Isovolumetric geochemical investigation of a buried granite saprolite near Columbia,SC, U.S.A.

Saprolites are residual soils which preserve the textures of their parent rocks and thus have evolved by an isovolumetric process of weathering (MILLOT, 1970, The Geology of Clays, Springer). Using bulk density, saprolite elemental analyses can be converted to units of g cm^?3. Furthermore, an empirical reaction progress diagram can be constructed for a suite of saprolite samples by plotting element concentrations (in g cm^?3) against bulk density (B.D.). Our data for a granite saprolite show that Al₂O₃ and SiO₂ decrease in a linear fashion from B.D. 2.1g cm^?3 to 1.5g cm^?3 but that K₂O follows a curvilinear trend such that it decreases from 75% of its fresh rock value at B.D. 1.6 g cm^?3 to nearly zero at B.D. 1.5 g cm^?3. The only hypothetical reaction paths that are compatible with these B.D. vs A1₂O₃, SiO₂ and K₂O constraints are those in which orthoclase alters to kaolinite through an intermediate potassium phase similar to KAl₃Si₃O₁₀(OH)₂ or KAl₂Si₂O₆(OH)₃ (hypothetical K-kaolinite). Normative mineral calculations, X-ray diffraction data and structural H₂O data are employed to test this conclusion.     

Selected geochemical factors influencing diagenesis of eocene carbonate rocks,peninsular Florida,U.S.A.

The geochemical significance of three selected ions (Mg²⁺, Na⁺, and Sr²⁺) supports a model of dolomitization by brackish groundwater. This groundwater zone contains sufficient quantities of Mg²⁺ to facilitate dolomitization ($\text{Mg}\text{Ca}\text{ratios 1}$). Rising and falling of sea level and fluctuations of the phreatic zone related to climatic variations account for the thickness of the dolomite layers and the chemical distributions within these layers. Sodium concentrations in the calcite are 70–185 ppm, indicating formation in brackish water. Dolomite has sodium concentrations between 50–1400 ppm, suggesting formation in waters of similar salinity.Strontium in calcite ranges from 320–600 ppm, suggesting diagenesis in slightly saline waters in an open system. Dolomite contains 241 ppm Sr²⁺ on the average and calcite has 418 ppm Sr²⁺. The Sr²⁺ concentrations of the dolomite are characteristic of diagenesis in water less saline than sea water. Average strontium concentrations in the dolomite occur in two distinct groups, 260 ppm for dolomite with 39–43 mole-% MgCo₃ and 195 ppm for the dolomite with 44–50 mole-% MgCO₃. The difference in the Sr²⁺ concentrations of the two dolomite groups indicates the higher mole-% MgCO₃ dolomite recrystallized in a less saline environment than the lower mole-% MgCO₃ dolomite. These different environments are attributed to a relatively more saline coastal environment and a less saline inland environment.The more nearly stoichiometric dolomite (44–50 mole-% MgCO₃) has less scatter when mole-% MgCO₃ is plotted against Sr²⁺ and Na⁺. This suggests a greater approach to equilibrium with the dolomitizing fluid than the lower mole-% MgCO₃ (39–43) dolomite. The more saline environment has higher Mg/Ca ratios and promotes more calcium-rich dolomite during diagenesis because of the inhibition from competing foreign ions and because it is thermodynamically a more favorable environment which causes more rapid crystallization. The less saline waters allow recrystallization to proceed more slowly, producing better ordering in the dolomites, textural preservation and development of subhedral to euhedral rhombic crystals.     

The distribution, speciation and geochemical cycling of selenium in a sedimentary environment, Kesterson Reservoir, California, U.S.A.

The well-defined and intensively studied episode of Se contamination at Kesterson Reservoir (Merced County, California, U.S.A.) provided a unique opportunity to describe the distribution, speciation and geochemical transformations of Se in a variety of geochemical and ecological settings, ranging from permanent ponds to semi-arid grasslands and salt flats. Kesterson Reservoir comprises 500 ha of land contaminated with Se from agricultural drain water. In most places. Se was concentrated in surficial organic detritus and the surficial decimeter of mineral soil. At dry sites, selenate ion predominated below 20 cm depth. Elemental selenium (Se⁰) also was prominent. The amount of zero-valent Se increased slowly with time. Although selenate is thermodynamically stable in the vadose zone in the presence of oxygen, Se⁰ is an additional, metastable product of the mineralization of organic selenium. Thiols and inorganic sulfides dramatically increase the solubility of Se⁰. Decreasing pH inhibits the reaction, explaining the observed decrease in solubility and biological availability of Se in soil and aquatic systems at low pH. Adding thiols or methionine to soil increases the emission of volatile Se compounds several-fold, suggesting that thiols play a major role in the microbial cycling of Se in soil.