Geochemistry of Early Cretaceous basaltic rocks from ODP Sites 123-765 and 123-766

The Early Cretaceous basaltic rocks obtained from Sites 765 and 766 in the eastern Indian Ocean floor were mostly iron-rich normal mid-ocean ridge basalts (N-MORB), which were derived from a depleted mantle source having strongly light rare earth element (LREE)-depleted rare-earth patterns and a high titanium/zirconium (Ti/Zr) ratio. Basaltic rocks in the upper part of the Site 765 basement section include megacrysts and gabbroic fragments of widely varying mineral chemistry. These megacrysts range from An90 plagioclase, including highly magnesian basaltic glass coexisting with augite of Mg# (= 100 Mg/[Fe+Mg]) at 85, to An50 plagioclase coexisting with hypersthene. This varying mineralogy of megacrysts and gabbroic fragments indicates that a considerable degree of fractional crystallization took place in the magma chamber. The unusual negative correlation between incompatible elements (e.g., TiO2) and FeO*/MgO observed among Site 765 basement basalts and fresh volcanic glasses suggest source-mantle heterogeneity in terms of FeO*/MgO. Strontium isotope ratios (87Sr/86Sr) of the basaltic rocks from both sites are between 0.7027 and 0.7033 and are comparable to those of mid-Indian Ocean ridge basalts (MIORB). The basalt pebbles encountered in the sedimentary section may have been transported from the basement highs nearer the Australian continent and include basaltic compositions ranging from primitive N-MORBs to evolved enriched (E)-MORBs. Their mantle source was not as depleted as that of the basement basalts. These rocks may be the products of earlier volcanism that took place during the rifting of the Australian continent.

Geochemistry of abyssal peridotites from ODP Hole 209-1274A

Aqueous dihydrogen (H2,aq) is produced in copious amounts when seawater interacts with peridotite and H2O oxidizes ferrous iron in olivine to ferric iron in secondary magnetite and serpentine. Poorly understood in this process is the partitioning of iron and its oxidation state in serpentine, although both impose an important control on dihydrogen production. We present results of detailed petrographic, mineral chemical, magnetic and Mößbauer analyses of partially to fully serpentinized peridotites from the Ocean Drilling Program (ODP) Leg 209, Mid-Atlantic Ridge (MAR) 15°N area. These results are used to constrain the fate of iron during serpentinization and are compared with phase equilibria considerations and peridotite-seawater reaction path models. In samples from Hole 1274A, mesh-rims reveal a distinct in-to-out zoning from brucite at the interface with primary olivine, followed by a zone of serpentine + brucite ± magnetite and finally serpentine + magnetite in the outermost mesh-rim. The compositions of coexisting serpentine (Mg# 95) and brucite (Mg# 80) vary little throughout the core. About 30-50% of the iron in serpentine/brucite mesh-rims is trivalent, irrespective of subbasement depth and protolith (harzburgite versus dunite). Model calculations suggest that both partitioning and oxidation state of iron are very sensitive to temperature and water-to-rock ratio during serpentinization. At temperatures above 330 °C the dissolution of olivine and coeval formation of serpentine, magnetite and dihydrogen depends on the availability of an external silica source. At these temperatures the extent of olivine serpentinization is insufficient to produce much hydrogen, hence conditions are not reducing enough to form awaruite. At T < 330 °C, hydrogen generation is facilitated by the formation of brucite, as dissolution of olivine to form serpentine, magnetite and brucite requires no addition of silica. The model calculations suggest that the iron distribution observed in serpentine and brucite is consistent with formation temperatures ranging from <150 to 250 °C and bulk water-to-rock ratios between 0.1 and 5. These conditions coincide with peak hydrogen fugacities during serpentinization and are conducive to awaruite formation during main stage serpentinization. The development of the common brucite rims around olivine is either due to an arrested reaction olivine -> brucite -> serpentine + brucite, or reflects metastable olivine-brucite equilibria developing in the strong gradient in silica activity between orthopyroxene (talc-serpentine) and olivine (serpentine-brucite).

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.

Stable carbon and oxygen isotope ratios of Miocene to Recent foraminifera from the Rio Grande Rise, South Atlantic

Miocene to Recent species of planktic foraminifera in the Globorotalia (Globoconella) lineage evolved entirely within the thermocline. All species are most abundant within subtropical-temperate watermasses throughout their history. The near stasis in distribution within the thermocline and the subtropical convergence suggests the major morphological changes in Globorotalia (Globoconella) may have occurred through habitat subdivision rather than by vicariant shifts into new watermasses. At the Rio Grande Rise, in the South Atlantic, modern G. inflata is 0.66-0.84? more positive for delta18O than the most enriched coexisting Globigerinoides sacculifer and probably grows in the mid thermocline deeper than 325 m. All extinct globoconellid species have mean delta18O ratios 0.5-0.8? more positive than Globigerinoides trilobus and G. sacculifer and probably lived within the thermocline as well. Major events in skeletal evolution are poorly correlated with changes in delta18O in this group. These include evolutionary transitions to compressed, smooth-walled tests and acquisition of keels. In addition, morphological reversals from the umbilically-inflated G. conomiozea to biconvex G. pliozea and to unkeeled G. puncticulata occur in the absence of changes in delta18O signature. Instead, the ranges of delta18O between different species almost completely overlap once corrected for temporal changes in delta18O of sea water. Foraminifera morphologies have been widely considered to evolve in response to changes in watermasses or depth habitats. However, the variety of skeletal shapes in the globoconellid lineage apparently are not adaptations to a progressive radiation from the surface mixed layer into deeper waters.

Crystal morphologies and pyroxene compositions in boninites and tholeiitic basalts at DSDP Holes 60-458 and 60-459B

Not all boninites are glassy lavas. Those of Hole 458 in the Mariana fore-arc region are submarine pillow lavas and more massive flows in which glass occurs only in quenched margins. Pillow and flow interiors have abundant Plagioclase spherulites, microlites, or even larger crystals but can be recognized as boninites by (1) occurrence of bronzite, (2) presence of augite-bronzite microphenocryst intergrowths, and (3) reversal of the usual basaltic groundmass crystallization sequence of plagioclase-augite to augite-plagioclase. The latter is accentuated by sharply contrasting augite and Plagioclase crystal morphologies near pillow margins, a consequence of rapid cooling rates. This crystallization sequence appears to be a consequence of boninites having higher SiO2 and Mg/Mg + Fe than basalts but lower CaO/Al2O3. Microprobe data are used to illustrate the effects of rapid cooling on the compositions of pyroxene and microphenocrysts in a glassy boninite sample and to estimate temperatures of crystallization of coexisting bronzite and augite. A range from 1320°C to 1200°C is calculated with an average of 1250°C. This is higher by 120°-230° than the known range for western Pacific arc tholeiites and by over 300° than for calc-alkalic andesites. Boninites of Hole 458 lack olivine and clinoenstatite but are otherwise chemically and petrographically similar to boninites that have these minerals. In order to distinguish the two types, the Hole 458 lavas are here termed boninites and the others are termed olivine boninites. Arc tholeiite pillow lavas from Holes 458 and 459B are briefly described and their textures compared to fractionated, moderately iron-enriched, abyssal tholeiites. Massive tholeiite flows contain striking quartz-alkali feldspar micrographic intergrowths with coarsely spherulitic textures resulting from in situ magmatic differentiation. Such intergrowths are rare in massive abyssal tholeiites cored by DSDP and probably occur here because arc tholeiites have higher normative quartz at comparable degrees of iron enrichment - a result of higher oxygen fugacities and earlier separation of titanomagnetite - than abyssal tholeiites.

Strontium and neodymium isotope data for barite separates and pore waters, and isotope and concentration data for foraminifera and fish teeth from DSDP Leg 85 sediments

Strontium and neodymium isotopic data are reported for barite samples chemically separated from Late Miocene to Pliocene sediments from the eastern equatorial Pacific. At a site within a region of very high productivity close to the equator, 87Sr/86Sr ratios in the barite separates are indistinguishable from those of foraminifera and fish teeth from the same samples. However, at two sites north of the productivity maximum barite separates have slightly, but consistently lower (averaging 0.000062) ratios than the coexisting phases, although values still fall within the total range of published values for the contemporaneous seawater strontium isotope curve. We examine possible causes for this offset including recrystallization of the foraminifera, fish teeth or barite, the presence of non-barite contaminants, or incorporation of older, reworked deep-sea barite; the inclusion of a small amount of hydrothermal barite in the sediments seems most consistent with our data, although there are difficulties associated with adequate production and transportation of this phase. Barite is unlikely to replace calcite as a preferred tracer of seawater strontium isotopes in carbonate-rich sediments, but may prove a useful substitute in cases where calcite is rare or strongly affected by diagenesis. In contrast to the case for strontium, neodymium isotopic ratios in the barite separates are far from expected values for contemporary seawater, and appear to be dominated by an (unobserved) eolian component with high neodymium concentration and low 143Nd/144Nd. These results suggest that the true potential of barite as an indicator of paleocean neodymium isotopic ratios and REE patterns will be realized only when a more selective separation procedure is developed.

Stable oxygen and carbon isotope composition of benthic foraminifera from the western Mediterranean Sea

The influence of microhabitat, organic matter flux, and metabolism on the stable oxygen and carbon isotope composition of live (Rose Bengal stained) and dead (empty tests) deep-sea benthic foraminifera from the Gulf of Lions (western Mediterranean Sea) have been studied. The total range of observed foraminiferal isotope values exceeds 1.0 per mil for d18O and 2.2 per mil for d13C demonstrating a wide range of coexisting disequilibria relative to d18O of equilibrium calcite (d18OEQ) and d13C of bottom water dissolved inorganic carbon (d13CDIC). The mean d18O values reveal strongest disequilibria for the studied epifaunal to shallow infaunal species (Cibicidoides pachydermus, Uvigerina mediterranea, Uvigerina peregrina) while values approach equilibrium in deep infaunal species (Globobulimina affinis, Globobulimina pseudospinescens). The mean d13C values decrease with increasing average living depths of the different species, thus reflecting a dominant microhabitat (pore water) signal. At the axis of the Lacaze-Duthier Canyon a minimum d13CDIC pore water gradient of approximately -2.1 per mil is assessed for the upper 6 cm of the surface sediment. Although live individuals of U. mediterranea were found in different depth intervals their mean d13C values are consistent with calcification at an average living depth around 1 cm. The deep infaunal occurrence of U. mediterranea specimens suggests association with macrofaunal burrows creating a microenvironment with geochemical characteristics similar to the topmost centimeter. This also explains the excellent agreement between stable isotope signals of live and dead individuals. The ontogenetic enrichment in both d18O and d13C values of U. mediterranea suggests a slow-down of metabolic rates during test growth similar to that previously observed in planktic foraminifera. Enhanced organic carbon fluxes and higher proportion of resuspended terrestrial organic material at the canyon axis are reflected by d13C values of U. mediterranea on average 0.58 per mil lower than those from the open slope. These results demonstrate the general applicability of the d13C signal of this species for the reconstruction of past organic matter fluxes in the Mediterranean Sea. Further studies on live specimens are needed for a more quantitative paleoceanographic approach.

Rare earth and other chemical element contents and partitions in bottom sediments, micronodules, and nodules from the bioproductive zone of the Pacific Ocean

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50-250, 250-500, and >500 ?m), coexisting macronodules, and host sediments were studied. Samples were collected at three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of surface waters. Influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, Ce concentration inversely correlates with micronodule size and drops to the lowest value in macronodules and host sediments. Decrease of Ce concentration is generally accompanied by Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with micronodule sizes. Contribution of the diagenetic source is maximal for macronodules. REE composition distinctions for micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. Relationship and general trend in chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.

Stable isotope analyses of Cretaceous sediment samples

We report the sulfur and oxygen isotope composition of sulfate (d34SSO4 and d18OSO4, respectively) in coexisting barite and carbonate-associated sulfate (CAS), which we use to explore temporal variability in the marine sulfur cycle through the middle Cretaceous. The d34SSO4 of marine barite tracks previously reported sulfur isotope data from the tropical Pacific. The d18OSO4 of marine barite exhibits more rapid and larger isotopic excursions than the d34SSO4 of marine barite; these excursions temporally coincide with Ocean Anoxic Events (OAEs). Neither the d34SSO4 nor the d18OSO4 measured in marine barite resembles the d34SSO4 or the d18OSO4 measured in coexisting CAS. Culling our data set for elemental parameters suggestive of carbonate recrystallization (low [Sr] and high Mn/Sr) improves our record of d18OSO4 in CAS in the Cretaceous. This suggests that the CAS proxy can be impacted by carbonate recrystallization in some marine sediments. A box model is used to explore the response of the d34SSO4 and d18OSO4 to different perturbations in the marine biogeochemical sulfur cycle. We conclude that the d34SSO4 in the middle Cretaceous is likely responding to a change in the isotopic composition of pyrite being buried, coupled possibly with a change in riverine input. On the other hand, the d18OSO4 is likely responding to rapid changes in the reoxidation pathway of sulfide, which we suggest may be due to anoxic versus euxinic conditions during different OAEs.

Morphological descriptions from the recent bivalve of the genus Calyptogena (Vesicomyidae)

The genus Calyptogena (Bivalvia: Vesicomyidae) comprises highly specialized bivalves living in symbiosis with sulphur-oxidizing bacteria in reducing habitats. In this study, the genus is revised using shell and anatomical features. The work is based on type material, as well as on the extensive collection of vesicomyids obtained during twelve expeditions to the Pacific and Indian Oceans. Nine Recent species are ascribed to the genus Calyptogena, four of which are new: C. pacifica Dall, 1891, C. fausta Okutani, Fujikura & Hashimoto, 1993, C. rectimargo Scarlato, 1981, C. valdiviae (Thiele & Jaeckel, 1931), C. gallardoi Sellanes & Krylova, 2005, C. goffrediae n. sp., C. starobogatovi n. sp., C. makranensis n. sp. and C. costaricana n. sp. The characteristic features of Calyptogena are: shell up to 90 mm in length, elongate-elliptical or elongate; presence of escutcheon; presence of broad posterior ramus (3b) of right subumbonal cardinal tooth as well as right posterior nymphal ridge; absence of pallial sinus as a result of attachment of intersiphonal septal retractor immediately adjacent to ventral surface of posterior adductor; absence of processes on inner vulva of inhalant siphon; presence of inner demibranch only, with descending and ascending lamellae with interlamellar septa not divided into separate tubes. The most closely related taxa to Calyptogena are probably the genus Isorropodon Sturany, 1896, and the group of species represented by 'Calyptogena' phaseoliformis Métivier, Okutani & Ohta, 1986. These groups have several characters in common, namely absence of pallial sinus, presence of single inner pair of demibranchs and absence of processes on inner vulva of inhalant siphon. The worldwide distribution of the genus Calyptogena suggests that methane seeps at continental margins are the major dispersal routes and that speciation was promoted by geographical isolation. Recent species diversity and fossil records indicate that the genus originated in the Pacific Ocean. Sufficient data to discuss the distribution at species level exist only for C. pacifica, which has a remarkably narrow bathymetric range. Published studies on the physiology of C. pacifica suggest that adaptation to a specific geochemical environment has led to coexisting vesicomyid genera. The bacteria-containing gill of C. pacifica and other Calyptogena species is one of the most specialized in the family Vesicomyidae and may reflect these ecological adaptations.