The effect of fluid pressure on oxygen isotope exchange between feldspar and water

The rate of oxygen isotope exchange between adularia and 2 M KCl solution has been measured at 650°C at pressures from 125 to 4000 bar. Isotropie diffusion coefficients calculated from these data show a positive dependence on the fluid pressure. This dependence is opposite to the predicted effect of hydrostatic pressure and is attributed to the activity of ‘water’ (H₂O, H⁺ or OH^?) in the feldspar.     

Rate constants of dissolution derived from the measurements of mass balance in hydrological catchments

The experimental rate constant of dissolution of oligoclase, 1.7 × 10 ^{? 2} mol · m^?2 · s^?1 (Busenberg and Clemency, 1976), is compared with rate constants, 5.2 × 10^?15 to 6.8 × 10^?13 mol · m^?2· s^?1, derived from mass-balance measurements of sodium in hydrological catchments. The wide range of the field-based rate constants mainly reflects the uncertainty in the evaluation of the specific wetted surface of rock in aquifer. The most probable order of magnitude of the field rate constant is 10^?14 mol · m^?2· s^?1. The difference between the experimental and field rate constant is only partly caused by lower temperature and lowerP_CO2 in the aquifer. The main reason for the discrepancy is the diverse history of the mineral surfaces undergoing reaction.It is suggested that the feldspar surfaces in an aquifer are old, compared to those of feldspars utilized in laboratory experiments. They have fewer defects and are smooth. The fresh surfaces of feldspars studied in the laboratory consist of many kinks and ledges and small-area terraces which dissolve faster.The differences in rate constants derived from field data on several specific catchments indicate that the anthropogenic processes which have operated during this century in Central Europe speed up the rate of dissolution by a factor of three. Modern agricultural practices speed up the rate by a factor of five.     

Dissolution kinetics of dolomite: Effects of lithology and fluid flow velocity

The dissolution kinetics of three stoichiometric dolomite specimens (hydrothermal single crystal, microcrystalline sedimentary rock, coarse-grained marble) were studied in aqueous carbonate solutions. Hydrodynamic conditions were controlled through use of a rotating dolomite disk in which one face was exposed to solution and fluid flow regime was defined by spinning rate. The resulting mass transfer properties were uniform across the disk surface. The dissolution experiments were begun at an initially undersaturated condition set by CO₂ at ~ 1 atm dissolved in deionized water. The reaction was followed by measuring concentrations of Ca²⁺, Mg²⁺, HCO₃^?, and pH over time in a free-drift type of experiment at 0, 15, and 25°C.Dissolution rates for all three samples were similar in form and value; grain size effects were insignificant. Ca/Mg was constant throughout each run at 0.81–0.96. From initial conditions, the dissolution rate decreased as the solution became more saturated. At solution conditions still far from equilibrium (ion activity product = 10^?19), rate dropped off sharply to a very low value. Surface morphology, determined by SEM, showed deep narrow holes in the single crystal, while the rocks dissolved along grain boundaries. These features suggested preferential dissolution of energetically favored sites and surface reaction rate control. Initial rates were used to calculate an apparent activation energy of 32 kJ mol^?1 (sedimentary dolomite) and 27 kJ mol^?1 (single crystal).Initial dissolution rates at 25°C and pH ~ 4 for all samples varied with spinning speed and ranged from 1–3 μmol m^?2 s^?1 for laminar flow conditions to almost 3–6 μmol m^?2 s^?1 as the transition to turbulence began. At lower temperatures, the rate was lower, and increasing spinning velocity had less effect. The strongest spinning rate dependence occurred far from equilibrium, and it became a less important factor as the saturation state increased.     

Temperature dependence of calcite dissolution kinetics between 1 and 62°C at pH 2.7 to 8.4 in aqueous solutions

The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole^?1 for Carrara marble and 46 ± 4 kJ mole^?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole^?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole^?1 and this high EAAE is consistent with transport dependence on product diffusion in this H⁺-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole^?1, also decreasing with increasing temperature. This is compatible with H⁺-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H⁺-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H⁺-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.     

Early Cretaceous mineralizing activity in the St. Andreasberg ore district (Southwest Harz,Federal Republic of Germany)

In the St. Andreasberg ore district, southwest Harz, at some time between the main and subsequent stages of mineralization sensu Wilke (1952), potassium feldspar (adularia) was formed hydrothermally. Based on isotopic dating (Rb/Sr, ⁴⁰Ar/³⁹Ar), the formation of this mineral is ascribed to the Early Cretaceous. Thus, part of the St. Andreasberg mineralization is proved to have been formed in the Late Mesozoic. The mineralization process forming feldspar does not coincide with magmatic phases of the area.     

Mineral chemistry and thermobarometry of Eocene monzogabbroic stocks from the Bafra (Samsun) area in Turkey: implications for disequilibrium crystallization and emplacement conditions

Monzogabbro stocks including felsic enclaves (monzosyenite) around the Bafra (Samsun) area at the western edge of the Eastern Pontides cut Eocene-aged volcanic and sedimentary units. The monzogabbros contain plagioclase, alkali feldspar, clinopyroxene, olivine, hornblende, biotite, apatite, and iron-titanium oxides, whereas the felsic enclaves contain alkali feldspar, plagioclase, hornblende, biotite, clinopyroxene, and iron-titanium oxides. Mineral chemistry data suggest that magmas experienced hydrous and anhydrous crystallization in deep and shallow crustal magma chambers. Several thermobarometers were used to estimate temperatures of crystallization and emplacement for the mafic and felsic magmas. Clinopyroxene thermobarometry yielded 1100–1232 C and 5.9–8.1 kbar for monzogabbros, and 931–1109 C and 1.8–6.9 kbar for felsic enclaves. Hornblende thermobarometry and oxygen fugacity estimates reveal 739–971°C, 7.0–9.2 kbar and 10^?9.71 for monzogabbros and 681–928°C, 3.0–6.1 kbar and 10^?11.34 for felsic enclaves. Biotite thermobarometry shows elevated oxygen fugacity varying from 10^?18.9–10^?11.07 at 632–904°C and 1.29–1.89 kbar for monzogabbros, to 10^?15.99 –10^?11.82 at 719–873°C and 1.41–1.77 kbar for felsic enclaves. The estimated zircon and apatite saturation temperatures are 504–590°C and 693–730°C for monzogabbros and 765–775°C and 641–690°C for felsic enclaves, respectively. These data imply that several phases in the gabbroic and syenitic magmas did not necessarily crystallize simultaneously and further indicate that the mineral compositions may register intervals of disequilibrium crystallization. Besides, thermobarometry contrasts between monzogabbro and felsic enclave may be partly a consequence of extended interactions between the mafic and felsic magmas by mixing/mingling and diffusion. Additionally, the hot felsic magma was close to liquidus conditions (crystallinity < 30%) when injected into cooler mafic magma (crystallinity > 50%), and thus, the monzogabbro stocks reflect hybrid products from the mingling and incomplete mixing of these two magmas.     

40Ar-39Ar age of the Shergotty achondrite and implications for its post-shock thermal history

Analyses of ⁴⁰Ar-³⁹Ar have been made on a whole rock sample and a maskelynite (feldspar) separate of the shocked Shergotty achondrite. The maskelynite gave a plateau age of 254 ± 10 Myr. The whole rock sample gave a complex release with apparent ages between 240 and 640 Myr. The slightly younger Rb-Sr isochron age of 165 Myr for Shergotty (Nyquistet al., 1978) suggests that the maskelynite as well as the whole rock was incompletely degassed. Reasonable Ar diffusion characteristics for Shergotty for shock heating temperatures of <400°C indicate D/a² of 10^?11?10^?13 sec^?1. The time required to lose 95% of the ⁴⁰Ar from the plagioclase would be ~10³–10⁴ yr. When this gas diffusion time is introduced into a thermal model of a cooling ejecta blanket of variable thickness, a post-shock cooling time of ? 10³ yr and a burial depth of ? 300 m are indicated for Shergotty. These conclusions are not seriously affected by uncertainties in the thermal model. Most likely the shock event occurred ~ 165 Myr ago, but no earlier than 250 Myr ago, when the Shergotty parent object experienced a collision in the asteroid belt. As a result of that collision, feldspar was converted to maskelynite, the K-Ar and Rb-Sr ages were completely or nearly completely reset, and the Shergotty meteorite was heated to <400°C and left to cool slowly inside the parent body.     

Adsorption of lead, ethylenediaminetetraacetic acid and lead-ethylenediaminetetraacetic acid complex onto granular activated carbon

This study investigated simultaneous removal of lead and ethylenediaminetetraacetic acid from synthetic wastewater samples using granular activated carbon adsorption. Data from a 1 × 10^?4 M lead-ethylenediaminetetraacetic acid adsorption isotherm study fitted well to Freundlich isotherm. Furthermore, for the pH-dependent 1 × 10?4 M lead-ethylenediaminetetraacetic acid study both lead and ethylenediaminetetraacetic acid adsorptions increased reaching values of 82 % and 93 % respectively at pH 5.8. However, a further increase in pH resulted in decreasing but near equal lead and ethylenediaminetetraacetic acid removals. Results for the 2 × ^10?4 M lead-ethylenediaminetetraacetic acid system showed a behavior that was qualitatively similar to the 1 × ^10?4 M lead-ethylenediaminetetraacetic acid findings. However, the 1×10^?3 M lead-ethylenediaminetetraacetic acid study showed only a decreasing adsorption trend. An increasing-decreasing type lead/ethylenediaminetetraacetic acid adsorption behavior was also noted for the 1× 10^?4 M lead/2 × 10^?4 M ethylenediaminetetraacetic acid system. Nevertheless for the 2×10^?4 M lead/1×10^?4 M ethylenediaminetetraacetic acid system, lead removal at increased pH was comparatively higher. Furthermore, results from a continuous column study completed at 1 × 10^?4 M lead and 0.75 × 10^?4 M ethylenediaminetetraacetic acid showed high saturation times both for lead and ethylenediaminetetraacetic acid. Results from the present work show that a notable removal of aqueous phase lead and ethylenediaminetetraacetic acid could be achieved using activated carbon adsorption. The details related to the effect of pH and pollutants’ concentration on the overall adsorption efficiency, as reported in the present work, would be of much use for an effective carbon adsorption process design for the treatment of respective wastewaters.     

Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure

We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm^?1 display a small frequency lowering (<4 cm^?1) and a moderate broadening (<10 cm^?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm^?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm^?1 respectively) and broadening (~30 cm^?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm^?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm^?1, at ?194 °C. They exhibit significant frequency increase (~20 cm^?1) and broadening (~70 cm^?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)_Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm^?1 (type (2); 3,550 cm^?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)_Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.     

Eight-phase alkali feldspars: low-temperature cryptoperthite, peristerite and multiple replacement reactions in the Klokken intrusion

Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460–340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab₉₁Or₁An₈), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical turbidity. We term this material ultra porous late feldspar (UPLF). It is composed predominantly of regions of microporous very Or-rich feldspar (mean Ab_2.5Or_97.4An_0.1) associated with very pure porous albite (Ab_97.0Or_1.6An_1.4) implying replacement below 170–90 °C, depending on degree of order. In TEM, UPLF has complex, irregular diffraction contrast similar to that previously associated with low-temperature albitization and diagenetic overgrowths. Replacement by UPLF seems to have been piecemeal in character. Ghost-like textural pseudomorphs of both braid and film parents occur. Formation of patch perthite, film perthite and peristerite occurred 10⁴–10⁵ year after emplacement, but there are no microtextural constraints on the age of UPLF formation.     

Effect of organic acids and fluoride on the dissolution kinetics of hydrous alumina. A model study using the rotating disc electrode

The dissolution of aluminium oxide was studied with an oxide film covered rotating disc aluminium electrode. This allows us to make measurements under conditions of well defined mass transport under conditions representative of those found in natural waters (conc. of Al, organic acids and fluoride), and permits us to distinguish between surface-controlled and transport-controlled rates.Under steady-state conditions, the dissolution current is a direct measure of the flux of dissolving Al ions at the aqueous interface of the amorphous hydrous oxide film.At pH 3–6 and in presence of organic ligands, dissolution is controlled by a surface process, i.e. the rate of detachment of surface complexes. Fluoride ions in concentrations ≥ 10^?6 M increase dramatically the dissolution rate: at pH = 4 the process is controlled by convertive diffusion of F^? from the solution to the surface (k_F- = (3.6 ± 0.5) × 10^?2cms^?1). Competitive and reversible adsorption of organic ligands (10^?6 ? 10^?2M) displacing fluoride slows down the rate of detachment of the surface complex which becomes the rate-limiting step. The affinity of ligands for the Al₂O₃ surface sites increases in the sequence: formate ~ chloride ~ carbonate < acetate < sulphate < salicylate < fumarate < maleate < malonate ? oxalate ? fluoride ≤ citrate.The results are compared with simulated weathering experiments and interpreted in terms of the surface complexation model.     

Origin of rapidly solidified metal-troilite grains in chondrites and iron meteorites

Inclusions of troilite and metallic Fe,Ni 0.2–4 mm in size with a dendritic or cellular texture were observed in 12 ordinary chondrites. Cooling rates in the interval 1400?950°C calculated from the spacing of secondary dendrite arms or cell widths and published experimental data range from 10^?7 to 10⁴°C/sec. In 8 of these chondrites, which are breccias containing some normal slow-cooled metal grains, the inclusions solidified before they were incorporated into the breccias. Their cooling rates of 1–300 °C/sec indicate cooling by radiation, or by conduction in contact with cold silicate or hot silicate volumes only 6–40 mm in size. This is quantitative evidence that these inclusions and their associated clasts were melted on the surface of a parent body (by impact), and were not formed at depth from an internally derived melt. In Ramsdorf, Rose City and Shaw, which show extensive reheating to ? 1000°C, Fe-FeS textures in melted areas are coarser and indicate cooling rates of 10^?1 to 10^?4°C/sec during solidification. This metal may have solidified inside hot silicate volumes that were 10–300 cm in size. As Shaw and Rose City are breccias of unmelted and melted material, their melted metal did not necessarily cool through 1000°C within a few m of the surface. Shock-melted, fine-grained, irregular intergrowths of metal and troilite formed in situ in many irons and some chondrites by rapid solidification at cooling rates of ? 10⁵°C/sec. Their kamacite and taenite compositions may result from annealing at ~250°C of metallic glass or exceedingly fine-grained quench products.     

Geochemical Charactristics and Genesis of Topaz—Bearing Porphyries in Yangbin Area of Taishun County,Zhejiang Province

The host rocks of the porphyry tin deposits in the Yangbin area are principally topaz-bearing porphyry dikes about 2 km long and 2–20m wide. Three lithologie types are identified for the dikes: topaz-bearing potassium feldspar granitic porphyry, topaz-bearing monzonitic granitic porphyry and topaz-bearing quartz porphyry. The content of topaz in the rocks ranges from 10 to 20 vol.%. Porphyritic texture is characteristic, with quartz, potassium feldspar and albite as main phenocryst minerals. The phenocryst occupies 10–20 vol% of the rocks. The rock groundmass consists of subhedral topaz, quartz and protolithionite. Topaz has a unit-cell parameter b=8.797 (Å), and F:OH=1.92:0.18, indicating a F-rich variety formed at high temperature. The topaz-bearing porphyries occurring in this area are strongly peraluminous (A/NKC=1.574–12.94), with high ratios of F/Cl (146–303) and Rb/Sr (5–122). They are rich in incompatible elements (Sn, 313 × 10^?6–1042 × 10^?6; W, 6 × 10^?6–218 × 10^?6; Nb, 27 × 10^?6–54 × 10^?6), but poor in compatible elements (Sr, 10 × 10^?6–28 × 10^?6; Ba, 58 × 10^?6–73 × 10^?6; V, 3 × 10^?6–12 × 10^?6, Cl, 150 × 10^?6–226 × 10^?6). The rocks are also characterized by high total REE amount (281.69 × 10^?6–319.76 × 10^?6), with strong Eu depletion (δEu=0.01–0.03) and low ratio of LREE/HREE (0.78–0.84). In summary, the authors propose an idea of S-type genesis for the topaz-bearing porphyries with tin mineralization, instead of I-type.     

Equilibration temperatures in enstatite chondrites

Equilibration temperatures for enstatite chondrites are calculated using a method suggested by Larimer (1968). The temperatures range from 640° to 840°C. The method yields temperatures which, in principle, are correct on a relative scale but the absolute error may be a large as 150°. There is a good correlation between the calculated temperatures and petrologic type as well as other mineralogic characteristics and bulk composition. Partial pressures of sulfur and oxygen at the time of equilibration were: pS₂ ~ 10^?8?10^?12 atm and pO₂ ~ 10^?28?10^?37.     

Types of Enclaves and Their Features and Origins in Intermediate-Acid Intrusive Rocks from the Tongling District, Anhui Province, China

Enclaves in intermediate-acid plutons from Tongling can be divided into three types: xenoliths, relics and magmatogenic enclaves. The magmatogenic enclaves consist of cumulates, micrograined dioritite mixtite and dioritic chilled border enclaves. Petrologically, relics with eyed and meta-poikilitic texture are characterized by high content of biotite (>80%) and low content of cordierite and grossular. The cumulates with accumulate texture consist of a great amount of pyroxene, hornblende and minor spinel and phlogopite. The micrograined dioritic mixtite is composed of more hornblendes and feldspar and less needle apatites and an ellipsoid basic core included in plagio-clase. The chilled border enclaves have the same mineral association, but more dark minerals than the host rocks consisting of plagioclase, quartz, alkaline feldspar, hornblende and biotite. Geochemically, the relics exhibit high REE content (455.8×10-6) and high ratio of LREE/HREE, more obvious Eu negative anomaly and are rich in Cr and     

Surface chemistry and dissolution kinetics of glassy rocks at 25°C

The weathering rates and mechanisms of three types of glassy rocks were investigated experimentally at 25 °C, pH 1.0 to 6.2, and reaction times as much as to 3 months. Changes in major element chemistry were monitored concurrently as a function of time in the aqueous solution and within the near surface region of the glass. Leach profiles, obtained by a HF leaching technique, displayed near-surface zones depleted in major cations. These zones increased in depth with increasing time and decreasing pH of reactions. Release rates into the aqueous solution were parabolic for Na and K and linear for Si and Al. A coupled weathering model, involving surface dissolution with concurrent diffusion of Na, K, and Al, produced a mass balance between the aqueous and glass phases. Steady state conditions are reached at pH 1.0 after approximately 3 weeks of reaction. Steady-state is not reached even after 3 months at pH 6.2.An interdiffusion model describes observed changes in Na diffusion profiles for perlite at pH 1.0. The calculated Na self-diffusion coefficient of 5 × 10^?19 cm²·s^?1 at 25°C approximates coefficients extrapolated from previously reported high temperature data for obsidian. The self-diffusion coefficient for H₃O⁺, 1.2 × 10^?20 cm²·s^?1, is similar to measured rates of water diffusion during hydration of obsidian to form perlite.     

Reaction overstepping and re-evaluation of peak P‒T conditions of the blueschist unit Sifnos,Greece: implications for the Cyclades subduction zone

ABSTRACT

Equilibrium thermodynamic modelling, quartz in garnet (QuiG) Raman geobarometry, and modelling of garnet nucleation at overstepped conditions were applied to three garnet-bearing blueschists from a 1.5 km-long transect across the eclogite-blueschist unit in Sifnos, Greece, in order to evaluate the accuracy of P?T conditions calculated via equilibrium thermodynamics. QuiG barometry uses the Raman shift of quartz inclusions in garnet to estimate the pressure of garnet nucleation and is independent of chemical equilibrium. Garnet nucleation temperatures were estimated by determining the stability field of the palaeo-assemblage inferred from garnet inclusion suites on mineral assemblage diagrams calculated in the MnNCKFMASH system and on temperatures obtained from Zr in rutile thermometry. These conditions were then compared to P?T conditions calculated at the equilibrium garnet isograd, and the method of intersecting isopleths. The P?T conditions calculated with intersecting garnet isopleths over- and underestimated the temperature of nucleation in samples SPH99-1a and SPH99-7, respectively, whereas they significantly underestimated nucleation pressure in SPH99-5. Nucleation of garnet in SPH99-1a at 12 kbar and ~484°C requires overstepping of ~6 kbar and a reaction affinity of 2.2 kJ mol^?1 O. SPH99-5 requires overstepping of ~8 kbar with garnet reaction affinities of at least 2.0 kJ mol^?1 O at 15 kbar and ~520°C. SPH99-7 requires overstepping of approximately 15 kbar and affinities of about 2.0–2.4 kJ mol^?1 O at ~23 kbar and ~530°C. The geotherms calculated from SPH99-7 (~6.7°C km^?1) and SPH99-5 (9.8°C km^?1) are in accordance with previous studies. The geotherm calculated from SPH99-1a, however, is warmer (11.3°C km^?1), and could reflect changes in the rate of subduction or differences in structural position within the down-going slab. The 10 kbar pressure difference between SPH99-7 and SPH99-1a can be explained by thrusting and accretion of thin slices of underplated wedge material facilitated by slab rollback and gravitational collapse.     

Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin: I. Calculation of the solubility of cassiterite at high pressures and temperatures

Estimation of equation of state parameters for Sn⁺⁺ and calculation of the thermodynamic properties of other aqueous species and dissociation constants for various stannous and stannic complexes as a function of temperature permit prediction of the high temperature solution chemistry of tin and calculation of the solubility of cassiterite in hydrothermal solutions. The results of these calculations indicate that in the absence of appreciable chloride and fluoride concentrations, Sn(OH)₂⁰ and Sn(OH)₄⁰ are the predominant tin species in H₂O up to 350°C at ~2 $\text{\$}\text{?}$pH $\text{\$}\text{?}$7.5. The calculations also indicate that chloride complexes of Sn⁺⁺ predominate by several orders of magnitude over their fluoride and hydroxide counterparts in 1–3 molal (m) NaCl solutions, except in the presence of geologically unrealistic concentrations of fluoride or a pH greater than ~3.5 at 250°C or ~5.0 at 350°C. At higher pH values, most of the tin in solution is present as hydroxide complexes, even at concentrations of NaCl as high as 3 m. Calculated values of the solubility of cassiterite at high temperatures compare favorably with experimental data reported in the literature. Depending on the fugacity of oxygen and solution composition, the solubility of cassiterite in hydrothermal solutions may exceed 100 ppm under geologically realistic conditions.     

Dissolution kinetics of chrysotile at pH 7 to 10

The rate of chrysotile dissolution over five days was studied in constant-pH, batch suspensions at 25°C. After the first day, release of Mg occurred at a constant rate and exhibited a fractional dependence on pH, [H⁺]^0.24. Interpreted in terms of a site-binding model for adsorption of protons on the surface, this fractional dependence implies that the rate is limited by a chemical reaction involving less than one adsorbed proton per Mg released into solution. The actual magnitude of the rate (10^?15.7 mol cm^?2 s^?1 at pH 8) supports this interpretation. The inorganics NO₃^?, Cl^?, HCO₃^? and SO₄^- and the organics catechol and oxalate affected the rate of Mg release only during the initial 12 to 24 hours of each experiment. Silica release was linear from the outset of each experiment, but showed no definite pH dependence.