Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and Uand up to 2 ppm Pb and 0.2 ppm U in the evolved. The range of isotopic compositions of the unleached rocks is: 87Sr/86Sr=0.70280-0.70299, average 0.70287+/-0.00005 (1 S.D., N=30 samples) (except one felsic vein with 87Sr/86Sr=0.7045), 143Nd/144Nd=0.51304-0.51314, average 0.51310+/-0.00002 (1 S.D., N=28), 206Pb/204Pb=17.43-18.55, 207Pb/204Pb=15.40-15.61 and 208Pb/204Pb=37.19-38.28. The range of Sr and the almost constant Nd isotopic composition resemble that found in the upper 500 m of Hole 735B, while Pb ranges to more radiogenic compositions. In general, there is a decrease in isotopic variation of Sr and Pb as well as ? (238U/204Pb), U and Pb with depth, with a trend towards relatively unradiogenic compositions. This correlates with a decrease in alteration and frequency of evolved rock-types in the core. Leached samples generally have less radiogenic Pb with values trending towards 206Pb/204Pb=17.35, 207Pb/204Pb=15.35 and 208Pb/204Pb=37.0, while their 87Sr/86Sr ratios deviate less systematically from unleached rocks and reach both higher, 0.70307, and lower values, 0.70276. Separated clinopyroxene has elevated 87Sr/86Sr up to 0.7035, while plagioclase generally has close to whole rock Sr. Leaching reduced 87Sr/86Sr in clinopyroxene and in two (out of nine) cases leached separates and whole rock display isotopic equilibrium. Relatively minor hydrothermal seawater alteration is thought to have increased 87Sr/86Sr in the rocks, while a secondary high temperature percolation of a mantle-derived agent is thought to be the cause for the trend towards radiogenic Pb. This material had intermediate 87Sr/86Sr and may have originated from non-MORB off axis mantle. The main primary igneous isotopic variation of the gabbros is suggested to have been derived from the MORB-mantle and is defined mainly by leached samples from both ODP Leg 176 and Leg 118 and can be explained by two-component mixing of an end-member with composition like Central Indian Ridge basalts and an end-member with composition unlike any MORB. The latter is characterized by very unradiogenic Pb, in particular 207Pb/204Pb, and may have an origin with affinity to old depleted mantle (DM). The isotopic composition of the magmas parental to the FeTi-oxide rich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Structural description and paleomagnetic directions of ODP Hole 152-917A

During Ocean Drilling Program Legs 152 and 163, we recovered core from the offshore East Greenland volcanic province. The basaltic core recovered included a set of structural elements reflecting the history of extrusion, cooling, postdeposition alteration, and minor tectonism. Brittle features in the basaltic core include faults and several generations of veins. Several minicore samples from the lower sections of core from Hole 917A were taken for paleomagnetic analysis, primarily to test whether there were any significant postdepositional tectonic rotations or whether the core could be reoriented using paleomagnetic techniques. The characteristic magnetization direction was used to estimate the in situ orientation of measured structural features within the core. Although significant uncertainty is associated with the analysis, the corrected attitudes of veins in basalt at Site 917 dip moderately west, with a smaller, conjugate group of veins dipping moderately east-southeast, parallel to other seaward-dipping faults in the area, which were interpreted from seismic lines.

Geochemistry of minerals at DSDP Holes 68-501 and 69-504B

The interaction of seawater with basalts in DSDP Hole 501 and the upper part of Hole 504B (Costa Rica Rift) produced oxidative alteration and a zonation of clay minerals along cracks. From rock edges to interiors in many cracks the following succession occurs, based on microscopic observations and microprobe analysis: iron hydroxides (red), "protoceladonite" (green), iddingsite (orange), and saponite (yellow). Clay minerals replace olivines and fill vesicles and cracks. Other secondary minerals are phillipsite, aragonite, and unidentified carbonates. Some glass is transformed to Mg-rich palagonite. Bulk rock chemistry is related to the composition of the secondary minerals. The zonation can be interpreted as a succession of postburial nonoxidative and oxidative diagenesis similar to that described in the Leg 34 basalts.

Geochemistry and isotopic composition of gabbros from ODP Hole 118-375B

Gabbros drilled from the shallow (720 m) east wall of the Atlantis II transform on the Southwest Indian Ridge (SWIR; 32°43.40', 57°16.00') provide the most complete record of the stratigraphy and composition of the oceanic lower crust recovered from the ocean basins to date. Lithologies recovered include gabbro, olivine gabbro, troctolite, trondhjemite, and unusual iron-titanium (FeTi) oxide-rich gabbro containing up to 30% FeTi oxides. The plutonic rock sequence represents a tholeiitic fractionation trend ranging from primitive magmas having Mg numbers of 67 to 69 that fractionated troctolites, to highly evolved liquids that crystallized two-pyroxene, FeTi oxide-rich gabbros and, ultimately, trondhjemite. Isotopic compositions of unaltered Leg 118 gabbros are distinct from Indian Ocean mid-ocean ridge basalts (MORB) in having higher 143Nd/144Nd (0.51301-0.51319) and lower 206Pb/204Pb values (17.35-17.67); 87Sr/86Sr values (0.7025-0.7030) overlap those of SWIR basalts, but are generally lower than MORBs from the Southeast Indian Ridge or the Rodrigues Triple Junction. More than one magma composition may have been introduced into the magma chamber during its crystallization history, as suggested by the higher 87Sr/86Sr, 206Pb/204Pb, and lower 143Nd/144Nd values of chromium-rich olivine gabbros from the bottom of Hole 735B. Whole-rock gabbro and plagioclase mineral separate 87Sr/86Sr values are uniformly low (0.7027-0.7030), irrespective of alteration and deformation. By contrast, 87Sr/86Sr values for clinopyroxene (0.7025-0.7039) in the upper half of Hole 735B are higher than coexisting plagioclase and reflect extensive replacement of clinopyroxene by amphibole. Hydrothermal veins and breccias have elevated 87Sr/86Sr values (0.7029-0.7035) and indicate enhanced local introduction of seawater strontium. Oxygen- and hydrogen-isotope results show that secondary amphiboles have uniform dD values of -49 to -54 per mil and felsic hydrothermal veins range from -46 to - 77 per mil. Oxygen-isotope data for secondary amphibole and visibly altered gabbros range to low values (+1.0-+5.5 per mil), and O-isotope disequilibrium between coexisting pyroxene and plagioclase pairs from throughout the stratigraphic column indicates that seawater interacted with much of the gabbro section, but at relatively low water/rock ratios. This is consistent with the persistence of low 87Sr/86Sr values, even in gabbros that were extensively deformed and altered.

Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Oxygen and sulfur isotopes of peridotite and gabbro from the Mid-Atlantic Ridge

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20'N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (~250-350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6-4.4 per mil), elevated sulfide-S, and high delta34S (up to ~2 wt% and 4.4-10.8 per mil). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated delta18O (up to 8.1 per mil), high sulfide-S (up to ~3000 ppm), and negative delta34S (to -32.1 per mil) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low delta34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-delta34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids +/- heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Geochemistry and fluxes at DSDP Hole 83-504B

This chapter documents the chemical changes produced by hydrothermal alteration of basalts drilled on Leg 83, in Hole 504B. It interprets these chemical changes in terms of mineralogical changes and alteration processes and discusses implications for geochemical cycling. Alteration of Leg 83 basalts is characterized by nonequilibrium and is heterogeneous on a scale of centimeters to tens or hundreds of meters. The basalts exhibit trends toward losses of SiO2, CaO, TiO2; decreases in density; gains of MnO, Na2O, CO2, H2O+ , S; slight gains of MgO; increased oxidation of Fe; and variable changes in A12O3. Some mobility of rare earth elements (REE) also occurred, especially the light REE and Eu. The basalts have lost Ca in excess of Mg + Na gains. Variations in chemical trends are due to differing water/rock ratios, substrate control of secondary mineralogy, and superimposition of greenschist and zeolite facies mineralogies. Zeolitization resulted in uptake of Ca and H2O and losses of Si, Al, and Na. These effects are different from the Na uptake observed in other altered basalts from the seafloor attributed to the zeolite facies and are probably due to higher temperatures of alteration of Leg 83 basalts. Basalts from the transition zone are enriched in Mn, S, and CO2 relative to the pillow and dike sections and contain a metal-sulfide-rich stockwork zone, suggesting that they once were located within or near a hydrothermal upflow zone. Samples from the bottom of the dike section are extensively fractured and recrystallized indicating that alteration was significantly affected by local variations in permeability.

Physical, geochemical and magnetic properties of several ODP Leg 192 sites, Ontong Java Plateau

In this manuscript, we present the results of a physical properties investigation carried out on basaltic cores recovered from the four Leg 192 basement sites, focusing on the relationship between physical properties and alteration in basalts. Variations in physical properties in the Leg 192 basement sites closely resemble each other and reflect the amount of alteration and vein formation in the basement basalts. P-wave velocities, magnetic susceptibilities, and densities for the dense massive basalts are higher than those of more altered and heavily veined basalts. Porosity-dependent alteration is observed at Leg 192 basement sites: P-wave velocity displays a general decrease with increasing loss on ignition and potassium content. These trends are consistent with trends documented for typical alteration of oceanic crust and suggest that basalt alteration is largely responsible for the variation of the physical properties exhibited by rocks at Leg 192 basement sites. Our physical property data support the conclusion that only low-temperature seawater-mediated alteration occurred in the lava flows of the Ontong Java Plateau (OJP). This lack of higher-temperature hydrothermal alteration is consistent with the idea that the OJP basement sites are far from their eruptive vents.

Distribution, depositional form and geochemical composition of tephra horizons in ODP Sites 186-1150 and 186-1151

Major element geochemical composition was established for 59 tephra horizons from Ocean Drilling Program Sites 1150 and 1151, located in the Japan forearc. These data, encompassing typically between 15 and 30 individual shard analyses per tephra horizon, were used to investigate the degree to which sediment reworking, postdepositional geochemical alteration, and geochemical uniqueness of individual eruptives facilitate or impede the potential for establishing a tephrostratigraphical framework for the Japan Trench, as well as usage of the tephra record to document arc evolution. Evidence was found that hydration (termed phase 1 alteration) of glass shards increases with age in the Pliocene-Pleistocene, but there is no indication that element leaching (phase 2 alteration) has occurred. Post- or syn-depositional differences in preservational style are shown to have no significant bearing on tephrogeochemical homogeneity and suitability for tephrostratigraphical analysis. Overall, therefore, the volcaniclastic record is suitable for investigating medium- to long-term changes in arc geochemistry and, provided consideration is given to the potential for nonunique geochemical signatures, is suitable for erecting tephrochronological frameworks. A limited number of Pleistocene tephra correlations are suggested in furtherance of this framework goal.

Chemical and isotopic compositions of altered MORB from ODP Holes 187-1154A, 187-1155B, and 187-1160B

Boron and Pb isotopic compositions together with B-U-Th-Pb concentrations were determined for Pacific and Indian mantle-type mid-ocean ridge basalts (MORB) obtained from shallow drill holes near the Australian Antarctic Discordance (AAD). Boron contents in the altered samples range from 29.7 to 69.6 ppm and are extremely enriched relative to fresh MORB glass with 0.4-0.6 ppm B. Similarly the d11B values range from 5.5? to 15.9? in the altered basalts and require interaction with a d11B enriched fluid similar to seawater ~39.5? and/or boron isotope fractionation during the formation of secondary clays. Positive correlations between B concentrations and other chemical indices of alteration such as H2O CO2, K2O, P2O5, U and 87Sr/86Sr indicate that B is progressively enriched in the basalts as they become more altered. Interestingly, d11B shows the largest isotopic shift to +16? in the least altered basalts, followed by a continual decrease to +5-6? in the most altered basalts. These observations may indicate a change from an early seawater dominated fluid towards a sediment-dominated fluid as a result of an increase in sediment cover with increasing age of the seafloor. The progression from heavy d11B towards lighter values with increasing degrees of alteration may also reflect increased formation of clay minerals (e.g., saponite). A comparison of 238U/204Pb and 206Pb/204Pb in fresh glass and variably altered basalt from Site 1160B shows extreme variations that are caused by secondary U enrichment during low temperature alteration. Modeling of the U-Pb isotope system confirms that some alteration events occurred early in the 21.5 Ma history of these rocks, even though a significant second pulse of alteration happened at ~12 Ma after formation of the crust. The U-Pb systematics of co-genetic basaltic glass and variably low temperature altered basaltic whole rocks are thus a potential tool to place age constraints on the timing of alteration and fluid flow in the ocean crust.