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.

Petrographic description and geochemistry of basalts and altered volcanic rocks from ODP Leg 183 sites

The basalts recovered during Legs 183 and 120 from the southern, central, and northernmost parts of the Kerguelen Plateau (Holes 1136A, 1138A, 1140A, and 747C, respectively), as well as those recovered from the eastern part of the crest of Elan Bank (Hole 1137A), represent derivates from tholeiitic melts. In the northern part of the Kerguelen Plateau (Hole 1140A), basalts may have formed from two sources located at different depths. This is reflected in the presence of both low- and high-titanium basalts. The basalts are variably altered by low-temperature hydrothermal processes (at temperatures up to 120°C), and some are affected by subaerial weathering. The hydrothermal alteration led mainly to the formation of smectites, chlorite minerals, mixed-layer hydromica-smectite and smectite-chlorite minerals, hydromica, serpentine(?), clinoptilolite, heulandite, stilbite, analcime, mordenite, thomsonite, natrolite(?), calcite, quartz, and dickite(?). Alteration of extrusive basalts is mainly related to horizontal fluid flow within permeable contact zones between lava flows. Under a nonoxidizing environment of alteration, the tendency to lose most of elements, including rare earth elements, from basalts dominates. Under on oxidizing environment, basalts accumulate many elements.

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.

Altered neurotransmitter function in CO2-exposed stickleback (Gasterosteus aculeatus): a temperate model species for ocean acidification research

Studies on the consequences of ocean acidification for the marine ecosystem have revealed behavioural changes in coral reef fishes exposed to sustained near-future CO2 levels. The changes have been linked to altered function of GABAergic neurotransmitter systems, because the behavioural alterations can be reversed rapidly by treatment with the GABAA receptor antagonist gabazine. Characterization of the molecular mechanisms involved would be greatly aided if these can be examined in a well-characterized model organism with a sequenced genome. It was recently shown that CO2-induced behavioural alterations are not confined to tropical species, but also affect the three-spined stickleback, although an involvement of the GABAA receptor was not examined. Here, we show that loss of lateralization in the stickleback can be restored rapidly and completely by gabazine treatment. This points towards a worrying universality of disturbed GABAA function after high-CO2 exposure in fishes from tropical to temperate marine habitats. Importantly, the stickleback is a model species with a sequenced and annotated genome, which greatly facilitates future studies on underlying molecular mechanisms.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Chemistry of altered basalts from ODP Hole 123-765D

Volcanic basement recovered at Hole 765D is characterized by nonpervasive, oxidative alteration, typical of seafloor weathering. Chilled margins and the mesostasis of the lavas are variably altered to assemblages of celadonite, Fe-oxyhydroxides, zeolites, and calcite with trace saponite. Plagioclase is partially altered to Ca-Na zeolites and/or albite. Well-developed alteration halos parallel fracture surfaces and extend several centimeters into the surrounding rock. These clay-rich halos are enriched in K2O and Fe2O3 relative to the adjacent clay-poor rock. The halos and adjacent rock are characterized by d18O values 2 per mil-3 per mil higher than those of fresh MORB. The "freshness" of the samples and the scarcity of saponite suggest that the duration of seawater circulation was short-lived. Albitization of plagioclase indicates that the volcanic rocks were altered initially at low temperatures and were subsequently reheated off-axis in a closed environment. Reheating did not result in significant modification of the bulk composition of the crust.

Platinum group elements and geochemistry of altered oceanic crust of ODP Hole 140-504B

Primary chemical heterogeneity in the sheeted dike complex in Deep Sea Drilling Project Hole 504B makes these rocks unsuitable for conventional mass balance calculations in determining element mobility associated with hydrothermal alteration. Due to the original heterogeneity and variable degrees of fractionation in the dikes, an appropriate reference sample on which calculations can be based is difficult to find. Therefore, the use of incompatible element ratios is developed to evaluate geochemical changes during alteration(s). For example, on a Zr/Yb-La/Yb plot, scatter along a straight line suggests tapping of a variably depleted mantle source and deviation from the line suggests element mobility (gain or loss). Using this method, our data indicates that the hydrothermal evolution of the sheeted dike complex was accompanied by significant loss of Cu, Zn, and Ti and some loss of La. The sheeted dike complex has low platinum group element (PGE) concentrations and steep PGE patterns, typical of mid-ocean ridge basalts (MORBs) on the global scale. We propose that the unusual PGE patterns of MORBs cannot be entirely generated by a partial melting and sulfide segregation model; instead, these patterns in part must have been inherited from their mantle source. The Au data show no evidence for mobilization during hydrothermal alteration of the dikes.

Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.

Mineral and oxygen isotopic compositions in a profile through the altered lower oceanic crust, ODP Hole 176-735B

ODP Hole 735B located on the Southwest Indian Ridge at 57°E is an in situ sampled long, continuous section of lower oceanic crust. Oxygen isotope compositions of constituent minerals of Leg 176 gabbros have been measured by UV-laser oxygen isotope microprobe. Together with existing data from Leg 118, a complete oxygen isotope profile through the lower oceanic crust has been obtained. Most clinopyroxenes and olivines have normal mantle values of ~5.5 per mil and ~5.2 per mil, respectively, while plagioclases show slight d18O enrichment relative to its mantle value of 6.1per mil. Down-hole variations of Hole 735B gabbro indicate a downward decreasing d18O profile, with a kink at a depth of about 800 m below sea floor. Above this depth, gabbros are depleted in 18O relative to unaltered basalts, while below ~800 m they show nearly unmodified d18O values. Abundant seawater penetration appears to be limited to the upper part of the lower crust at ODP site 735 (~800 m into the gabbroic layer and ~2-2.5 km into the oceanic crust from the top of pillow basalts). Mass balance calculations show that the lower crust formed under this ultra-slow-spreading ridge has an average d18O value of 5.5 per mil. The whole crust at Site 735 has an overall 18O enrichment with d18O values of 6.0 per mil to 7.8 per mil, depending on the possible variation of the d18O values of the upper pillow basalts and sheeted dykes. The apparent difference in oxygen isotope compositions of ocean crusts formed with different spreading rates has important implications on the buffering of ocean water over geological time, as well as on the oxygen recycling between crust and mantle through subduction. The difference of seawater penetration between fast- and slow-spreading ridges could be related to their particular magmatic-tectonic history during the formation and aging of the crust. However, more analyses on continuous sections through oceanic and ophiolitic crust in different tectonic settings are required to derive any predictive models.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.