Composition of phyllosilicates from hydrothermally altered basalts of DSDP Hole 83-504B, Costa Rica Rift, Pacific Ocean

Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or olivine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from < 100 A to a few hundred A. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystallinity of saponite. By contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of A thick. The Si/(Si + A1) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe + Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+A1) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite ± mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.

Element oxides in basaltic glass fragments from ODP Hole 203-1243B

Sand-sized basaltic glass fragments were recovered in the liner of Core 203-1243B-19R, the deepest recovery from Hole 1243B. Microprobe analysis of 582 glassy cuttings cluster into five compositionally distinct groups, most of which are unlike the lithologic units described on board ship. Drilling operations intended to sweep cuttings from the caving hole and differences between the cuttings and geochemically distinct lithologic units of the upper part of the basement indicate that the cuttings came mainly, if not entirely, from the lower part of the hole. They give information about the part of Hole 1243B that had poor core recovery. Enriched mid-ocean-ridge basalt (MORB) from the upper part of the hole and transitional MORB from two groups of cuttings from sources low in the hole may be a trace of the Galápagos plume on the Pacific plate or may be a normal consequence of eruptions from two distinct magmas on fast-spreading crust.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Geochemistry at DSDP Hole 69-504B

Cores from Deep Sea Drilling Project Holes 501, 504B and 505B have an unusual near-vein zonation in basalts. Megascopically, zonation occurs as differently colored strips and zones whose typical thickness does not exceed 6 to 7 cm. Microscopically, the color of zones depends on variably colored clay minerals which are the products of low-temperature hydrothermal alteration in basalt. These differently colored zones form the so called "oxidative" type of alteration of basalts. Another "background," or, less precisely termed, "non-oxidative," type of alteration in basalts is characterized by large-scale, homogeneous replacement of olivine, and filling of vesicles and cracks by an olive-brown or olive-green clay mineral. The compositions of clay minerals of the "background" type of alteration, as well as the composition of co-existing titanomagnetites, were determined with an electron microprobe. There are sharp maxima in potassium and iron content, and minima in alumina, silica, and magnesia in clay minerals in the colored zones near veins. Coloring of clay and rock-forming minerals by iron hydroxides and a decrease of the amount of titanomagnetite, which apparently was the source of redeposited iron, occur frequently in colored zones. We assume that the large-scale "background" alteration in the basalts occurred under the effect of pore waters slowly penetrating through bottom sediments. Faulting can facilitate access of fresh sea water to basalts; thus above the general homogeneous background arise zones of "oxidative" alteration along fractures in basalts. The main factors controlling these processes are time (age of basalt), grain size, temperature, thickness of sedimentary cover, and heat flow.

Stable isotope (carbonates), organic carbon, calcium carbonate and occurrence of coccoliths at DSDP Hole 71-511

Thin but discrete pelagic limestone beds intercalated among the black mudstones near the top of the extensive Mesozoic black shale sequence of the Falkland Plateau are reminiscent of similar occurrences in the central and North Atlantic and may be cyclic in nature. They have been studied via carbonate, organic carbon, stable isotope, nannofloral, and ultrastructural analysis in an attempt to determine their mode of origin. Nannofossil diversity and preservation suggest that selective dissolution or diagenesis did not produce the interbedded coccolith-rich and coccolith-poor layers, nor did blooms of opportunistic species play a role. Stable isotope measurements of carbonate do not adequately constrain the origin of the cyclicity; however, the d13C data suggest that the more nannofossil-rich intervals may be due to higher nutrient supply and overturn of deeper waters at the site rather than influxes of well-oxygenated waters into an otherwise anoxic environment. Such an explanation is in accord with the nannofloral evidence

Major-oxides and trace-elements at DSDP Hole 78-543A

Four chemically distinct basalts were cored in 44 m of basement penetration at Deep Sea Drilling Project Site 543, in Upper Cretaceous crust just seaward of the deformation front of the Barbados Ridge and north of the Tiburon Rise. All four types are moderately fractionated abyssal tholeiites. The four types have different magnetic inclinations, all of reversed polarity, suggesting eruption at different times which recorded secular variation of the earth's magnetic field. Extensive replacement of Plagioclase by K-feldspar has occurred at the top of the basalts, giving analyses with K2O contents up to 5 %. The earliest stages of alteration were dominantly oxidative, resulting in fractures lined with celadonite and dioctahedral smectite, and pervasive replacement of olivine and most intersertal glass with iron hydroxides and green clay minerals. Latef, non-oxidative alteration resulted in formation of olive-green clays and pyrite veins in a portion of the rocks. Basalts affected by this alteration actually lost K2O (to abundances lower than in adjacent fresh basalt glasses), and gained MgO (to abundances higher than in the glasses). Finally, fractures and interpillow voids were lined with calcite, sealing in much fresh glass. Oxygen-isotope measurements on the calcite indicate that this occurred at 12 to 25C. Either altering fluids were warm or the basalts had become buried with a considerable thickness of sediments, such that temperatures increased until a conductive thermal gradient was established, when the veining occurred.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.