Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Chemistry of basalts of ODP Hole 111-504B

The effect of oxygen fugacity (fO2) on the partition relationship of Mg and Fe between Plagioclase and sillicate liquid was investigated at 1 atm for basaltic samples recovered during ODP Leg 111 from Hole 504B. Samples 111-504B-143R-2 (Piece 8) and 111-504B-169R-1 (Piece 1) have Plagioclase as the liquidus phase. The distribution coefficient of Mg between Plagioclase and melt is constant at about 0.04 against the variation of fO2, whereas that of Fe (total Fe) varies from 0.3 at f(O2) = 0.2 atm to 0.03 at f(o2) = 10**-11.5 at 1200°C. The distribution coefficient of Mg is slightly higher than that calculated from the phenocryst and bulk-rock compositions, suggesting a kinetic disequilibrium effect on the distribution of Mg in Plagioclase. Because Mg, Fe, and Fe3+ have similar diffusion coefficients in silicate melt, the disequilibrium effect is greatly reduced for the exchange reaction of Mg and total Fe between Plagioclase and liquid. The exchange partition coefficient is highly dependent on fo2, with log fo2 ranging from -0.7 to - 11.5 at approximately 1200°C. Using this relationship, the f(O2) of crystallization of the magmas is estimated to be near the one defined by the fayalite-quartz-magnetite assemblage.

C1-C8 hydrocarbons in marine sediments

Light hydrocarbon (C1-C8) profiles are compared for three wells of varying maturities: two immature DSDP wells (Site 397 near the Canary Islands and Site 530A near the Walvis Ridge in the south-east Atlantic) and a mature well, the East Cameron well in the Texas Gulf Coast. Primary migration of C1 and C2 appears to be occurring in all of the sedimentary rocks examined. Primary migration of C3+ components becomes important only as fine-grained sedimentary rocks enter the catagenetic hydrocarbon generation zone or over short distances in more permeable sections. Lateral migration along bedding planes was more important than vertical migration in sedimentary rocks of all maturities. The lightest (methane, ethane and propane gases) hydrocarbon show greater fractionation than do the C4-C8 alkanes which generally show minimal fractionation during the migrational process. Subsurface diffusion coefficients for these p.p.b. quantities of C2-C5 alkanes from immature sediments from DSDP Site 530 are estimated to be several orders of magnitude less than values reported in the literature for diffusion of much larger amounts of these compounds from mature water wet sediments into air or sandstones. Since our calculations suggest light hydrocarbons are present in amounts less than their reported solubilities in pure water at 25°C, we postulate that the sediment organic matter has a substantial effect on retarding the movement of these light hydrocarbons.