Authigenic carbonate of ODP SIte 104-643

Different generations of complex authigenic carbonates formed in siliceous muds (lithologic Unit IV) and hemipelagic clays (lithologic Unit V) of ODP Site 643, Leg 104 Norwegian Sea. The dominant phase in Unit IV is an early diagenetic Mn, Fe-calcite with a strong negative d13C ( -14 to -16 per mil) signature, and slightly negative d180 values. The strong negative d13C results from extensive incorporation of 12C-enriched CO2 derived from bacterial degradation of marine organic matter into early Mn, Fe - calcite cements. Concomitant framboidal pyrite precipitation and abundant SEM microtextures showing excellent preservation of delicate structures of fragile diatom valves by outpourings with early Mn-calcites strongly support their shallow burial formation before the onset of compaction. Later generations of authigenic mineralizations in lithologic Unit IV include minor amounts of a second generation of calcite with platy crystals, possibly precipitated along with opal-A dissolution, and finally opal-CT crystallization in deeper seated environments overgrowing earlier precipitates with films and lepispheres. The last mineralization is collophane (fluor apatite) forming amorphous aggregates and tiny hexagonal crystals. Authigenic mineral assemblages in lithologic Unit V consist of rhodochrosites, transitional rhodochrosite/manganosiderites, and apatite. A negative d13C ( -7.1 to -15.6 per mil) and a fluctuating d18O signal indicates that the micritic to sparitic rhodochrosites, transitional rhodochrosites/manganosiderites were formed at various burial depths. CO2 resulted from organic matter degradation in the lowermost sulfate reduction zone and from biogenic methane generation in the lowermost sediments, resulting in variable and negative d13C signals. The change in carbonate mineralogy reflects major compositional differences compared to sediments in Unit IV. Most prominent is an increase in altered ash as a primary sediment component and a sudden decrease of siliceous microfossils. Upward diffusion of cations, lowered salinities in pore waters, and elevated temperatures provide diagenetic environments favoring increased remobilization processes.

The distributions, C- and O-isotopic compositions, and frequency of giant-ooids

Early Triassic oceans were characterized by deposition of a number of "anachronistic facies", including microbialites, seafloor carbonate cement fans, and giant ooids. Giant ooids were particularly prevalent in Lower Triassic sections across South China and exhibit unusual features that may provide insights into marine environmental conditions following the end-Permian mass extinction. The section at Moyang (Guizhou Province) contains abundant giant ooids ranging in size between 2 and 6 mm (maximum 12 mm) and exhibiting various cortical structures, including regular, deformed, compound, regenerated and "domed". Preservation of ooid cortical structure is generally good as indicated by petrographic observations, and trace element and carbon isotope analyses suggest that diagenesis occurred in a closed diagenetic system. All ooids exhibit fine concentric laminae, frequently alternating between light-colored coarsely crystalline and dark-colored finely crystalline layers probably reflecting variation in organic content or original mineralogy. Under scanning electron microscope, biomineralized filaments or biofilms and tiny carbonate fluorapatite (CFA) crystals are commonly found in the finely crystalline layers. We infer that the precipitation of CFA was related to adsorption of P via microbial activity on the surfaces of ooids following episodic incursions of deep waters rich in carbon dioxide, hydrogen sulfide and phosphate into shallow-marine environments. Giant ooid precipitation may have been promoted in shallow ramp settings during these events by increased watermass agitation and supersaturation with respect to calcium carbonate, as well as reduced carbonate removal rates through biotic skeletal formation. Spatio-temporal distribution data reveal that giant ooids were widespread in the Tethyan region during the Early Triassic, and that they were most abundant immediately after the end-Permian crisis and disappeared gradually as metazoans repopulated marine environments.

Chemical and isotope composition of carbonate nodules and host bottom sediments from Core DM9-666, Gulf of California

Results of mineralogical and isotopic analyzes of sulfur and carbon in carbonate nodules and host bottom sediments and results of 14C measurement in carbonate nodules are reported. It is proved that the carbonate nodules formed 11-22 thousand years ago in anaerobic diagenesis of bottom sediments rich in organic matter. Isotopic light metabolic carbon dioxide was a source of carbonate for nodules. It formed during microbial degradation of organic matter of bottom sediments.

Foraminiferal assemblages and stable isotopes across the early Paleogene carbonate facies of Perth Abyssal Plain off Western Australia

Bulk carbonate content, planktic and benthic foraminiferal assemblages, stable isotope compositions of bulk carbonate and Nuttallides truempyi (benthic foraminifera), and non-carbonate mineralogy were examined across ~30 m of carbonate-rich Paleogene sediment at Deep Sea Drilling Project (DSDP) Site 259, on Perth Abyssal Plain off Western Australia. Carbonate content, mostly reflecting nannofossil abundance, ranges from 3 to 80% and generally exceeds 50% between 35 and 57 mbsf. A clay-rich horizon with a carbonate content of about 37% occurs between 55.17 and 55.37 mbsf. The carbonate-rich interval spans planktic foraminiferal zones P4c to P6b (~57-52 Ma), with the clay-rich horizon near the base of our Zone P5 (upper)-P6b. Throughout the studied interval, benthic species dominate foraminiferal assemblages, with scarce planktic foraminifera usually of poor preservation and limited species diversity. A prominent Benthic Foraminiferal Extinction Event (BFEE) occurs across the clay-rich horizon, with an influx of large Acarinina immediately above. The delta13C records of bulk carbonate and N. truempyi exhibit trends similar to those observed in upper Paleocene-lower Eocene (~57-52 Ma) sediment from other locations. Two successive decreases in bulk carbonate and N. truempyi delta13C of 0.5 and 1.0? characterize the interval at and immediately above the BFEE. Despite major changes in carbonate content, foraminiferal assemblages and carbon isotopes, the mineralogy of the non-carbonate fraction consistently comprises expanding clay, heulandite (zeolite), quartz, feldspar (sodic or calcic), minor mica, and pyrolusite (MnO2). The uniformity of this mineral assemblage suggests that Site 259 received similar non-carbonate sediment before, during and after pelagic carbonate deposition. The carbonate plug at Site 259 probably represents a drop in the CCD from ~57 to 52-51 Ma, as also recognized at other locations.

Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.

(Table 2) Oxygen, carbon, and strontium isotopic composition of carbonate-brucite material from the Lost City hydrothermal field

The isotopic (dD, d18O, d13C, and 87Sr/86Sr) and geochemical characteristics of hydrothermal solutions from the Mid-Atlantic Ridge and the material of brucite-carbonate chimneys at the Lost City hydrothermal field at 30°N, MAR, were examined to assay the role of the major factors controlling the genesis of the fluid and hydrothermal chimneys of the Lost City field. The values of dD and d18O in fluid samples indicates that solutions at the Lost City field were produced during the serpentinization of basement ultramafic rocks at temperatures higher than 200°C and at relatively low fluid/rock ratios (<1). The active role of serpentinization processes in the genesis of the Lost City fluid also follows from the results of the electron-microscopic studying of the material of hydrothermal chimneys at this field. The isotopic (d18O, d13C, and 87Sr/86Sr) and geochemical (Sr/Ca and REE) signatures indicate that, before its submarine discharging at the Lost City field, the fluid filtered through already cold altered outer zones of the Atlantis Massif and cooled via conductive heat loss. During this stage, the fluid could partly dissolve previously deposited carbonates in veins cutting serpentinite at the upper levels of the Atlantis Massif and the carbonate cement of sedimentary breccias underlying the hydrothermal chimneys. Because of this, the age of modern hydrothermal activity at the Lost City field can be much younger than 25 ka.

(Table 1) Oxygen and carbon isotopes and calcium carbonte of bulk carbonate at DSDP Hole 72-516F

A detailed oxygen and carbon isotope study of the upper Maestrichtian-lower Paleocene section of Hole 516F from the Rio Grande Rise reveals that large isotopic anomalies are clearly associated with the Cretaceous/Tertiary boundary. Across the Cretaceous/Tertiary boundary, the total carbonate content reaches a maximum exceeding 80% before rapidly decreasing in covariance with the carbon isotope record. This strong covariance between d13C and percent CaCO3 suggests either a significant reduction in primary productivity or a rapid shoaling of the calcium carbonate compensation depth. Importantly, the d13C record 2 Ma after the Cretaceous/Tertiary boundary remained depleted in 13C by at least 0.5 per mil compared to the late Maestrichtian.

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

Mineralogy, grain size composition, bulk carbonate isotopic ratios and ages of ODP Site 182-1128 sediments

This report presents mineralogic and geochemical data from Ocean Drilling Program Leg 182 Site 1128 in the Great Australian Bight. Clay mineralogy is dominated by mixed-layer illite-smectite, followed by minor amounts of kaolinite and illite, with intervals of pure smectite. Carbonate mineralogy is exclusively low-Mg calcite, except for one interval of dolomite in lower Oligocene sediments. Carbonate increases significantly in upper Eocene sediments, decreases through the lower Oligocene, then increases again in the Neogene. Quartz is present as a minor component that covaries inversely with carbonate. High-resolution sampling associated with Chron 13 normal (early Oligocene) reveals high-frequency (~23 k.y.) fluctuations in clay mineralogy and carbonate abundance and a positive oxygen and carbon isotope excursion (in bulk carbonates) related to Antarctic glaciation.

Calcium carbonate mineralogy and stable isotopic composition of Leg 182 sites, Great Australian Bight

An intensive stable isotopic investigation was conducted on sediments recovered from the Great Australian Bight during Ocean Drilling Program Leg 182 at Sites 1127, 1129, and 1131. The sites comprise a transect from the shelf edge to upper slope through a thick sequence of predominately Quaternary cool-water carbonate sediments. Detailed mineralogic and stable isotopic (d18O and d13C) analyses of sediments from a total of 306 samples are presented from all three sites.

TOC, carbonate, opal composition and trace element concentration from ODP Holes 175-1082A and 175-1084A

Distinctive light-dark color cycles in sediment beneath the Benguela Current Upwelling System indicate repetitive alternations in sediment delivery and deposition. Geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid-Pleistocene intervals from ODP Sites 1082 and 1084. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1%. Concentrations of CaCO3 vary inversely to TOC and Al, which suggests that both carbonate dissolution and terrigenous dilution contribute to the light-dark cycles. Opal concentrations are independent of both TOC and CaCO3, therefore eliminating diatom production and lateral transport of shelf material as causes of the light-dark cycles. d13Corg and d15Ntot values do not vary across light-dark sediment intervals, implying that the extent of relative nutrient utilization did not change. The stable d15Ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the TOC-rich layers. Parallel changes in concentrations of indicator trace elements and TOC imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen. Cu, Ni, and Zn are enriched in the darker sediment as a consequence of greater organic matter delivery. Redox-sensitive metals vary due to loss (Mn and Ba) or enrichment (Mo) under reducing conditions created by TOC oxidation. Organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution, sulfate reduction and the concentration of metals. Thus, export production is considered ultimately responsible for the generation of the color cycles.