constants and the calculated D′_Aδ demonstrate that the effect of water content on the grain boundary diffusion rate in monomineralic albite and polymineralic pyroxene (+ spinel) aggregates is small, consistent with recent studies of monomineralic enstatite and forsterite rims. Received: 1 July 1995 / Accepted: 1 August 1996     

A computer simulation approach to modelling the structure,thermodynamics and oxygen isotope equilibria of silicates

We use an atomistic model to simulate the structure, lattice dynamics and thermodynamics of silicate minerals. Our approach uses the Born model of a solid, in which the interaction between atoms is described by an interatomic pair potential. We have extended the study of thermodynamics to its very limit by looking at the subtle reaction of oxygen isotope exchange. We have modelled equilibria involving the important metamorphic minerals; albite, diopside, forsterite, pyrope, quartz and wollastonite. The predicted structural and thermodynamic data for these silicates are in very good agreement with the observed values. In addition, we predict not only the correct direction for the phase equilibria for oxygen isotope exchange, but also fractionation factors for the reaction to within a factor of two of the available experimental data. Hence, the potentials used in our approach have shown excellent transferability and have performed very well against the most stringent of tests.