Biomedical subjects

E M Stolper

Publications and source records attributed to E M Stolper.

5 recordsLinked to original sources

PubMed1997

Low-temperature carbonate concretions in the Martian meteorite ALH84001: evidence from stable isotopes and mineralogy.

The martian meteorite ALH84001 contains small, disk-shaped concretions of carbonate with concentric chemical and mineralogical zonation. Oxygen isotope compositions of these concretions, measured by ion microprobe, range from delta18O = +9.5 to +20.5 per thousand. Most of the core of one concretion is homogeneous (16.7 +/- 1.2 per thousand) and over 5 per thousand higher in delta18O than a second concretion. Orthopyroxene that hosts the secondary carbonates is isotopically homogeneous (delta18O = 4.6 +/- 1.2 per thousand). Secondary SiO2 has delta18O = 20.4 per thousand. Carbon isotope ratios measured from the core of one concretion average delta13C = 46 +/- 8 per thousand, consistent with formation on Mars. The isotopic variations and mineral compositions offer no evidence for high temperature (>650 degrees C) carbonate precipitation and suggest non-equilibrium processes at low temperatures (< approximately 300 degrees C).

Carbon Isotopes↗

PubMed1992

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents.

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

Desiccation↗

PubMed1991

Water diffusion in a basaltic melt.

Water is the most abundant volatile component in terrestrial basalts and is a significant constituent of the gases that escape from basaltic magmas. Knowledge of the diffusivity of water (and other volatiles) in basaltic melts is important for understanding the degassing of basaltic magma and for assessing the fractionation of volatiles during degassing. We report here measurements of water diffusivity in a basaltic liquid. The water concentration profiles through the samples, determined by Fourier-transform infrared spectroscopy, cannot be modelled adequately on the basis of a constant water diffusivity, but instead can be fitted by assuming that only molecular H2O is diffusing and that there is a local equilibrium between H2O molecules and OH groups. The concentration-dependent total water diffusivities in the basaltic melt at 1,300-1,500 degrees C are 30-50 times as large as those in rhyolitic melts, and are greater than the total CO2 diffusivity in basaltic melts, contrary to previous expectations. These results suggest that diffusive fractionation would increase the ratio of water to carbon dioxide in growing bubbles relative to equilibrium partitioning, and decrease the ratio in interface melts near an advancing anhydrous phenocryst.

Carbon Dioxide↗

PubMed1991

Diffusion of a multi-species component and its role in oxygen and water transport in silicates.

An important but poorly understood factor that affects diffusion rates is the role of speciation during diffusion of a multi-species component. The diffusion of such a component is complicated by the different diffusion coefficient of each species and the interconversion reactions among the species. These complexities can be treated by a diffusion equation that incorporates the diffusive fluxes of all species contributing to the concentration of the component. The effects of speciation on the diffusion of the component can be investigated experimentally in some simple cases by measuring concentration profiles of all species developed during diffusion experiments or by studying some of their other consequences. Experimental data on water diffusion in rhyolitic glasses indicate that although dissolved water is present as two species, H2O molecules and OH groups, molecular H2O is the dominant diffusing species at very low to high water concentrations. This explains the apparently complex behavior of water diffusion. Experimental data on oxygen diffusion in some silicates using 18O tracers in the form of H2(18O) are consistent with the idea that 18O transport is dominated by diffusion of H2O molecules even at lower water contents (ppm or less). This explains why oxygen transport depends on the presence of water and generally depends on water fugacity linearly. For this mode of oxygen transport, there is a simple theoretical relationship between the effective total oxygen diffusion coefficient and the total water diffusion coefficient that is a function of only the water concentration of the silicate at low water content. This relationship appears to describe quantitatively the existing data over a wide range in water contents and diffusion coefficients in several phases.

Diffusion↗

PubMed1991

Diffusion of water in rhyolitic glasses.

Water dehydration experiments on rhyolitic glasses have been carried out at 400-550 degrees C under a N2 atmosphere. Concentration profiles of both H2O molecules and OH groups were measured by Fourier transform infrared spectroscopy. As found in previous studies of water diffusion in rhyolitic melts, the measured total water concentration profiles do not match expectations based on a single constant diffusion coefficient for total water. The diffusion of total water is described by considering the diffusion of both H2O molecules and OH groups and the reaction between them. The concentration relationship between the two species has been obtained from direct infrared measurement on quenched experimental charges. The quench is inferred to be rapid enough to preserve concentrations of both species at experimental temperature based on experimental results designed to examine reaction kinetics. The measured species concentrations along diffusion profiles show that local equilibrium between H2O and OH is approximately reached at high temperatures and high water contents. However, at lower water content or lower temperature, local equilibrium is not reached. In treating the diffusion problem, this disequilibrium effect is partially compensated by using empirical relationships between H2O and OH concentrations based on measurements, instead of using an equilibrium relationship. It is thus possible to obtain diffusion coefficients for both species from their concentration profiles. The diffusion coefficient of OH is found to be negligible compared to that of H2O at 403-530 degrees C (DOH < 0.02 DH2O and could be much smaller); i.e., H2O is the dominant diffusing species even at total water concentration as low as 0.2 wt%. The variation of OH concentration along the diffusion profile is inferred to be due to the local interconversion between OH groups and H2O molecules; the reaction also provides the diffusing H2O species. DH20 values are found to vary by less than a factor of 2 over a total water concentration range of 0.2 to 1.7 wt%. This simple model, coupled with the assumption of local equilibrium between H2O and OH, yields a very good fit to the data from diffusion-couple experiments of LAPHAM et al. (1984) at 850 degrees C. When our data are combined with DH2O obtained from that fit, DH2O (in m2/s) is given by: ln DH2O = (-14.59 +/- 1.59) - (103000 +/- 5000) / RT; 673 K < or = T < or = 1123 K, where T is temperature in K and R is the gas constant in J K-1 mol-1. This equation also approximates well DH2O values calculated from previous measurements of concentration-dependent bulk water diffusion coefficients of KARSTEN et al. (1982). The diffusion of H2O is also compared to the diffusion of the noble gas elements. The activation energy for diffusion in rhyolitic glasses is well correlated with neutral species radii of He, Ne, H2O, and Ar. This supports the contention that the diffusing species for "water" is neutral molecular H2O. The role of speciation may also be important in understanding the diffusion of many other multi-species components, and the effect can be treated in a similar fashion as that during water diffusion.

Diffusion↗