Chemistry of bulk-rocks and minerals of ODP Hole 120-748C

Five hundred meters of a unique Upper Cretaceous Cr-rich glauconitic sequence (Unit III) that overlies a 3-m-thick alkali-basalt flow with underlying epiclastic volcanogenic sediments was drilled at ODP Leg 120 Site 748. The Cr-rich glauconitic sequence is lithostratigraphically and biostratigraphically divided into three subunits (IIIA, IIIB, IIIC) that can also be recognized by the Cr concentration of the bulk sediment, which is low (<200 ppm) in Subunits IIIC and IIIA and high (400-800 ppm) in Subunit IIIB. The Cr enrichment is caused by Cr-spinel, which is the only significant heavy mineral component beside Fe-Ti ores. Other Cr-bearing components are glauconite pellets and possibly some other clay minerals. The glauconitic sequence of Subunit IIIB was formed by reworking of glauconite and volcanogenic components that were transported restricted distances and redeposited downslope by mass-transportation processes. The site of formation was a nearshore, shallow inner shelf environment, and final deposition may have been on the outer part of a narrow shelf, at the slope toward the restricted, probably synsedimentary, faulted Raggatt Basin. The volcanic edifices uncovered on land were tholeiitic basalts (T-MORB), alkali-basaltic (OIB) and (?)silicic volcanic complexes, and ultramafic rocks. The latter were the ultimate source for the Cr-spinel contribution. Terrestrial aqueous solutions carried Fe, K, Cr, Si, and probably Al into the marine environment, where, depending on the redox conditions of microenvironments in the sediment, green (Fe- and K-rich) or brown (Al-rich) glauconite pellets formed. The Upper Cretaceous glauconitic sequence at Site 748 on the Southern Kerguelen Plateau constitutes the transition in space and time from terrestrial to marine, from magmatically active subaerial to magmatically passive submarine conditions, and from a tranquil platform to active rifting conditions.

Age determination and stable isotope ratios of three sediment cores from the Great Belt

The marine transgression Into the Baltic Sea through the Great Belt took place around 9,370 calibrated C-14-years B.P. The sedimentary sequence from the early brackish phase and the change to marine conditions has been investigated in detail through C-14-datings, and oxygen and carbon isotope measurements, and is interpreted by comparison with modern analogs. The oldest brackish sediments are the strongly laminated clays and silts rich in organic carbon followed by non-laminated heavily bioturbated silts. The bedding and textural characteristics and stable isotope analyses on Ammonia beccarii (dextral) and A. beccarii (sinistral) show that the deposltlonal conditions respond to a change at about 9,100 cal. a B.P. from an unstratified brackish water environment in the initial stage of the Littorina Transgression to a thermohaline layered milieu in the upper unit. The oxygen isotope results indicate that the bottom waters of this latter period had salinities and temperatures comparable to the present day Kiel Bay waters. The isotopic composition of the total organic carbon and the d13C-values of A. beccarii reveal a gradual change from an initially lacustrine/terrestrial provenance toward a brackish/marine dominated depositional environment. A stagnation of the sea level at around 9,100 to 9,400 B.P. is indicated.

Geochemical composition and atomic formulas of saponites, celadonites and clays from ODP Leg 168 sites

A drilling transect across the sedimented eastern flank of the Juan de Fuca Ridge, conducted during Leg 168 of the Ocean Drilling Program, resulted in the recovery of samples of volcanic basement rocks (pillow basalts, massive basalts, and volcanic glass breccias) that exhibit the effects of low-temperature hydrothermal alteration. Secondary clays are ubiquitous, with Mg-rich and Fe-rich saponite and celadonitic clays commonly accounting for several percent, and up to 10%-20% by volume. Present-day temperatures of the basement sites vary from 15° to 64°C, with the coolest site being about 0.8 Ma, and the warmest site being about 3.5 Ma. Whereas clays are abundant at sites that have been heated to present temperatures of 23°C and higher, the youngest site at 15°C has only a small trace of secondary clay alteration. Alteration increases as temperatures increase and as the volcanic basement ages. The chemical compositions of secondary clays were determined by electron microprobe, and additional trace element data were determined by both conventional nebulization inductively coupled plasma-mass spectroscopy (ICP-MS) and laser-ablation ICP-MS. Trioctahedral saponite and pyrite are characteristic of the interior of altered rock pieces, forming under conditions of low-oxygen fugacity. Dioctahedral celadonite-like clays along with iron oxyhydroxide and Mg-saponite are characteristic of oxidized haloes surrounding the nonoxidized rock interiors. Chemical compositions of the clays are very similar to those determined from other deep-sea basalts altered at low temperature. The variable Mg:Fe of saponite appears to be a systematic function both of the Mg:Fe of the host rock and the oxidation state during water-rock interaction.

Simulated changes in ocean physics and carbon cycle for LGM experiments with shifting positions of the Southern Hemisphere westerly winds using the MITgcm, links to model results in NetCDF format

We explore the impact of a latitudinal shift in the westerly wind belt over the Southern Ocean on the Atlantic meridional overturning circulation (AMOC) and on the carbon cycle for Last Glacial Maximum background conditions using a state-of-the-art ocean general circulation model. We find that a southward (northward) shift in the westerly winds leads to an intensification (weakening) of no more than 10% of the AMOC. This response of the ocean physics to shifting winds agrees with other studies starting from preindustrial background climate, but the responsible processes are different. In our setup changes in AMOC seemed to be more pulled by upwelling in the south than pushed by downwelling in the north, opposite to what previous studies with different background climate are suggesting. The net effects of the changes in ocean circulation lead to a rise in atmospheric pCO2 of less than 10 atm for both northward and southward shift in the winds. For northward shifted winds the zone of upwelling of carbon- and nutrient-rich waters in the Southern Ocean is expanded, leading to more CO2 outgassing to the atmosphere but also to an enhanced biological pump in the subpolar region. For southward shifted winds the upwelling region contracts around Antarctica, leading to less nutrient export northward and thus a weakening of the biological pump. These model results do not support the idea that shifts in the westerly wind belt play a dominant role in coupling atmospheric CO2 rise and Antarctic temperature during deglaciation suggested by the ice core data.

Chemical composition of sepiolites and palygorskites from bottom sediments of the Eastern Indian

In fault zones of the East Indian Ridge and adjacent areas of ocean floor almost monomineral sepiolite- and palygorskite clays have been found. They have been studied by a complex of optical and physical methods. Formation of authigenic sepiolites and palygorskite had occurred under influence of Mg- and Si-rich hydrothermal solutions by metasomatic replacement of montmorillonite clays, or by precipitation from saturated solutions in cracks of various rocks.

Cenozoic sediments facies and geochemistry of ODP Hole 103-637A

The late Cenozoic deposits recovered at ODP Site 637 from the Iberian Abyssal Plain near the continental margin off northwestern Spain include three main facies groups. Turbidites are the dominant facies association (two-thirds of the total thickness), followed by pelagites (one-fourth), and subordinate amounts of contourites (one-tenth). Slump deposits occur locally in the upper Miocene and middle Pliocene. Turbidity currents and pelagic settling were the significant sediment depositional processes from the Pliocene to the Pleistocene, whereas bottom currents predominated during the late Miocene. Fine-grained, base-cut-out turbidites, normally starting with the Td division, are the most abundant sequence type. The pelagites include both carbonate-rich pelagic and hemipelagic facies. The two types of contourites, sandy and calcareous-rich or fine-grained terrigenous, record two types of bottom-current processes. The Cenozoic deposits at Site 637 show a general upward transition from contourites in the upper Miocene to turbidites in the Pliocene-Quaternary. The entire section is rhythmically bedded and has a poorly developed cyclic pattern defined by variations in the total carbonate content. The low sedimentation rates also show the same cyclicity, with lower values for the late Miocene and late Pliocene. This evolution reflects the predominant depositional processes and the dissolution of carbonates by a lower CCD during the late Miocene.

Chemical and mineral compositions of recent and ancient sediments and sedimentary rocks from the Mariana Trench

On the bed and on the ocean slope of the southern latitudinal part of the Mariana Trench ancient sediments, as well as sedimentary and igneous rocks are exposed. In the lower part of the sampled part of the studied section Late Oligocene to Early Miocene chalk-like limestones and marls occur. Upward marly tuffites and tuffs (apparently alternating with carbonate rocks) occur. These rocks are overlain by Early Miocene tuffaceous clays and siliceous-clayey muds. In the upper part of the section there are Pleistocene pelagic clays and ethmodiscus oozes.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

(Table 1) Lithofacies interpretation and distribution in sediment core CRP-3

Seven hundred and nineteen samples from throughout the Cainozoic section in CRP-3 were analysed by a Malvern Mastersizes laser particle analyser, in order to derive a stratigraphic distribution of grain-size parameters downhole. Entropy analysis of these data (using the method of Woolfe & Michibayashi, 1995) allowed recognition of four groups of samples, each group characterised by a distinctive grain-size distribution. Group 1, which shows a multi-modal distribution, corresponds to mudrocks, interbedded mudrock/sandstone facies, muddy sandstones and diamictites. Group 2, with a sand-grade mode but showing wide dispersion of particle size, corresponds to muddy sandstones, a few cleaner sandstones and some conglomerates. Group 3 and Group 4 are also sand-dominated, with better grain-size sorting, and correspond to clean, well-washed sandstones of varying mean grain-size (medium and fine modes, respectively). The downhole disappearance of Group 1, and dominance of Groups 3 and 4 reflect a concomitant change from mudrock- and diamictite-rich lithology to a section dominated by clean, well-washed sandstones with minor conglomerates. Progressive downhole increases in percentage sand and principal mode also reflect these changes. Significant shifts in grain-size parameters and entropy group membership were noted across sequence boundaries and seismic reflectors, as recognised in other studies.

Geochemistry of basal dolomitic and Fe-Mn sediments from the Tyrrhenian Sea

In the Tyrrhenian Sea (Western Mediterranean), unusual reddish, soft to lithified, dolomitic sediments up to 45 m thick overlie igneous crust at the base of thick Pliocene-Quaternary deep-sea sediment successions in the Marsili (Site 650) and Vavilov (Site 651) basins. These sediments also overlie the Gortani Ridge, a basaltic Seamount near the base of the Sardinian continental margin (Site 655). At both basinal sites (650, 651), the lowest sediments are dolomitic, with manganese oxide (MnO) segregations. Whole-rock X-ray diffraction indicates abundant dolomite and quartz, with subordinate calcite, illite (authigenic), feldspar and minor kaolinite, chlorite, and anhydrite. Chemical analyses show strong enrichment in magnesium oxide (MgO) and MnO relative to shale or deep-sea clay. Mg and Mn correlate positively and exhibit decreasing concentrations up the succession in the Marsili Basin (Site 650). The following scenario is proposed: peridotites were exposed on the seafloor in the Vavilov Basin (Site 651) and then eroded, depositing talc in local fine-grained dolomitic sediments within the igneous basement. After local magmatism ended, the igneous basement at each site subsided rapidly (about 800 m/m.y.) and was blanketed with calcareous and clay-rich oozes. During early diagenesis (from isotopic evidence; McKenzie et al., this volume) tepid fluids, of modified seawater composition, reacted with and dolomitized the overlying deep-sea sediments. At Site 651 additional Mg may have been extracted from asthenosphere peridotite cored at shallow depths (about 100 m). One can hypothesize that fluids rich in Mg and Mn were flushed from the igneous basement, triggered by extensional faulting and local tilting during subsidence of the basement, and that these fluids then dolomitized the base of the overlying sediment succession. Late tectonic movements in the Vavilov Basin (Site 651) fractured already lithified dolomitic sediments and more reducing (? hydrothermal) fluids locally remobilized Fe and Mn and corroded dolomite crystals.

Chemistry of secondary minerals from the deep sheeted dike complex of ODP Holes 137-504B and 140-504B

Dolerites sampled from the lower sheeted dikes from Hole 504B during Ocean Drilling Program Legs 137 and 140, between 1562.4 and 2000.4 mbsf, were examined to document the mineralogy, petrography, and mineral parageneses associated with secondary alteration, to constrain the thermal history and composition of hydrothermal fluids. The main methods used were mineral chemical analyses by electron microprobe, X-ray diffraction, and cathodoluminescence microscopy. Temperatures of alteration were estimated on the basis of single and/or coexisting mineral chemistry. Permeability is important in controlling the type and extent of alteration in the studied dike section. At the meter-scale, intervals of weakly altered dolerites containing fresh olivine are interpreted as having experienced restricted exposure to hydrothermal fluids. At the centimeter- or millimeter-scale, alteration patches and extensively altered halos adjacent to veins reflect the permeability related to intergranular primary porosity and cracks. Most of the sheeted dike alteration in this case resulted from non-focused, pervasive fluid-rock interaction. This study confirms and extends the previous model for hydrothermal alteration at Hole 504B: hydrothermal alteration at the ridge axis followed by seawater recharge and off-axis alteration. The major new discoveries, all related to higher temperatures of alteration, are: (1) the presence of hydrothermal plagioclase (An80-95), (2) the presence of deuteric and/or hydrothermal diopside, and (3) the general increasing proportion of amphiboles, and particularly magnesio-hornblende with depth. We propose that the dolerites at Hole 504B were altered in five stages. Stage 1 occurred at high temperatures (less than 500° to 700°C) and involved late-magmatic formation of Na- and Ti-rich diopside, the hydrothermal formation of Na, Ti-poor diopside and the hydrothermal formation of an assemblage of An-rich plagioclase + hornblende. Stage 2 occurred at lower temperatures (250°-320°C) and is characterized by the appearance of actinolite, chlorite, chlorite-smectite, and/or talc (in low permeability zones) and albite. During Stage 3, quartz and epidote precipitated from evolved hydrothermal fluids at temperatures between 310° and 320°C. Anhydrite appeared during Stage 4 and likely precipitated directly from heated seawater. Stage 5 occurred off-axis at low temperatures (250°C) with laumontite and prehnite from evolved fluids.

Composition and structural formulas of ODP Site 200-1224 Eocene ferrobasalt minerals

The ~46-m.y.-old igneous basement cored during Leg 200 in the North Pacific represents one of the few cross sections of Pacific oceanic crust with a total penetration into basalt of >100 m. The rocks, emplaced during the Eocene at a fast-spreading rate (~14 cm/yr; full rate) are strongly differentiated tholeiitic basalts (ferrobasalts) with 7-4.5 wt% MgO, relatively high TiO2 (2-3.5 wt%), and total iron as Fe2O3 (9.1-16.8 wt%). The differentiated character of these lavas is related to unusually large amounts of crystallization differentiation of plagioclase, clinopyroxene, and olivine. The lithostratigraphy of the basement (cored to ~170 meters below seafloor) is divided into three units. The deepest unit (lithologic Unit 3), is a succession of lava flows of no more that a few meters thickness each. The intermediate unit (lithologic Unit 2) is represented by intermixed thin flows and pillows, whereas the shallowest unit (lithologic Unit 1), comprises two massive flows. The rocks range from aphyric to sparsely clinopyroxene-plagioclase-phyric (phenocryst content = <3 vol%) and from holocrystalline to hypohyaline. Chilled margins of pillow fragments show holohyaline to sparsely vitrophyric textures. Site 1224 oxide minerals present a type of alteration not previously seen, where titanomagnetite is only partially destroyed and the pure magnetite component is partially removed from the mineral, leaving, in the most extreme case, a nearly pure ulvöspinel residuum. As a result of this dissolution, iron, mainly in the oxidized state, is added to the circulating solvent fluids. This means that a considerable metal source can result from low-temperature reactions throughout the upper ocean crust. The coarsest-grained lithologic Unit 1 rocks have interstitial myrmekitic intergrowths of quartz and sodic plagioclase (~An12), roughly similar in mineralogy and bulk composition to tonalite/trondhjemite veinlets in abyssal gabbros from the southwest Indian Ocean and Hess Deep, eastern equatorial Pacific. Based on idiomorphic relationships and projections into the simplified Q-Ab-Or-H2O granite ternary system, the myrmekitic intergrowths formed at the same time as, or just after, the oxide minerals coprecipitated and at low water vapor pressure (~0.5 kbar). Their compositions correspond to SiO2-oligoclase intergrowths that are considerably less potassic than dacitic glasses that erupt, although rarely, along the East Pacific Rise or that have been produced experimentally by partial melting of gabbro. Based on the crystallization history and comparison to experimental data, the original interstitial siliceous liquids resulted from late-stage immiscible separation of siliceous and iron-rich liquids. The rare andesitic lavas found along the East Pacific Rise may be hybrid rocks formed by mixing of these immiscible siliceous melts with basaltic magma.

Interactive effects of salinity and elevated CO2 levels on juvenile eastern oysters, Crassostrea virginica

Rising levels of atmospheric CO2 lead to acidification of the ocean and alter seawater carbonate chemistry, which can negatively impact calcifying organisms, including mollusks. In estuaries, exposure to elevated CO2 levels often co-occurs with other stressors, such as reduced salinity, which enhances the acidification trend, affects ion and acid-base regulation of estuarine calcifiers and modifies their response to ocean acidification. We studied the interactive effects of salinity and partial pressure of CO2 (PCO2) on biomineralization and energy homeostasis in juveniles of the eastern oyster, Crassostrea virginica, a common estuarine bivalve. Juveniles were exposed for 11 weeks to one of two environmentally relevant salinities (30 or 15 PSU) either at current atmospheric PCO2 (400 µatm, normocapnia) or PCO2 projected by moderate IPCC scenarios for the year 2100 (700-800 µatm, hypercapnia). Exposure of the juvenile oysters to elevated PCO2 and/or low salinity led to a significant increase in mortality, reduction of tissue energy stores (glycogen and lipid) and negative soft tissue growth, indicating energy deficiency. Interestingly, tissue ATP levels were not affected by exposure to changing salinity and PCO2, suggesting that juvenile oysters maintain their cellular energy status at the expense of lipid and glycogen stores. At the same time, no compensatory upregulation of carbonic anhydrase activity was found under the conditions of low salinity and high PCO2. Metabolic profiling using magnetic resonance spectroscopy revealed altered metabolite status following low salinity exposure; specifically, acetate levels were lower in hypercapnic than in normocapnic individuals at low salinity. Combined exposure to hypercapnia and low salinity negatively affected mechanical properties of shells of the juveniles, resulting in reduced hardness and fracture resistance. Thus, our data suggest that the combined effects of elevated PCO2 and fluctuating salinity may jeopardize the survival of eastern oysters because of weakening of their shells and increased energy consumption.