On the origin of multi‐layer coronas between olivine and plagioclase at the gabbro–granulite transition,Valle Fértil–La Huerta Ranges,San Juan Province,Argentina

Troctolitic gabbros from Valle Fértil and La Huerta Ranges, San Juan Province, NW‐Argentina exhibit multi‐layer corona textures between cumulus olivine and plagioclase. The corona mineral sequence, which varies in the total thickness from 0.5 to 1 mm, comprises either an anhydrous corona type I with olivine|orthopyroxene|clinopyroxene+spinel symplectite|plagioclase or a hydrous corona type II with olivine|orthopyroxene|amphibole|amphibole+spinel symplectite|plagioclase. The anhydrous corona type I formed by metamorphic replacement of primary olivine and plagioclase, in the absence of any fluid/melt phase at <840 °C. Diffusion controlled metamorphic solid‐state replacement is mainly governed by the chemical potential gradients at the interface of reactant olivine and plagioclase and orthopyroxene and plagioclase. Thus, the thermodynamic incompatibility of the reactant minerals at the gabbro–granulite transition and the phase equilibria of the coronitic assemblage during subsequent cooling were modelled using quantitative μMgO–μCaO phase diagrams. Mineral reaction textures of the anhydrous corona type I indicate an inward migration of orthopyroxene on the expense of olivine, while clinopyroxene+spinel symplectite grows outward to replace plagioclase. Mineral textures of the hydrous corona type II indicate the presence of an interstitial liquid trapped between cumulus olivine and plagioclase that reacts with olivine to produce a rim of peritectic orthopyroxene around olivine. Two amphibole types are distinguished: an inclusion free, brownish amphibole I is enriched in trace elements and REEs relative to green amphibole II. Amphibole I evolves from an intercumulus liquid between peritectic orthopyroxene and plagioclase. Discrete layers of green amphibole II occur as inclusion‐free rims and amphibole II+spinel symplectites. Mineral textures and geochemical patterns indicate a metamorphic origin for amphibole II, where orthopyroxene was replaced to form an inner inclusion‐free amphibole II layer, while clinopyroxene and plagioclase were replaced to form an outer amphibole+spinel symplectite layer, at <770 °C. Calculation of the possible net reactions by considering NCKFMASH components indicates that the layer bulk composition cannot be modelled as a ‘closed’ system although in all cases the gain and loss of elements within the multi‐layer coronas (except H₂O, Na₂O) is very small and the main uncertainties may arise from slight chemical zoning of the respective minerals. Local oxidizing conditions led to the formation of orthopyroxene+magnetite symplectite enveloping and/or replacing olivine. The sequence of corona reaction textures indicates a counter clockwise P–T path at the gabbro–granulite transition at 5–6.5 kbar and temperatures below 900 °C.     

Models for orthopyroxene–plagioclase and other corona reactions in metanorites, Dahomeyide orogen, West Africa

Coronal reaction textures occur in metanorite and related intrusions in the Pan-African Dahomeyide orogen of West Africa; they apparently formed by retrograde subsolidus reactions during cooling of the intrusions from 900 to 700 °C at c. 9±1 kbar. The coronas that formed around orthopyroxene (Opx) consist of sequential layers of diopside (Dio), hornblende (Hbl), garnet (Grt) and plagioclase (Pl) with inclusions of kyanite (Ky) or sillimanite (Sil). Three well-organized mineral assemblage sequences have been identified and modelled using steady-state diffusion theory for closed and open systems. The mineral sequence Opx|Hbl+Qtz|Hbl|Pl+Ky, formed by diffusion-controlled reactions in a closed system as layer thicknesses are very sensitive to relative component mobilities defined by Onsager diffusion coefficient (L_ii). Models of this corona (type i) that satisfy modes require L_CaCa≥L_MgMg≥L_FeFe>L_AlAl～L_SiSi ; however, small open-system fluxes involving loss of Al and gain of Ca are required to obtain the best fit between model and observed mineral proportions. Under steady-state diffusion, the monomineralic hornblende layer grew by replacing plagioclase whereas the |Hbl+Qtz| grew by Opx replacement. The type ii corona, which consists of the sequence Opx|Dio|Grt+Dio|Pl+Sil, is also stable under steady-state diffusion in a closed system. Modelling results show that the diopside grew by replacing Opx whereas most of Grt+Dio grew by replacing plagioclase. Stable solutions to the closed-system diffusion model that approximate the mode are restricted to the L-ratio regions where Fe, Mg and Ca are more mobile than Si and Al but are unstable when L_AlAl>100 L_SiSi . However, type ii corona mineral proportions were only closely matched when open-system loss of Al and gain of small amounts of Fewere considered in the diffusion models and relative mobilities were L_FeFe≥L_CaCa≥L_MgMg>L_AlAl～L_SiSi . The modelling results indicate that Ca and Mg were the most mobile elements in the formation of type i corona whereas Fe and Ca were the most mobile components in the growth of type ii coronas. A third corona type, consisting of the mineral sequence Act|Hbl|Grt|Pl+Sil, is only stable in open systems and requires large external fluxes involving gain of Fe, Al, Mg and Na and loss of Ca to obtain a solution of the diffusion model that approximates the estimated mineral proportions. Extensive recrystallization of plagioclase to produce sillimanite or kyanite inclusions accompanying corona formation may explain the open-system behaviour indicated by the diffusion models.     

Thermodynamic studies of pyrrhotite-pyrite equilibria in the Ag-Fe-S system by solid-state galvanic cell technique at 518-723 K and total pressure of 1 atm

The reaction FeS₂(cr) + 2Ag(cr) = ‘FeS’(cr) + Ag₂S(cr) was studied by measuring the temperature dependence of the electromotive force (EMF) of the all-solid-state galvanic cell with common gas space:

(-)Pt|Ag|AgI|Ag₂S,‘FeS’,FeS₂|Pt(+)     

Diffusion in coronas around clinopyroxene: modelling with local equilibrium and steady state,and a non-steady-state modification to account for zoned actinolite-hornblende

Retrograde coronas of Caledonian age, between clinopyroxene and plagioclase in the Jotun Nappe Complex, Norway, illustrate the effects of diffusion kinetics on mineral distributions among layers and on the compositions of hornblende-actinolite. One corona type comprises a symplectite of epidote + quartz adjacent to plagioclase, and a less well-organized intergrowth of amphibole + quartz replacing clinopyroxene. The observed mineral proportions imply an open-system reaction, but the similarity of Al/Si ratios in reactant plagioclase and product symplectite indicates approximate conservation of Al₂O₃ and SiO₂. The largest inferred open-system flux is a loss of CaO, mostly derived from consumption of clinopyroxene. The approximate layer structure, Pl|Ep + Qtz|Hbl + Qtz|Act±Hbl + Qtz|Cpx, is modelled using the theory of steady-state diffusion-controlled growth with local equilibrium. To obtain a solution, it is necessary to use a reactant plagioclase composition which takes into account aluminous (epidote) inclusions. The results indicate that, in terms of Onsager diffusion coefficients L _ii , Ca is more mobile than AL (L _CaCa/L _AlAl3.) (where means greater than or approximately equal to). This behaviour of Ca is comparable with that of Mg in previously studied coronas around olivine. Si is non-diffusing in the present modelling, because of silica saturation. Oxidation of some Fe²⁺ to Fe³⁺ occurs within the corona. Mg diffuses towards its source (clinopyroxene) to maintain local equilibrium. Other coronas consist of two layers, hornblende adjacent to plagioclase and zoned amphibole + quartz adjacent to clinopyroxene. In the zoned layer, actinolitic hornblende forms relict patches, separated from quartz blebs by more aluminous hornblende. A preliminary steady-state, local-equilibrium model of grain-boundary diffusion explains the formation of low-Al and high-Al layers as due to Al immobility. Zoning and replacement are qualitatively explained in terms of evolution of actinolite to more stable aluminous compositions. This is modelled by a non-steady-state modification of the theory, retaining local equilibrium in grain boundaries while relatively steep zoning profiles develop in grain interiors through slow intracrystalline diffusion. Replacement of actinolite by hornblende does not require a change in P–T conditions if actinolite is a kinetically determined, non-equilibrium product. The common preservation of a sharp contact between hornblende and actionolite layers may be explained by ineffectiveness of intracrystalline diffusion: according to the theory, given sufficient grain-boundary Al flux, a metastable actinolite + quartz layer in contact with hornblende may be diffusionally stable and may continue to grow in a steady state.     

Diffusion-controlled olivine corona textures in granitic rocks from Lofoten, Norway: calculation of Onsager diffusion coefficients, thermodynamic modelling and petrological implications

Reactions occurring during cooling of charnockitic intrusives on the Lofoten Islands produce characteristic diffusion-controlled textures around fayalite and Fe–Ti oxides. Thermobarometry indicates the corona textures formed at 780–840 °C and pressures of 4–10 kbar, whereas the magmatic assemblage of the charnockite (clinopyroxene–olivine–quartz) crystallized at about 850–870 °C and 4 kbar. The succession olivine|orthopyroxene+magnetite|orthopyroxene+garnet and olivine|orthopyroxene+magnetite|amphibole developed where olivine reacted with adjacent plagioclase or K-feldspar, but the modes and the thicknesses of the corona textures vary according to the feldspar type, indicating that the primary magmatic ternary feldspar was already exsolved into albitic plagioclase and alkali feldspar when the corona formation began. Simultaneously, in other parts of the rock, primary magmatic clinopyroxene reacted to amphibole and Fe–Ti oxides reacted to orthopyroxene+garnet coronas or to amphibole. Textures demonstrate significant Al diffusion in the rocks under granulite facies conditions and they suggest that no pervasive fluid influx occurred and that amphibole formation was dependant on a local source of H₂O probably related to water-release during the last stages of magmatism. Calculation of the net reaction by accounting for all observed reactions at different sites in the rock indicates that the system can be regarded as balanced on a hand-specimen scale with respect to all elements except for Na and H₂O. The larger variety of textures developed in rocks of granitic bulk composition provide more constraints than textures from gabbroic compositions, and permitted calculation of a set of relative diffusion coefficients which also reproduce textures in the gabbroic and anorthositic rocks from the Lofoten Islands. The following set of relative diffusion coefficients (L_i/L_Fe) reproduces the observed textures in the Lofoten rocks: Si=0.82, Mg=0.59, Mn=0.05, Na=0.38, K=0.39, Al=0.05 and Ca=0.07.     

Cation sorption on the muscovite (0 0 1) surface in chloride solutions using high-resolution X-ray reflectivity

The structure and mechanism of cation sorption at the (0 0 1) muscovite-water interface were investigated in 0.01 and 0.5 m KCl, CsCl, and CaCl₂ and 0.01 m BaCl₂ solutions at slightly acidic pH by high-resolution X-ray reflectivity. Structural relaxations of atom positions in the 2M₁ muscovite were small (?0.07 Å) and occurred over a distance of 30 to 40 Å perpendicular to the interface. Cations in all solutions were sorbed dominantly in the first and second solution layers adjacent to the mineral surface. The derived heights of the first solution layer in KCl and CsCl solutions, 1.67(6)-1.77(7) and 2.15(9)-2.16(2) Å, respectively, differ in magnitude by the approximate difference in crystallographic radii between K and Cs, and correspond closely to the interlayer cation positions in bulk K- and Cs-mica structures. The first solution layer heights in CaCl₂ and BaCl₂ solutions, 2.46(5)-2.56(11) and 2.02(5) Å, respectively, differ in a sense opposite to that expected based on crystallographic or hydrated radii of the divalent cations. The derived ion heights in all solutions imply that there is no intercalated water layer between the first solution layer and the muscovite surface. Molecular compositions were assigned to the first two solution layers in the electron density profiles using models that constrain the number density of sorbed cations, water molecules, and anions by considering the permanent negative charge of the muscovite and average solution density. The models result in partial charge balance (at least 50%) by cations sorbed in the first two layers in the 0.01 m solutions and approximately full charge balance in the 0.5 m solutions. Damped oscillations of model water density away from the first two solution layers agree with previous X-ray reflectivity results on the muscovite (0 0 1) surface in pure water.     

An experimental study of crystalline basalt dissolution from 2 ? pH ? 11 and temperatures from 5 to 75 °C

Steady-state element release rates from crystalline basalt dissolution at far-from-equilibrium were measured at pH from 2 to 11 and temperatures from 5 to 75 °C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures ?25 °C but slower at alkaline pH and temperatures ?50 °C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Calcium is primarily present in plagioclase, which exhibits a U-shaped dissolution rate dependence on pH. In contrast, Mg and Fe are contained in pyroxene and olivine, minerals whose dissolution rates decrease monotonically with pH. As a result, crystalline basalt preferentially releases Mg and Fe relative to Ca at acidic conditions. The injection of acidic CO₂-charged fluids into crystalline basaltic terrain may, therefore, favour the formation of Mg and Fe carbonates rather than calcite. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study.     

Molecular dynamics simulations of the orthoclase (0 0 1)- and (0 1 0)-water interfaces

Molecular dynamics simulations of water in contact with the (0 0 1) and (0 1 0) surfaces of orthoclase (KAlSi₃O₈) were carried out to investigate the structure and dynamics of the feldspar-water interface, contrast the intrinsic structural properties of the two surfaces, and provide a basis for future work on the diffusion of ions and molecules in microscopic mineral fractures. Electron density profiles were computed from the molecular dynamics trajectories and compared with those derived experimentally from high-resolution X-ray reflectivity measurements by Fenter and co-workers [Fenter P., Cheng L., Park C., Zhang H. and Sturchio N. C. (2003a) Structure of the orthoclase (0 0 1)- and (0 1 0)-water interfaces by high-resolution X-ray reflectivity. Geochim. Cosmochim. Acta67, 4267-4275]. For each surface, three scenarios were considered whereby the interfacial species is potassium, water, or a hydronium ion. Excellent agreement was obtained for the (0 0 1) surface when potassium is the predominant interfacial species; however, some discrepancies in the position of the interfacial peaks were obtained for the (0 1 0) surface. The two surfaces showed similarities in the extent of water ordering at the interface, the activation energies for water and potassium desorption, and the adsorption localization of interfacial species. However, there are also important differences between the two surfaces in the coordination of a given adsorbed species, adsorption site densities, and the propensity for water molecules in surface cavities and those in the first hydration layer to coordinate to surface bridging oxygen atoms. These differences may have implications for the extent of dissolution in the low-pH regime since hydrolysis of Si(Al)OSi(Al) bonds is a major dissolution mechanism.     

Geology of the mineralized zone of the Wanapitei complex,Grenville Front,Ontario

The Wanapitei Complex (6 km×2.5 km), lying 0.4 km southeast of the Grenville Front, consists of a northwestern zone of gabbro and folded injection breccia and a southeastern layer of intensely folded hornblendeplagioclase gneiss. Disseminated Ni-Cu sulphides are unevenly distributed in a zone between the injection breccia and the folded gneiss.Rocks of the mineralized zone occur in southeastern and northeastern areas. The former area consists of hornblende norite, the major host rock of the sulphides, and olivine norite. Steeply-dipping cross-bedded primary layers and chemical trends indicate the top faces southeast. In the latter area olivine norite, hornblende norite, and hornblende gabbro grade eastward into recrystallized rocks and breccia. The olivine norites are characterized by corona reaction rims. Reactions are: olivine+plagioclase bronzite+diopside-spinel; olivine+pyroxene bronzite; and pyroxene+plagioclase diopside-spinel. Molecular proportion ratio variation diagrams suggest that rocks evolved from a common parent magma that underwent fractionation dominated by olivine and plagioclase. Sulphide mineralization (pyrrhotite, chalcopyrite, pentlandite, pyrite) is interstitial to the silicates and appears to be of primary magmatic origin.Northeasterly-trending shear zones, felsic dikes, and matic dikes are metamorphosed to the same degree as the rocks they cut (amphibolite facies). The sequence of events for the mineralized zone are: intrusion deep in the crust; tilting; brecciation; shearing; felsic and mafic dike emplacement; metamorphism; and injection of granite pegmatite dikes.Deceased (8-16-1986)     

Olivines and olivine coronas in mesosiderites

Olivines and their surrounding coronas in mesosiderites have been studied texturally and compositionally by optical and microprobe methods. Most olivine is compositionally homogeneous but some is irregularly zoned. It ranges from Fo_58–92 and shows no consistent pattern of distribution within and between mesosiderites. Olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. One is in Emery, the other in Vaca Muerta, and they are both shock-modified olivine orthopyroxenites. $\text{FeO}\text{MnO}$ ratios in olivine exhibit a variety of differing trends and range from 22–46, most commonly 35–40. These values are lower than those in olivine from diogenites sensu stricto (45–50) and have therefore experienced a different history. Some of the olivine clasts could have coexisted with some of the large orthopyroxene clasts as equilibrium assemblages, but some could not. Much of the olivine may be derived from mesosiderite olivine orthopyroxenites, which differ from diogenites sensu stricto. More magnesian olivine may be a residue from one or more source rocks, with varying degrees of melting. These events probably occurred in a highly evolved and differentiated parent body.Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites (Simondium, Hainholz, Pinnaroo) and those without tridymite in their matrices (Bondoc, Veramin). Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merrillite and ilmenite and are similar to the matrix, but lack metal and tridymite. Coronas contain abundant orthopyroxene but are unusually rich in chromite (up to 7%) and merrillite (up to 20%). The outer parts of the corona grade into the matrix, but have little or no metal and tridymite. Texturally the innermost part of the corona can be divided into three stages of development: I Radiating acicular; II Intermediate; III Granular. Stage I is the result of the greatest disequilibrium between olivine and matrix orthopyroxene and Stage III has the least disequilibrium. Coronas are the result of the reaction olivine + tridymite = orthopyroxene, probably because FeO (and MgO) diffuse from olivine to tridymite in the matrix. Absence of metal and concentration of chromite in the corona are probably the result of an FeO potential gradient away from the olivine. Merrillite concentrations are a result of P₂O₅ migration into the corona but are controlled by the availability of calcic pyroxene, or possibly plagioclase. Although the coronas are texturally similar to terrestrial and lunar counterparts, they are unique and represent different kinds of reactions marked by a large degree of intra-corona diffusion under dry conditions. Opaque oxide-silicate-metal buffer assemblages yield apparent equilibration conditions of about 840°C and fO₂ near 10^?20. Poikiloblastic pyroxene textures in some coronas suggest a closing of reaction systems between 900 and 1000°C and such systems may record a higher temperature stage of development.     

Experimental modelling of corona textures

Formation of corona textures along olivine–plagioclase and orthopyroxene–plagioclase interfaces has been experimentally reproduced at 670 and 700 °C and 5 kbar with either a pure H₂O fluid phase or 0.1 and 37 m NaCl–H₂O solution fluid. In these experiments, we investigate the interaction of primary olivine and/or orthopyroxene and plagioclase in powders and polished crystals, and in small samples of a natural gabbro. The experiments result in the formation of corona textures with several layers of different assemblages (according to the experimental conditions) consisting of garnet (grossular), clinopyroxene, orthopyroxene, amphibole, chlorite and phlogopite. The experiments show major differences in the number of layers, the mineral assemblages and mineral composition, and in the trends of composition of plagioclase in coronas around olivine and orthopyroxene. The fluid phase composition influences the corona assemblages and the composition of the minerals in the experimental coronas; for example, garnet appears in the coronas in the second experiment where the NaCl–H₂O ratio is low. Experimental modelling of corona textures confirms a model of simultaneous growth of layers by the mechanism of diffusion metasomatism with participation of a fluid phase through which mass is transferred. Zoning in the experimental coronas shows opposing diffusion of Al and Ca from plagioclase and Mg and Fe from olivine/orthopyroxene; difference in the mobility of the components is inferred from observations in the coronas. The experimental corona textures are compared with natural coronas from the Belomorian belt (Baltic shield), developed at 670–690 °C and 7–8 kbar, and the Marun‐Keu complex (Polar Urals), developed at 670–700 °C and 14–16 kbar, where the corona textures correspond to a transitional stage of the gabbro‐to‐eclogite transformation.     

Adsorption of Rb and Sr at the orthoclase (0 0 1)-solution interface

Adsorption of Rb⁺ and Sr²⁺ at the orthoclase (0 0 1)-solution interface is probed with high-resolution X-ray reflectivity and resonant anomalous X-ray reflectivity. Specular X-ray reflectivity data for orthoclase in contact with 0.01 m RbCl solution at pH 5.5 reveal a systematic increase in electron density adjacent to the mineral surface with respect to that observed in contact with de-ionized water (DIW). Quantitative analysis indicates that Rb⁺ adsorbs at a height of 0.83 ± 0.03 Å with respect to the bulk K⁺ site with a nominal coverage of 0.72 ± 0.10 ions per surface unit mesh (55.7 Å²). These results are consistent with an ion-exchange reaction in which Rb⁺ occupies an inner-sphere adsorption (IS) site. In contrast, X-ray reflectivity data for orthoclase in contact with 0.01 m Sr(NO₃)₂ solution at pH 5.3 reveal few significant changes with respect to DIW. Resonant anomalous X-ray reflectivity was used to probe Sr²⁺ adsorption and to image its vertical distribution. This element-specific measurement reveals that Sr²⁺ adsorbs with a total coverage of 0.37 ± 0.02 ions per surface unit mesh, at a substantially larger height (3.28 ± 0.05 Å) than found for Rb⁺, and with a relatively broad density distribution (having a root-mean-square width of 1.88 ± 0.08 Å for a single-peak model), implying that Sr²⁺ adsorbs primarily as a fully-hydrated outer-sphere (OS), species. Comparison to a two-height model suggests that 13 ± 5% of the adsorbed Sr²⁺ may be present as an IS species. This partitioning implies a ∼5 kJ/mol difference in free energy between the IS and OS Sr²⁺ on orthoclase. Differences in the partitioning of Sr²⁺ between IS and OS species for orthoclase (0 0 1) and muscovite (0 0 1) suggest control by the geometry of the IS adsorption site. Results for the OS distribution are compared to predictions of the Poisson-Boltzmann equation in the strong coupling regime, which predicts an intrinsically narrow vertical diffuse ion distribution; the OS distribution might thus be thought of as the diffuse ion profile in the limit of high surface charge.     

Development of corona textures around olivine in anorthosites of the Korosten’ pluton, Ukrainian Shield: Mineralogy, geochemistry, and fluid inclusions

New data on the composition of minerals in corona textures around olivine and crystal-fluid inclusions in olivine from anorthosites of the Korosten’ pluton (sampled in the Golovino quarry), Ukrainian Shield were obtained using electron and ion microprobe analyses, Raman spectroscopy, scanning electron microscopy, and cryo- and thermometry. The corona textures developed around olivine grains in contact with plagioclase and consist of inner orthopyroxene rims around olivine and outer rims of orthopyroxene-clinopyroxene-orthoclase-plagioclase symplectites. The symplectites and orthopyroxene rims most probably developed nearly simultaneously and grew in the opposite directions from the original contact of the magmatic olivine and plagioclase and replaced both olivine and plagioclase. The Al₂O₃ and CaO concentrations in the symplectitic orthopyroxene increase toward the contact with magmatic plagioclase, whereas the Al₂O₃ and CaO concentrations in the symplectitic plagioclase simultaneously decrease and its Na₂O and K₂O increase. Optically discernible crystalline and fluid phases of crystal-fluid inclusions in olivine were identified as pyroxenes (orthopyroxene and clinopyroxene), actinolite, Ca-and Fe, Mg-carbonates, and magnetite, along with practically pure highdensity CO₂. The mineral assemblages of corona texture in the Korsten’ anorthosites were produced by autometasomatic processes at a high CO₂ activity, and the local variations in the chemistry of corona minerals were likely controlled by the content and chemistry of the interstitial fluid and primary minerals. The coronas developed under subsolidus conditions, via the reaction interaction of olivine and plagioclase under the effect of an integranular fluid, with the dissolution of olivine and plagioclase at T = 980–860°C and P > 5 kbar. Inasmuch as corona textures do not occur ubiquitously in the rocks, the origin of the former was most probably controlled by the amount of the intergranular fluid.     

Characterization of elemental release during microbe-granite interactions at T = 28 °C

This study used batch reactors to characterize the mechanisms and rates of elemental release (Al, Ca, K, Mg, Na, F, Fe, P, Sr, and Si) during interaction of a single bacterial species (Burkholderia fungorum) with granite at T = 28 °C for 35 days. The objective was to evaluate how actively metabolizing heterotrophic bacteria might influence granite weathering on the continents. We supplied glucose as a C source, either NH₄ or NO₃ as N sources, and either dissolved PO₄ or trace apatite in granite as P sources. Cell growth occurred under all experimental conditions. However, solution pH decreased from ∼7 to 4 in NH₄-bearing reactors, whereas pH remained near-neutral in NO₃-bearing reactors. Measurements of dissolved CO₂ and gluconate together with mass-balances for cell growth suggest that pH lowering in NH₄-bearing reactors resulted from gluconic acid release and H⁺ extrusion during NH₄ uptake. In NO₃-bearing reactors, B. fungormum likely produced gluconic acid and consumed H⁺ simultaneously during NO₃ utilization.Over the entire 35-day period, NH₄-bearing biotic reactors yielded the highest release rates for all elements considered. However, chemical analyses of biomass show that bacteria scavenged Na, P, and Sr during growth. Abiotic control reactors followed different reaction paths and experienced much lower elemental release rates compared to biotic reactors. Because release rates inversely correlate with pH, we conclude that proton-promoted dissolution was the dominant reaction mechanism. Solute speciation modeling indicates that formation of Al-F and Fe-F complexes in biotic reactors may have enhanced mineral solubilities and release rates by lowering Al and Fe activities. Mass-balances further reveal that Ca-bearing trace phases (calcite, fluorite, and fluorapatite) provided most of the dissolved Ca, whereas more abundant phases (plagioclase) contributed negligible amounts. Our findings imply that during the incipient stages of granite weathering, heterotrophic bacteria utilizing glucose and NH₄ only moderately elevate silicate weathering reactions that consume atmospheric CO₂. However, by enhancing the dissolution of non-silicate, Ca-bearing trace minerals, they could contribute to high Ca/Na ratios commonly observed in granitic watersheds.     

Phase relations on the diopside-jadeite-hedenbergite join up to 24 GPa and stability of Na-bearing majoritic garnet

Phase relations on the diopside (Di)-hedenbergite (Hd)-jadeite (Jd) system modeling mineral associations of natural eclogites were studied for the compositions (mol %) Di₇₀Jd₃₀, Di₅₀Jd₅₀, Di₃₀Jd₇₀, Di₂₀Hd₈₀, and Di₄₀Hd₁₀Jd₅₀ using a toroidal anvil-with-hole (7 GPa) and a Kawai-type 6-8 multianvil apparatus (12-24 GPa). We established that Di, Hd, and Jd form complete series of solid solutions at 7 GPa, and melting temperatures of pure Di (1980 °C) and Jd (1870 °C) for that pressure were estimated experimentally. The melting temperature for the Di₅₀Jd₅₀ composition at 15.5 GPa is 2270 °C. The appearance of garnet is clearly dependent on initial clinopyroxene composition: at 1600 °C the first garnet crystals are observed at 13.5 GPa in the jadeite-rich part of the system (Di₃₀Jd₇₀), whereas diopside-rich starting material (Di₇₀Jd₃₀) produces garnet only above 17 GPa. The proportion of garnet increases rapidly above 18 GPa as pyroxene dissolves in the garnet structure and pyroxene-free garnetites are produced from diopside-rich starting materials. In all experiments, garnet coexists with stishovite (St). At a pressure above 18 GPa, pyroxene is completely replaced by an assemblage of majorite (Maj) + St + CaSiO₃-perovskite (Ca-Pv) in Ca-rich systems, whereas Maj is associated with almost pure Jd up to a pressure of 21.5 GPa. Above ∼22 GPa, Maj, and St are associated with NaAlSiO₄ with calcium ferrite structure (Cf). We established that an Hd component also spreads the range of pyroxene stability up to 20 GPa. In the Di₇₀Jd₃₀ system at 24 GPa an assemblage of Maj + Ca-Pv + MgSiO₃ with ilmenite structure (Mg-Il) was obtained. The experimentally established correlation between Na, Si, and Al contents in Maj and pressure in Grt(Maj)-pyroxene assemblages, may be the basis for a “majorite” geobarometer. The results of our experiments are applicable to the upper mantle and the transition zone of the Earth (400-670 km), and demonstrate a wide range of transformations from eclogite to perovskite-bearing garnetite. In addition, the mineral associations obtained from the experiments allowed us to simulate parageneses of inclusions in diamonds formed under the conditions of the transition zone and the lower mantle.     

Melt inclusions in olivine and pyroxene phenocrysts from lamprophyres of Chhaktalao Area,Madhya Pradesh,India

Melt inclusions in olivine and pyroxene phenocrysts in kersantite and camptonite at Chhaktalao in Madhya Pradesh, India are mainly of the evolved type forming daughter minerals of olivine, pyroxene, plagioclase, spinel, mica, titanomagnetite and sulphides. Heating studies exhibit a temperature range from 1215° to 1245°C for the melt inclusions in olivine in camptonite and 1220–1245°C for olivine in kersantite. The temperature for melt inclusions in pyroxene ranged from 1000° to 1150°C in camptonite and 850–1100°C for pyroxene in kersantite. The bubble inside these melt inclusions is mainly CO₂. The T_h°C of CO₂ into liquid phase occurred between 26° and 31°C in olivine and 25–30°C in pyroxene from kersantite and camptonite. The maximum density estimated is 0.72 g/cm³ and the minimum is 0.45 g/cm³. The depth of entrapment of the melt inclusion is estimated between 10–15 km. The pressure of entrapment of melt inclusion in olvine is 4.6 kbar where as that in pyroxene is 3.7 kbar. The lamprophyres in the Chhaktalao area are considered to be derived from low depth and low pressure region, possibly within spinel lherzolite zone.     

Fe(II) adsorption on hematite (0 0 0 1)

The surface structure of α-Fe₂O₃(0 0 0 1) was studied using crystal truncation rod (CTR) X-ray diffraction before and after reaction with aqueous Fe(II) at pH 5. The CTR results show the unreacted α-Fe₂O₃(0 0 0 1) surface consists of two chemically distinct structural domains: an O-layer terminated domain and a hydroxylated Fe-layer terminated domain. After exposing the α-Fe₂O₃(0 0 0 1) surface to aqueous Fe(II), the surface structure of both co-existing structural domains was modified due to adsorption of Fe at crystallographic lattice sites of the substrate, resulting in six-coordinated adsorbed Fe at the surface. The average Fe-O bond lengths of the adsorbed Fe are consistent with typical Fe(III)-O bond lengths (in octahedral coordination), providing evidence for the oxidation of Fe(II) to Fe(III) upon adsorption. These results highlight the important role of substrate surface structure in controlling Fe(II) adsorption. Furthermore, the molecular scale structural characterization of adsorbed Fe provides insight into the process of Fe(II) induced structural modification of hematite surfaces, which in turn aids in assessing the effective reactivity of hematite surfaces in Fe(II) rich environments.     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as

     

Iron partitioning and hydrogen generation during serpentinization of abyssal peridotites from 15°N on the Mid-Atlantic Ridge

Aqueous dihydrogen (H₂,aq) is produced in copious amounts when seawater interacts with peridotite and H₂O oxidizes ferrous iron in olivine to ferric iron in secondary magnetite and serpentine. Poorly understood in this process is the partitioning of iron and its oxidation state in serpentine, although both impose an important control on dihydrogen production. We present results of detailed petrographic, mineral chemical, magnetic and Mößbauer analyses of partially to fully serpentinized peridotites from the Ocean Drilling Program (ODP) Leg 209, Mid-Atlantic Ridge (MAR) 15°N area. These results are used to constrain the fate of iron during serpentinization and are compared with phase equilibria considerations and peridotite-seawater reaction path models. In samples from Hole 1274A, mesh-rims reveal a distinct in-to-out zoning from brucite at the interface with primary olivine, followed by a zone of serpentine + brucite ± magnetite and finally serpentine + magnetite in the outermost mesh-rim. The compositions of coexisting serpentine (Mg# 95) and brucite (Mg# 80) vary little throughout the core. About 30-50% of the iron in serpentine/brucite mesh-rims is trivalent, irrespective of subbasement depth and protolith (harzburgite versus dunite). Model calculations suggest that both partitioning and oxidation state of iron are very sensitive to temperature and water-to-rock ratio during serpentinization. At temperatures above 330 °C the dissolution of olivine and coeval formation of serpentine, magnetite and dihydrogen depends on the availability of an external silica source. At these temperatures the extent of olivine serpentinization is insufficient to produce much hydrogen, hence conditions are not reducing enough to form awaruite. At T < 330 °C, hydrogen generation is facilitated by the formation of brucite, as dissolution of olivine to form serpentine, magnetite and brucite requires no addition of silica. The model calculations suggest that the iron distribution observed in serpentine and brucite is consistent with formation temperatures ranging from <150 to 250 °C and bulk water-to-rock ratios between 0.1 and 5. These conditions coincide with peak hydrogen fugacities during serpentinization and are conducive to awaruite formation during main stage serpentinization. The development of the common brucite rims around olivine is either due to an arrested reaction olivine → brucite → serpentine + brucite, or reflects metastable olivine-brucite equilibria developing in the strong gradient in silica activity between orthopyroxene (talc-serpentine) and olivine (serpentine-brucite).     

Petrological implications of some corona structures

Reactions between olivine and plagioclase, and between pyroxenes and plagioclase, commonly produce corona assemblages of lower volume and entropy. These coronas imply that assemblages representative of intermediate-and high-pressure granulite facies, and of eclogite facies (emphacite + garnet), can be produced by the cooling of dry olivine + plagioclase and pyroxene + plagioclase assemblages from igneous temperatures within the continental crust. They further imply that eclogite is a stable assemblage within the deeper parts of the continental crust; this in turn requires that dP/dT > 0 for the equilibrium curves for the relevant reactions. The general relations between T and rates of nucleation, growth and diffusion suggest that these coronas will only be formed in relatively deep-seated rocks (P > 6 kb ?). The formation of such coronasby regional or contact metamorphism, or by metasomatism, is unlikely; they are best regarded as retrograde features.