Modelling the effect of water on the surface structure and stability of forsterite

 We describe the application of atomistic simulation techniques to investigate the effect of associative and dissociative adsorption of water on the structures and stabilities of the low-index surfaces of forsterite. All surfaces are amenable to associative adsorption of water, while dissociative adsorption is energetically favourable on all but the non-dipolar {1 0 0} surface. Often, otherwise unstable (dipolar) surfaces are stabilised to a large extent by hydration, e.g. the dipolar {0 1 0} surface. However, on thermodynamic grounds we do not expect associatively adsorbed water to dissociate on all surfaces, as the energies released for dissociative adsorption of water on the non-dipolar {0 1 0} and {1 0 0} surfaces are less than those released for associative adsorption. As such, there is no energetic incentive for the associatively adsorbed water molecules to dissociate. The stabilities of the two terminations of the {0 1 0} surface, the main cleavage plane of forsterite, are reversed when hydroxylated, indicating that some dissolution of the magnesium ions may occur upon hydration, which is shown to be an exothermic process for both surface terminations. The equilibrium morphology was calculated as a way of assessing the change in surface energies. The experimental morphology of forsterite is adequately reproduced, suggesting that the relative stabilities of the surfaces, both unhydrated and hydroxylated, are calculated correctly. Received: 4 August 1999 / Revised, accepted: 11 October 1999     

锆石柱面中Hf、Y的配位差异性及其对晶型的控制效应

天然锆石的形态并不简单地依照PBC理论发育,它同时受到生长温度 、熔体扩散系数等物理参数的影响,以及置换Zr的杂质离子的种类和浓度等化学因素的制约 ,即杂质离子选择性地置换Zr而降低晶面的生长速度。通过对{100}和{110}柱面的半定量分 析发现,Hf4+、Y3+离子同O2-离子的成键数目在{100}与{110}生长层 上是不同的,且Hf-O的键强比Zr-O的大,而Y-O的键强比Zr-O的小。如果假定晶体与岩浆熔体并未达到真正的平衡,而是各晶面与岩浆熔体分别达到平衡,按热力学中浓度与能量变化的指数律去处理Hf和Y在{100}与{110}晶面上的配分可以得到,{100}晶面上趋于富Hf贫 Y,{110}晶面上趋于富Y贫Hf,从而导致富Hf的锆石上{100}优先发育,富Y的锆石上{110}优 先发育。     

Phase Transformations and Proton Promoted Dissolution of Hydrous Manganite (γ-MnOOH)

The objective of this study was to describe the proton promoted disproportion of synthetic manganite (γ-MnOOH) and to characterise the resulting phase transformations. The solution and remaining solid phase after disproportionation was analysed by techniques including atomic absorbance spectroscopy, X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). In suspensions with pH between 5 and 7, −log[H⁺] was monitored for 17 months and equilibrium constants were determined at 9, 12 and 17 months of reaction time for the following reaction (25 °C, 0.1 M (Na)NO₃):

黄铁矿成因形态学

在1981—1986年野外工作的基础上,作者对胶东三县四个金矿床黄铁矿晶体形态进行了系统研究,对其中2495粒晶体进行了统计,对300粒晶体进行了测角,对60粒晶体进行了微形貌观察。根据以上实际工作及国内外有关资料提出了黄铁矿晶休常见单形出现频率的定量资料与晶体微形貌的特点,特别是{210}面上负条纹的特征与成因探讨。并讨论了黄铁矿晶体形态与分带性,与形成温度,与主、微量成分,与共生组合及与矿化等的关系。查明黄铁矿形态及其晶面微形貌的发育与硫逸度、温度、冷却速度等密切相关。在以上基础上提出了胶东四个金矿床中蚀变岩型金矿及石英脉型金矿两种成因类型黄铁矿形态特征上的五点差异。最后对黄铁矿研究方法要点进行了总结。     

Atomistic simulation of the effect of impurities on vacancy migration at the {4 1 0}/[0 0 1] tilt grain boundary of MgO

We present the results of atomistic simulations to calculate the effect of impurities on vacancy migration at the {4 1 0} tilt grain boundary of MgO. We show that impurities within the mantle could significantly modify vacancy migration within the mantle due to segregation to grain boundaries. This segregation increases with increasing impurity size and with increasing pressure. The impurities have little effect on vacancy migration at 0 GPa but at higher pressures the impurities alter the activation energies such that the vacancies prefer to migrate towards them. This suggests that at mantle conditions the vacancies will be pinned both by the compression of the boundary and also the impurities, slowing diffusion. Received: 22 February 1999 / Revised, accepted: 1 June 1999     

Mechanical twinning in calcite considered with the concept of ferroelasticity

The mechanical twinning of calcite is compared with ferroelastic behavior. For calcite a paraelastic prototype phase does not exist, therefore a virtual prototype is defined with cubic m3m symmetry. Using this condition the strain tensors of all domain states of mechanical twinning are calculated. With the use of the strain tensors, application of Sapriel's strain compatibility law gives the crystallographic orientations of all possible twin planes between different domain states. The findings indicate that the twin walls are {1 0 0} and {1 1 0} planes with respect to the morphological rhombohedral lattice. These twin plane orientations from the equated strain tensors are in accordance with the r-and e-twin systems commonly observed in calcite. Received: 17 December 1998 / Revised, accepted: 24 April 1999     

Copper-gold endoskarns and high-Mg monzodiorite–tonalite intrusions at Mt. Shea,Kalgoorlie, Australia: implications for the origin of gold–pyrite–tennantite mineralization in the Golden Mile

Five Cu–Au epidote skarns are associated with the Mt. Shea intrusive complex, located in the 2.7–2.6 Ga Eastern Goldfields Province of the Archean Yilgarn craton, in greenstones bounded by the Boulder Lefroy and Golden Mile strike-slip faults, which control the Golden Mile (1,435 t Au) at Kalgoorlie and smaller “orogenic” gold deposits at Kambalda. The Cu–Au deposits studied are oxidized endoskarns replacing faulted and fractured quartz monzodiorite–granodiorite. The orebodies are up to 140 m long and 40 m thick. Typical grades are 0.5% Cu and 0.3 g/t Au although parts are richer in gold (1.5–4.5 g/t). At the Hannan South mine, the skarns consist of epidote, calcite, chlorite, magnetite (5–15%), and minor quartz, muscovite, and microcline. Gangue and magnetite are in equilibrium contact with pyrite and chalcopyrite. The As–Co–Ni-bearing pyrite contains inclusions of hematite, gold, and electrum and is intergrown with cobaltite and Cu–Pb–Bi sulfides. At the Shea prospect, massive, net-textured, and breccia skarns are composed of multistage epidote, actinolite, albite, magnetite (5%), and minor biotite, calcite, and quartz. Gangue and magnetite are in equilibrium with Co–Ni pyrite and chalcopyrite. Mineral-pair thermometry, mass-balance calculations, and stable-isotope data (pyrite δ³⁴S_CDT = 2.5‰, calcite δ¹³C_PDB = −5.3‰, and δ¹⁸O_SMOW = 12.9‰) indicate that the Cu–Au skarns formed at 500 ± 50°C by intense Ca–Fe–CO₂–S metasomatism from fluids marked by an igneous isotope signature. The Mt. Shea stock–dike–sill complex postdates the regional D1 folding and metamorphism and the main phase of D2 strike-slip faulting. The suite is calc-akaline and comprises hornblende–plagioclase monzodiorite, quartz monzodiorite, granodiorite, and quartz–plagioclase tonalite porphyry. The intrusions display a wide range in silica content (53–73 wt% SiO₂), in ratio (0.37–0.89), and in ratio (0.02–0.31). Chromium (62–345 ppm), Ni (23–158), Sr (311–1361 ppm), and Ba (250–2,581 ppm) contents are high, Sr/Y ratios are high (24–278, mostly >50), and the rare earth element patterns are fractionated . These features and a negative niobium anomaly relative to the normal mid-ocean ridge basalt indicate that the suite formed by hornblende fractionation from a subduction-related monzodiorite magma sourced from metasomatized peridotite in the upper mantle. The magnesian composition of many intrusions was enhanced due to hornblende crystallization under oxidizing hydrous conditions and during the subsequent destruction of igneous magnetite by subsolidus actinolite–albite alteration. At the Shea prospect, main-stage Cu–Au epidote skarn is cut by biotite–albite–dolomite schist and by red biotite–albite replacement bands. Post-skarn alteration includes 20-m-thick zones of sericite–chlorite–ankerite schist confined to two D3 reverse faults. The schists are mineralized with magnetite + pyrite + chalcopyrite (up to 0.62% Cu, 1.6 g/t Au) and are linked to skarn formation by shared Ca–Fe–CO₂ metasomatism. Red sericitic alteration, marked by magnetite + hematite + pyrite, occurs in fractured porphyry. The biotite/sericite alteration and oxidized ore assemblages at the Shea prospect are mineralogically identical to magnetite–hematite-bearing gold lodes at Kambalda and in the Golden Mile. Published fluid inclusion data suggest that a “high-pressure”, oxidized magmatic fluid (2–9 wt% NaCl equivalent, , 200–400 MPa) was responsible for gold mineralization in structural sites of the Boulder Lefroy and Golden Mile faults. The sericite–alkerite lodes in the Golden Mile share the assemblages pyrite + tennantite + chalcopyrite and bornite + pyrite, and accessory high-sulfidation enargite with late-stage sericitic alteration zones developed above porphyry copper deposits.     

Interaction of Freshly Precipitated Silica Gel with Aqueous Silicic Acid Solutions under Ambient and Near Neutral pH-conditions: A Detailed Analysis of Linear Rate Law

Interaction of freshly precipitated silica gel with aqueous solutions was studied at laboratory batch experiments under ambient and near neutral pH-conditions. The overall process showed excellent reversibility: gel growth could be considered as an opposite process to dissolution and a linear rate law could be applied to experimental data. Depending on the used rate law form, the resulting rate constants were sensitive to errors in parameters/variables such as gel surface area, equilibrium constants, Si-fluxes, and reaction quotients. The application of an Integrated Exponential Model appeared to be the best approach for dissolution data evaluation. It yielded the rate constants k _dissol ∼ (4.50 ± 0.68) × 10⁻¹² and k _growth ∼ (2.58 ± 0.39) × 10⁻⁹ mol m⁻² s⁻¹ for zero ionic strength. In contrast, a Differential Model gave best results for growth data modeling. It yielded the rate constants k _dissol ∼ (1.14 ± 0.44) × 10⁻¹¹ and k _growth ∼ (6.08 ± 2.37) × 10⁻⁹ mol m⁻² s⁻¹ for higher ionic strength (I ∼ 0.04 to 0.11 mol L⁻¹). The found silica gel solubility at zero ionic strength was somewhat lower than the generally accepted value. Based on the and standard Gibbs free energy of silica gel formation was calculated as and −850,318 ± 20 J mol⁻¹, respectively. Activation energies for silica gel dissolution and growth were determined as and respectively. An universal value for growth of any silica polymorph, is not consistent with the value for silica gel growth, which questions the hypothesis about one unique activated complex controlling the silica polymorph growth.     

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO₃ was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω_calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL.Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.     

Molecular-scale surface processes during the growth of calcite in the presence of manganese

This paper deals with the growth behaviour of the Mn-Ca-CO₃-H₂O solid solution-aqueous solution system on calcite {104} surfaces. This system represents a model example, which allows us to study the effect of a number of controlling factors on the crystallisation: (1) the supersaturation function, β(x), and nucleation rate function, J(x), for the Mn-Ca-CO₃-H₂O system, (2) the relationship of such functions to the molecular scale growth mechanisms operating on growing surfaces, and (3) the surface structure of the calcite {104} faces. In situ atomic force microscopy (AFM) growth experiments revealed a wide variety of surface phenomena, such as the transition between growth mechanisms, anisotropic changes in the step rates, and the influence of the Mn-bearing newly formed surface on subsequent growth (step stoppage followed by the formation of two-dimensional nuclei and the reproduction of the original calcite {104} surface microtopography). These phenomena result from the interplay between the controlling parameters and are explained in those terms.     

Sector-zoned augite megacrysts in Aleutian high alumina basalts: implications for the conditions of basalt crystallization and the generation of calc-alkaline series magmas

Several high alumina basalts from the Aleutian volcanic centers of Cold Bay and Kanaga Island contain large (up to 1.5 cm diameter) megacrysts of sector-zoned augite. The megacrysts are invariably euhedral with well developed {001}, {010} and {111} forms. All crystals display concentric bands that are rich in mineral and glass inclusions. The sector zonation typically occurs as well developed (010), (100), (111) and (110) sectors which grew at different rates. A comparison of the width of synchronous growth bands indicates that following relative growth rates: (111) ≫ (100) ∼ (110) > (010). Compositionally, SiO₂ and MgO abundances decrease, and TiO₂, Al₂O₃, FeO and Na₂O abundances increase in the different sectors in the order (111), (100) ∼ (110), (010). This order is identical to that deduced for the relative growth rates, implying that growth rate clearly had a role in the development of the sector zonation. Calculated pre-eruption H₂O contents of the basalts range from 1 to 3 wt% but actual (measured) post-eruption H₂O contents range from 0.01 to 0.3 wt%. Deteurium isotopic values are heavily depleted and range from −110 to −141‰ . Together these indicate significant vapor (H₂O) exsolution prior to eruption. Maximum H₂O abundances in primitive glass inclusions, thought to be most representative of the host liquid reservoir at the time of melt entrapment, systematically decrease from the core to the rim of one augite megacryst studied in detail. We conclude that the presence of sector-zoned augite is due to augite supersaturation and rapid crystallization brought about by magma decompression and volatile (H₂O) exsolution. The calculated pre-eruption H₂O contents of 1–3 wt% limit vapor exsolution and basalt crystallization to depths of less than 3 and more likely 1.5 km. Very rapid crystallization at very shallow depths makes it unlikely that the time scales between initial crystallization and final eruption are sufficient to permit appreciable amounts of fractional crystallization. Given that high alumina basalt fractionation is the dominant process for generating more evolved andesite, dacite and rhyolite magmas of the calc-alkaline suite, the inability of parental high alumina basalt to yield such derivative magmas in the low pressure environment places the likely site of fractionation in the high pressure environment, at or near the base of the crust. Received: 1 December 1997 / Accepted: 23 December 1998     

The non-oxidative dissolution of galena nanocrystals: Insights into mineral dissolution rates as a function of grain size, shape, and aggregation state

The acidic, non-oxidative dissolution of galena (PbS) nanocrystals has been studied in detail using transmission electron microscopy (TEM) to follow the evolution of the size and shape of the nanocrystals before and after dissolution experiments, X-ray photoelectron spectroscopy (XPS) to follow particle chemistry, and dissolution rate analysis to compare dissolution rates between nanocrystalline and bulk galena. Dissolution characteristics were also studied as a function of nanocrystal access to bulk vs. confined solution due to the degree of proximity of next-nearest grains. Nearly monodisperse galena nanocyrstals with an average diameter of 14.4 nm were synthesized for this study, and samples were exposed to pH 3, deoxygenated HCl solutions for up to 3 h at 25 °C. Detailed XPS analysis showed the nanocrystals to be free of unwanted contamination, surface complexes, and oxidative artifacts, except for small amounts of lead-containing oxidation species in both pre- and post-dissolution samples which have been observed in fresh, natural bulk galena. Depending on the calculation methods used, galena nanocrystals, under the conditions of our experiments, dissolve at a surface area normalized rate of one to two orders of magnitude faster than bulk galena under similar conditions. We believe that this reflects the higher percentage of reactive surface area on nanocrystalline surfaces vs. surfaces on larger crystals. In addition, it was shown that {1 1 1} and {1 1 0} faces dissolve faster than {1 0 0} faces on nanocrystals, rationalized by the average coordination number of ions on each of these faces. Finally, dissolution was greatly inhibited for galena nanocrystal surfaces that were closely adjacent (1-2 nm, or less) to other nanocyrstals, a direct indication of the properties of aqueous solutions and ion transport in extremely confined spaces and relevant to dissolution variations that have been suspected within aggregates.     

Comparison of the surface structure of the tetrahedral sheets of muscovite and phlogopite by AFM

 The surface structure of the tetrahedral sheet of dioctahedral mica muscovite was compared to that of the tetrahedral sheet of trioctahedral mica phlogopite using atomic force microscopy (AFM). AFM revealed distinct structural differences between the tetrahedral sheet surfaces of the two micas. The hexagonal ring in the AFM image of muscovite elongates in the [3 1 0] direction, and the groove runs perpendicular to the [3 1 0] direction. On the phlogopite surface, the hexagonal ring contracts slightly in the a axis direction, but the groove is not apparent. These results were consistent with the bulk structure data of the two micas determined by X-ray diffraction (XRD). The degree of surface relaxation was much larger in muscovite than in phlogopite. In muscovite, the interlayer K reduces the amount of tetrahedral rotation that actually occurs, since the interlayer K is too large for its hexagonal hole after full tetrahedral rotation. Thus, it is naturally expected that muscovite will show more tetrahedral rotation after removal of the interlayer K. It is also expected that muscovite will show more tilting of SiO₄ tetrahedra after cleaving, since an attractive force between the hydrogen in the OH group and the lower basal oxygen should be in operation, due to the decreased distance between them following interlayer K removal. Received: 14 March 2000 / Accepted: 29 July 2000     

Computer simulation of the structure and stability of forsterite surfaces

The aim of this paper is to demonstrate that atomistic simulations can be used to evaluate the structure of mineral surfaces and to provide reliable data for forsterite surfaces up to a plane index of 2 using the code METADISE. The methods used to calculate the surface structure and energy which have more commonly been used to study ceramics are briefly explained as is a comparison with experimental data, most notable the crystal morphology. The predicted morphologies show that all the methods (Donnay-Harker, Attachment energies and equilibrium) show most of the surfaces that are expressed in observed crystals. The equilibrium morphology calculated from the relaxed surface energies is the only method which expresses the {201} surfaces and the {101} surfaces, which appear only upon relaxation. The more stable surfaces are shown to be those which have the highest surface density and more closely resemble close packed structures with highly coordinated surface ions and silicon as far from the surface as possible. The most stable surfaces the {100} which has alternating layers of MgO and SiO₂ terminating with an MgO layer. The structure is similar to the MgO {100} surfaces and has a similar energy (1.28?Jm^?2 compared to 1.20). The second most stable are the {201} which have a stepped surface topology, but is also compact with a relaxed surface energy of 1.56?Jm^?2. The results indicate that atomistic simulation is well suited to the prediction of surface structure and morphology although care must be taken in choosing potentials which model the structure and elastic properties accurately.     

Crustal Growth Rate of the North China Platform：a Method of Estimating Mass Equilibrium between Crust and Mantle

The following equation is proposed in this paper to estimate the crustal growth rate of the North China Platform on the basis of mass equilibrium between the crust and the mantle:

平武板状绿柱石{0001}晶面的溶蚀像特征与晶体生长

板状绿柱石产于花岗岩云英岩化边部或晶洞壁的白云母-钠长石-绿柱石-水晶的矿物组合中,钠长石呈自形晶,绿柱石的洁净度与透明度相对较差。晶体测量表明,晶体的单形晶面发育依次为c{0001}→s{11 2-1}→p{10 1-1}→m{10 1-0}→v{21 3-1}、n{45 9-4}、a{11 2-0}。微分干涉显微镜(DIC)及扫描电镜(SEM)研究表明:各单形晶面上生长纹(微形貌)反映面网结构的对称性,c{0001}单形晶面上的六边形溶蚀坑(50～170μm)是由平行晶体C轴的各单形晶面生长层从晶体中心向外叠堆组成,层生长机理制约晶体生长全过程,平行双面(c)的生长层较薄(5～8μm)且较稳定,六方双锥(s)生长层较厚且圆滑,六方柱(m)生长层由晶体中心往外其厚度由厚逐渐变薄(12～20μm),台间隔由窄变宽。晶体溶蚀是从面网密度最大的c{0001}开始,溶蚀面积依平行双面(c)、六方双锥(s)单形晶面由大变小,六方柱(a)、复六方双锥(v、n)单形晶面因面网密度小而未受到溶蚀。据矿物共生组合、流体包裹体均一法测量与拉曼光谱(LRS)分析表明板状绿柱石是在中–高温(303℃)、过饱和度较大、成矿介质的钠长石化发育且热动力环境相对稳定的条件下形成,气液包裹体主要由H2O、CO2及微量CH4、N2组成,CO2及微量CH4、N2可能与碳酸盐围岩有关。     

In situ atomic force microscopy measurements of biotite basal plane reactivity in the presence of oxalic acid

We have used a direct imaging technique, in situ atomic force microscopy (AFM), to observe the dissolution of the basal biotite surface by oxalic acid over a range of temperatures close to ambient conditions, using a specially designed AFM liquid cell and non-invasive intermittent contact mode of operation. From the 3-dimensional nanometre-resolution data sets, we observe a process characterised by the slow formation of shallow etch pits in the (0 0 1) surface and fast growth of etch pits from the resulting steps, which represent proxies for the {h k 0} surface. Measurements of dissolution rates as a function of temperature allow a determination of an apparent activation energy (E_a,app) for the process, via mass-loss calculations from image analysis. We obtain a value of E_a,app = 49 ± 2 kJ mol⁻¹, which is consistent with separate calculations based on planar area etch pit growth, and measurements of etch pit perimeters, indicating that this value of E_a,app is representative of {h k 0} surface dissolution. The measurement of etch pit perimeters also enables an estimation of apparent activation energy as a function of step density indicating substantially higher apparent activation energy, up to E_a,app = 140 kJ mol⁻¹, on extrapolation towards a pristine surface with no defects. We suggest that this higher value of E_a,app represents the slow formation of etch pits into the (0 0 1) surface.     

Evaluation of the Crystallization Conditions for the Calcalkaline Russian Peak Intrusive Complex, Klamath Mountains, Northern California

The mid-Jurassic calcalkaline Russian Peak intrusive complex,located in the Klamath Mountains of northern California, consistsof an elliptical peridotite-to-quartz diorite suite intrudedby two plutons of granodiorite. Several techniques were usedto decipher the crystallization conditions for ultramafic rocks,quartz diorite, and granodiorite, including comparison of parageneseswith crystallization experiments, application of geothermometersand barometers, and evaluation of phase equilibria. Contactmetamorphic assemblages, hornblende barometry, and amphibolesubstitution schemes indicate that pressures of intrusion were{small tilde}3 kbar. Plagioclase and pyroxene thermometry indicateintrusion temperatures of {small tilde}1000C for quartz dioriteand 900C for granodiorite. Phase equilibrium analysis for thereaction phlogopite+quartz=K-feldspar+enstatite+H₂O, coupledwith an estimate of the water-saturated quartz diorite solidus,suggests that the solidus of two-pyroxene quartz diorite wasat {small tilde}780C with a mole fraction of water of {smalltilde}0•55. The composition of granodiorite is very similarto that used in several crystallization experiments and indicatesa solidus of 70025C. Estimates of oxygen fugacity, obtainedfrom equilibrium relations of olivine, orthopyroxene, and spinelin ultramafic rocks, magnetite and ilmenite in quartz diorite,and magnetite, K-feldspar, and biotite in quartz diorite andgranodiorite are 2•1–2•5 and 1•0–1•3log units above the quartz-fayalite-magnetite (QFM) buffer forgranodiorite and quartz diorite at their respective solidustemperatures; and 1•0–4•0 log units above QFMfor ultramafic rocks and quartz diorite at subsolidus temperatures.Thus, the quartz diorite magma was hotter, drier, and slightlyreduced relative to the grandiorite magma, differences thatset important constraints on the genesis of the Russian Peakmagmas. These results also indicate that quartz diorite wasundersaturated with respect to H₂O as it reached its solidus,a condition that is consistent with the absence of deutericalteration in this unit. In contrast, granodiorite shows extensivedeuteric alteration and features pegmatites, quartz pods, andradial dikes as might be expected for H₂O-saturated conditions. Although calcalkaline plutonic complexes present serious difficultiesin estimating the intensive parameters of crystallization, judiciousapplication of appropriate methods may result in the successfulevaluation of the conditions of crystallization of such complexes.     

In situ Atomic Force Microscopy study of dissolution of the barite (0 0 1) surface in water at 30 °C

The dissolution behavior of the barite (0 0 1) surface in pure water at 30 °C was investigated using in situ Atomic Force Microscopy (AFM), to better understand the dissolution mechanism and the microtopographical changes that occur during the dissolution, such as steps and etch pits. The dissolution of the barite (0 0 1) surface started with the slow retreat of steps, after which, about 60 min later, the <hk0> steps of one unit cell layer or multi-layers became two-step fronts (fast “f” and slow “s” steps) with a half-unit cell layer showing different retreat rates. The “f” step had a fast retreat rate (≈(14 ± 1) × 10⁻² nm/s) and tended to have a jagged step edge, whereas the “s” step (≈(1.8 ± 0.1) × 10⁻² nm/s) had a relatively straight front. The formation of the “f” steps led to the formation of a new one-layer step, where the front of the “s” step was overtaken by that of the immediate underlying “f” step. The “f” steps also led to the decrease of the <hk0> steps and the increase in the percentage of stable steps parallel to the [0 1 0] direction during the dissolution.Etch pits, which could be observed after about 90 min, were of three types: triangular etch pits with a depth of a half-unit cell, shallow etch pits, and deep etch pits. The triangular etch pits were bounded by the step edges parallel to [0 1 0], [1 2 0], and [] and had opposite orientations in the upper half and lower half layers. Shallow etch pits that had a depth of two or more half-unit cell layers had any two consecutive pits pointing in the opposite direction of each other. The triangular etch pit appeared to grow by simultaneously removal of a row of ions parallel to each direction from the three step edges. At first, deep etch pits were elongated in the [0 1 0] direction with a curved outline and then gradually developed to an angular form bounded by the {1 0 0}, {3 1 0}, and (0 0 1) faces. The retreat rate of the (0 0 1) face was much slower than those of the {1 0 0} and {3 1 0} and tended to separate into two rates ((0.13 ± 0.01) × 10⁻² nm/s for the deep etch pits derived from a screw dislocation and (0.07 ± 0.01) × 10⁻² nm/s for those from other line defects).The changes in the dissolution rate of a barite (0 0 1) surface during the dissolution were estimated using the retreat rates and densities of the various steps as well as the growth rates, density, and areas of the lateral faces of the deep etch pits that were obtained from this AFM analysis. Our results showed that the dissolution rate of the barite (0 0 1) surface gradually increased and approached the bulk dissolution rate because of the change in the main factor determining the dissolution rate from the density of the steps to the growth and the density of the deep etch pits on the surface.     

Origin of optical variation in chabazite

At a low degree of supersaturation a crystal forming from solution grows by repeated addition of layers to the crystal faces. A three-dimensional structure is therefore formed by the stacking of two-dimensional nets. The two-dimensional atomic arrangement exposed on the growing faces and its symmetry controls the ordering of cations and/or anions added to the surface. The distribution of Al and Si seems to be particularly prone to ordering of this kind. In chabazite the optical properties corresponding to the degree of ordering differ from growth sector to growth sector produced on the vicinal faces {hkill} of growth hillocks. The optically triclinic sectors in chabazite form on a vicinal face which inclines to the morphological mirror plane and the c-axis, and the mirror plane of the growth hillock becomes the twin plane of the sector. Thus, chabazite showing rhombohedral form consists of six twinned sectors corresponding to six {10ulbar;11} faces in which some small twinned sectors correlated with the symmetrical vicinal faces can be seen under the optical microscope.