Carbon isotopic fractionation in synthetic aragonite and calcite: Effects of temperature and precipitation rate

: Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

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A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

Sulfur, the 10th most abundant element in the universe and the 14th most abundant element in the Earth’s crust, is the defining element of sulfide minerals and provides insights into the origins of these minerals through its stable isotopes. The insights come from variations in the isotopic composition of sulfide minerals and related compounds such as sulfate minerals or aqueous sulfur species, caused by preferential partitioning of isotopes among sulfur-bearing phases, known as fractionation. These variations arise from differences in temperature, or more importantly, oxidation and reduction reactions acting upon the sulfur. The oxidation and reduction reactions can occur at high temperature, such as in igneous systems, at intermediate temperatures, such as in hydrothermal systems, and at low temperature during sedimentary diagenesis. At high temperatures, the reactions tend to occur under equilibrium conditions, whereas at low temperatures, disequilibrium is prevalent. In addition, upper atmospheric processes also lead to isotopic fractionations that locally appear in the geologic record.

Sulfur isotope geochemistry as a subdiscipline of the geological sciences began in the late 1940s and early 1950s with early publications by Thode et al. (1949) and Szabo et al. (1950) on natural variations of sulfur isotopes, and Macnamara and Thode (1950) on the isotopic composition of terrestrial and meteoritic sulfur. Sakai (1957) presented an early scientific summary of sulfur isotope geochemistry, with a particular emphasis on high-temperature processes. Thode et al. (1961) also presented an early summary, but with an emphasis on low-temperature processes. Both of these summaries outlined salient aspects of the global sulfur cycle. Sulfur isotope geochemistry understandably has had a long history of application to the study of sulfide-bearing mineral deposits. Early noteworthy papers include those by Kulp et al. (1956) and Jensen (1957, 1959). Similarly, there is also a legacy of contributions to understanding …

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Sulfur Isotope Geochemistry of Sulfide Minerals

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes.

Geologic evidence indicates that net vertical uplift occurred on a large (kilometer) scale and at accelerating rates during the middle and late Cenozoic in plateaus of southern Asia and the American west. Based on this evidence, General Circulation Model sensitivity tests were run to isolate the unique effects of plateau uplift on climate. The experiments simulated significant climatic changes in many places, some far from the uplifted regions. The basic direction of most of these simulated responses to progressive uplift is borne out by changes found in the geologic record: winter cooling of North America, northern Europe, northern Asia, and the Arctic Ocean; summer drying of the North American west coast, the Eurasian interior, and the Mediterranean; winter drying of the North American northern plains and the interior of Asia; and changes over the North Atlantic Ocean conducive to increased formation of deep water. The modeled changes result from increased orographic diversion of westerly winds, from cyclonic and anticyclonic surface flow induced by summer heating and winter cooling of the uplifted plateaus, and from the intensification of vertical circulation cells in the atmosphere caused by exchanges of mass between the summer-heated (and winter-cooled) plateaus and the mid-latitude oceans. Disagreements between the geologic record and the model simulations in Alaska and the Southern Rockies and plains may be related mainly to the lack of narrow mountain barriers in the model orography. Taken together, the observed regional trends comprise much of the pattern of “late Cenozoic climatic deterioration” in the northern hemisphere that culminated in the Plio-Pleistocene ice ages. The success of the uplift sensitivity experiment in simulating the correct pattern and sign of most of the observed regional climatic trends points to uplift as an important forcing function of late Cenozoic climatic change in the northern hemisphere at time scales longer than orbital variations; however, the modest amplitude of the uplift-induced cooling simulated at high latitudes indicates a probable need for additional climatic forcing.

Antonio C. Lasaga

Papers

Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

An Improved Geochemical Model of Atmospheric CO2 Fluctuations Over the Past 100 Million Years

Multicomponent exchange and diffusion in silicates

Isotopic exchange in mineral-fluid systems. I. Theoretical evaluation of oxygen isotopic exchange accompanying surface reactions and diffusion

The kinetics of dissolution of nepheline (NaAlSiO4)