Relative stabilities of sedimentary rearranged sterenes as calculated by molecular mechanics: a key to unravel further steroid diagenesis

Molecular mechanics calculations of rearranged cholestenes revealed that diacholest-13(17)-enes with 10α stereochemistry are more stable than their 10β counterparts and that a partly rearranged sterene with a Δ⁸ double bond and 10β, 14β stereochemistry (compound 7) is relatively stable at thermodynamic equilibrium. The calculated data are in good agreement with sedimentary and experimental data and thus reinforce recent propositions for early-stage diagenesis of steroids.     

Sandstone diagenesis in the Pattani Basin (Gulf of Thailand): history of water-rock interaction and comparison with the Gulf of Mexico

In the Pattani Basin, a failed-rift basin, extensive water-rock interaction has occurred between subquartzose alluvial sandstones of Miocene age and their pore fluids. Diagenetic rates and pathways have been strongly influenced by high geothermal gradients, high CO₂ fugacities, and low pore water salinities. Depositional pore water was fresh to brackish, depending on the depositional environment of the sediments. Chloride concentrations in modern formation water are believed primarily to reflect the proportions of river and sea water in the depositional environment. However, the concentration of other important solutes and the isotopic composition of the formation waters can not be explained by roportional mixing of these two end-member waters. Dissolution of detrital plagioclase (An = 3) and K- feldspar are reactions of major significance that are reflected chemically in the Na/Cl and K/Cl ratios of the formation water. Despite the high temperature of the sandstones (120–200°C), diagenetic albite does not occur. Geochemical calculations indicate the formation water is undersaturated with respect to both orthoclase and albite. This style of feldspar diagenesis differs significantly from that of sandstones of similar composition in other basins, and has probably influenced other aspects of silicate diagenesis.Important authigenic minerals are: 1. locally abundant calcite cement (δ¹³C= −12.8, δ¹⁸O= −17.3 PDB), an early diagenetic phase that formed at about 60°C; 2. pore-filling kaolinite (δ¹⁸O= 9.9, δD= −83.5SMOW) that was closely associated with feldspar dissolution and formed over a range of temperatures; and 3. fibrous pore-lining and pore-bridging illite (δ¹⁸O = 9.8, δD = − 86.7 SMOW, the last significant cement, formed at temperatures of 120 to 150°C. Potassium/argon dates on illite indicate that sandstone diagenesis took place during a period of rapid sedimentation in the first two-thirds of the burial history.Comparison of Pattani Basin diagenesis with diagenesis of sandstones of similar age in other sedimentary basins demonstrates that chemical diagenesis, relative to mechanical compaction, has been especially rapid in the Pattani Basin. This reflects the effect of high temperatures on reaction rates. The net effect is a high average rate of porosity loss with burial (11% km).     

He,Pb, Sr and Nd isotope constraints on magma genesis and mantle heterogeneity beneath young Pacific seamounts

Pb, Sr and Nd isotope variations are correlated in diverse lavas erupted at small seamounts near the East Pacific Rise. Tholeiites are isotopically indistinguishable from MORB (²⁰⁶Pb/²⁰⁴Pb=18.1–18.5; ⁸⁷Sr/⁸⁶Sr=0.7023–0.7028; ¹⁴³Nd/¹⁴⁴Nd=0.51326-0.51308); associated alkali basalts always show more radiogenic Pb and Sr signatures (²⁰⁶Pb/²⁰⁴Pb=18.8–19.2; ⁸⁷Sr/⁸⁶Sr=0.7029–0.7031) and less radiogenic Nd (¹⁴³Nd/¹⁴⁴Nd=0.51289–0.51301). The isotopic variability covers 80% of the variability for Pacific MORB, due to the presence of small-scale heterogeneity in the underlying mantle. Isotope compositions also correlate with trace element ratios such as La/Sm. Tholeiites at these seamounts have ³He/⁴He between 7.8–8.7 R _A(R _A= atmospheric ratio), also indistinguishable from MORB. He trapped in vesicles of alkali basalts, released by crushing in vacuo, has low ³He/⁴He (1.2–2.6 R)_Ain conjunction with low helium concentrations ([He]<5×10^–8 ccSTP/g). In many cases post-eruptive radiogenic ingrowth has produced He isotope disequilibrium between vesicles and glass in the alkali basalts; subatmospheric ³He/⁴He ratios characterize the He dissolved in the glass which is released by melting the crushed powders. The narrow range of ³He/⁴He in the vesicles of the alkali basalts suggests that low ³He/⁴He is a source characteristic, but given their low [He] and high (U + Th), pre-eruptive radiogenic ingrowth cannot be excluded as a cause for low inherited ³He/⁴He ratios. Pb, Sr and Nd isotope compositions in lavas erupted at Shimada Seamount, an isolated volcano on 20 m.y. old seafloor at 17°N, are distinctly different from other seamounts in the East Pacific (²⁰⁶Pb/²⁰⁴Pb=18.8–19.0, ⁸⁷Sr/ ⁸⁶Sr0.7048 and ¹⁴³Nd/¹⁴⁴Nd0.51266). Relatively high ²⁰⁷Pb/²⁰⁴Pb (15.6–15.7) indicates ancient (>2 Ga) isolation of the source from the depleted upper mantle, similar to Dupal components which are more prevalent in the southern hemisphere mantle. ³He/⁴He at Shimada Seamount is between 3.9–4.8 R _A. Because the helium concentrations range up to 1.5×10^–6, the low ³He/⁴He can not be due to radiogenic accumulation of ⁴He in the magma for reasonable volcanic evolution times. The low ³He/⁴He may be due to the presence of enriched domains within the lithosphere with high (U + Th)/He ratios, possibly formed during its accretion near the ridge. Alternatively, the low ³He/⁴He may be an inherent characteristic of an enriched component in the mantle beneath the East Pacific. Collectively, the He-Pb-Sr-Nd isotope systematics at East Pacific seamounts suggest that the range of isotope compositions present in the mantle is more readily sampled by seamount and island volcanism than by axial volcanism. Beneath thicker lithosphere away from the ridge axis, smaller degrees of melting in the source regions are less efficient in averaging the chemical characteristics of small-scale heterogeneities.