Geology topics

T.M.L. Wigley

Publications and source records attributed to T.M.L. Wigley.

4 recordsLinked to original sources

USGS1979

Carbon dioxide in the ocean surface: The homogeneous buffer factor

The amount of carbon dioxide that can be dissolved in surface seawater depends at least partially on the homogeneous buffer factor, which is a mathematical function of the chemical equilibrium conditions among the various dissolved inorganic species. Because these equilibria are well known, the homogeneous buffer factor is well known. Natural spatial variations depend very systematically on sea surface temperatures, and do not contribute significantly to uncertainties in the present or future carbon dioxide budget.

Science↗

USGS1978

Mass transfer and carbon isotope evolution in natural water systems

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Geochimica et Cosmochimica Acta↗

USGS1976

Mixing of carbonate waters

When mineral solutions of different compositions are mixed, the molalities and activities of individual ions in the mixture are often non-linear functions of their end-member values. This non-linearity is particularly significant in determining mineral saturation levels. Mixtures of saturated solutions may be either undersaturated or supersaturated depending on the end-member compositions and the physical conditions in which end-members and their mixtures exist. In carbonate solutions important non-linear effects occur due to redistribution of carbonate species. In extreme cases this causes mixture pH to be below both the end-member pH values. A simple but precise computer program (WATMIX) has been developed for calculating mixture composition for closed and open system mixing of arbitrary end-members. A number of mixing examples are considered which allow one to isolate three important processes leading to non-linear behaviour: the algebraic effect, the δP CO 2 effect, and the ionic strength effect.

Geochimica et Cosmochimica Acta↗

USGS1976

The dissolution of calcite in CO 2 -saturated solutions at 25°C and 1 atmosphere total pressure

The dissolution of Iceland spar in CO 2 -saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

Geochimica et Cosmochimica Acta↗