Silicate minerals

Abstract: It is suggested that the partial pressure of carbon dioxide in the atmosphere is buffered, over geological time scales, by a negative feedback mechanism, in which the rate of weathering of silicate minerals (followed by deposition of carbonate minerals) depends on surface temperature, which in turn depends on the carbon dioxide partial pressure through the greenhouse effect. Although the quantitative details of this mechanism are speculative, it appears able to partially stabilize the earth's surface temperature against the steady increase of solar luminosity, believed to have occurred since the origin of the solar system.

Abstract: A simple general equation is presented for estimating the Fe 3 § concentrations in ferromagnesian oxide and silicate minerals from microprobe analyses. The equation has been derived using stoichiometric criteria assuming that iron is the only element present with variable valency and that oxygen is the only anion. In general, the number of Fe 3 + ions per X oxygens in the mineral formula, F, is given by; F = 2X(1 - T/S) where T is the ideal number of cations per formula unit, and S is the observed cation total per X oxygens calculated assuming all iron to be Fe 2 § Minerals for which this equation is appropriate include pyralspite and ugrandite garnet, aluminate spinel, magnetite, pyroxene, sapphirine and ilmenite. The equation cannot be used for minerals with cation vacancies (e.g. micas, maghemite) unless, as in the case of amphiboles, the number of ions of a subset of elements in the formula can be fixed. Variants of the above equation are presented for some of the numerous published schemes for the recalculation of amphibole formulae. The equation is also inappropriate for minerals showing SP += 4H § substitution (e.g. staurolite, hydrogarnet), minerals containing an unknown proportion of an unanalysed element other than oxygen (e.g. boron-bearing kornerupine) and minerals containing two or more elements with variable valency.

Abstract: This paper reports systematic changes in mudrock composition through time on a single con- tinental cmstal block. The changes reflect both sediment recycling processes and changes through time in the composition of crystalline material being added to the sedimentary system and are related to tectonic evolution as the block matures from a series of accreted arc terranes to a stable craton. The major and trace element distributions reflect different aspects of the provenance of the mudrocks in this study. Major elements record sediment recycling processes as well as changing proportions of sedi- mentary and first-cycle source rocks. With the exceptions of KzO (which tends to increase), and SiOz and A&O3 (which show no trend), most major oxides tend to decline in relative abundance in younger mud- rocks. Patterns shown by the Index of Compositional Variability ( ( Fe03 + KrO + NaaO + CaO + MgO + MnO + TiOJIAlrO,) and by K20/A1203 indicate that the major oxide trends are due to decreasing proportions of nonclay silicate minerals and a concomitant increase in the proportion of clay minerals, probably due to decreasing input of first cycle detritus coupled with recycling of sedimentary material. Excursions from progressive trends, marked by increases in MgO, K20, and CaO, reflect episodes of large- scale input of nonclay first-cycle minerals from crystalline source rocks due to large-scale basement uplift. The chemistry of low-solubility trace elements, in contrast, is not sensitive to recycling effects and reflects the composition of first-cycle input. Incompatible elements are progressively enriched relative to compatible elements in younger mudrocks, and values for chondrite normalised rare earth elements also increase. In addition, the Eu anomaly becomes systematically more negative in younger samples. These trends cMnot be explained by diagenetic or weathering processes, and, therefore, indicate that the proportion of fnc- tionated granitic first-cycle detritus being added to the sedimentary system becomes greater with time. These results confirm the importance of tectonic setting in controlling mudrock chemistry, and also demonstrate that there is a dynamic relationship between the tectonic evolution of a continental block and the composition of its sedimentary mantle.

Abstract: The correlation between decreasing reaction rates of silicate minerals and increasing duration of chemical weathering was investigated for both experimental and field conditions. Column studies, using freshly prepared Panola Granite, produced ambient plagioclase weathering rates that decreased parabolically over 6 years to a final rate of 7.0×10−14 mol m−2 s−1. In contrast, the corresponding plagioclase reaction rate for partially kaolinized Panola Granite, after reaching steady-state weathering after 2 months of reactions, was significantly less (2.1×10−15 mol m−2 s−1). Both rates were normalized to plagioclase content and BET surface area. Extrapolation of decreasing rates for the fresh plagioclase with time indicated that several thousand years of reaction would be required to replicate the rate of the naturally weathered plagioclase under identical experimental conditions. Both rates would remain orders of magnitude faster than field weathering rates previously measured for a weathering profile in the Panola Granite. Additional trends in weathering rates with time were established from a tabulation of previously reported experimental and field rates for plagioclase, K-feldspar, hornblende and biotite. Discrepancies in the literature, produced by normalization of weathering rates with respect to surface areas measured by gas absorption (BET) and geometric methods, were overcome by developing a time-dependent roughness factor. Regression curves through the corrected rates produced strong correlations with time that were similar for the four silicate minerals. The average silicate weathering rate R (mol m−2 s−1) was described by the power function R=3.1×10 −13 t −0.61 which was similar to the relationship describing the decrease in the fresh Panola plagioclase with time and suggesting control by transport-limited reaction. The time dependency of silicate weathering is discussed in terms of processes intrinsic to the silicate mineral and those extrinsic to the weathering environment. Intrinsic surface area, which increases with the duration of weathering, was shown to account for a third of the exponential decrease in the weathering rate shown by the above equation. Other factors, including progressive depletion of energetically reactive surfaces and accumulation of leached layers and secondary precipitates, must explain differences for fresh and weathered plagioclase reacting under identical experimental conditions. Extrinsic controls, including low permeability, high mineral/fluid ratios and increased solute concentrations, produce weathering reactions close to thermodynamic equilibrium under field conditions compared to highly unsaturated conditions during experimental reaction of fresh and weathered plagioclase. These differences explain the time-dependent difference in field and lab rates.

Abstract: Mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (KFMASHTO) using thermocalc and its internally consistent thermodynamic dataset constrain the effect of TiO2 and Fe2O3 on greenschist and amphibolite facies mineral equilibria in metapelites. The end-member data and activity–composition relationships for biotite and chloritoid, calibrated with natural rock data, and activity–composition data for garnet, calibrated using experimental data, provide new constraints on the effects of TiO2 and Fe2O3 on the stability of these minerals. Thermodynamic models for ilmenite–hematite and magnetite–ulvospinel solid solutions accounting for order–disorder in these phases allow the distribution of TiO2 and Fe2O3 between oxide minerals and silicate minerals to be calculated. The calculations indicate that small to moderate amounts of TiO2 and Fe2O3 in typical metapelitic bulk compositions have little effect on silicate mineral equilibria in metapelites at greenschist to amphibolite facies, compared with those calculated in KFMASH. The addition of large amounts of TiO2 to typical pelitic bulk compositions has little effect on the stability of silicate assemblages; in contrast, rocks rich in Fe2O3 develop a markedly different metamorphic succession from that of common Barrovian sequences. In particular, Fe2O3-rich metapelites show a marked reduction in the stability fields of staurolite and garnet to higher pressures, in comparison to those predicted by KFMASH grids.