Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.

Stable isotope ratios measured on carbonate tests from the Kara Sea

River discharge of Ob and Yenisei to the Kara Sea is highly variable on seasonal and interannual time scales. River water dominates the shallow bottom water near the river mouths, making it warmer and less saline but seasonally and interannually more changeable than bottom water on the deeper shelf. This hydrographic pattern shows up in measurements and modelling, and in stable isotope records (delta18O, delta13C) along the growth axis of bivalve shells and in multiple analyses of single benthic foraminiferal shells. Average isotope ratios increase, but sample-internal variability decreases with water depth and distance from river mouths. However, isotope records of bivalves and foraminifera of a sediment core from a former submarine channel of Yenisei River reveal a different pattern. The retreat of the river mouth from this site due to early Holocene sea level rise led to increasing average isotope values up core, but not to the expected decrease of the in-sample isotope variability. Southward advection of cold saline water along the palaeo-river channel probably obscured the hydrographic variability during the early Holocene. Later, when sediment filled the channel, the hydrographic variability at the core location remained low, because the shallowing proceeded synchronously with the retreat of the river mouth.

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.

Calcium carbonate, biogenic opal, and organic carbon content and d15N ratios of sediments from the Bering Sea

Millennial-scale paleoceanographic changes in the Bering Sea during the last 71 kyrs were reconstructed using geochemical and isotope proxies (biogenic opal, CaCO3, and total organic carbon (TOC), nitrogen and carbon isotopes of sedimentary organic matters) and microfossil (radiolaria and foraminifera) data from two cores (PC23A and PC24A) which were collected from the northern continental slope area at intermediate water depths. Biogenic opal and TOC contents were generally high with high sedimentation rates during the last deglaciation. Laminated sediment depositions during the Early-Holocene (EH) and Bølling-Allerød (BA) were closely related with the increased primary productivity recorded by high biogenic opal and TOC contents and high d15N values. Enhanced surface-water productivity was attributed to increased nutrient supply from strengthened Bering Slope Current (BSC) and from increased amount of glacial melt-water, resulting in high C/N ratios and low d13C values, and high proportion of Rhizoplegma boreale during the last deglaciation. In contrast, low surface-water productivity during the last glacial period was due to depleted nutrient supply caused by strong stratification and to restricted phytoplankton bloom by extensive sea ice distribution under cold climates. Extensive formation of sea ice produces more oxygen-rich intermediate-water, leading to oxic bottom-water conditions due to active ventilation, which favored good preservation of oxic benthic foraminifera species. Remarkable CaCO3 peaks coeval with high biogenic opal and TOC contents in both cores during MIS 3 to MIS 4 are most likely correlated with Dansgaard-Oeschger (D-O) events. High d15N and d13Corg values during D-O interstadials support increased surface-water productivity resulting from nutrients supplied mainly by intensified BSC. During the EH, BA and D-O interstadials, dominant benthic foraminifera species indicate dysoxic bottom-water conditions as a result of increased surface-water productivity and weak ventilation of intermediate-water with mitigated sea ice development caused by strengthening of the Alaskan Stream. It is of note that the bottom-water conditions and formation of intermediate-water in the Bering Sea during the last glacial period are related to the variation of dissolved oxygen concentration of the bottom-water in the northeastern Pacific and to strong ventilation of intermediate-water in the northwestern Pacific. Thus, the millennial-scale paleoceanographic events in the Bering Sea during the D-O interstadials are closely associated with the intermediate-water ventilation, ultimately leading to weakening of North Pacific Intermediate Water.

Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Late Quaternary carbonate and isotope stratigraphy of DSDP Site 90-594 east of South Island, New Zealand

The late Quaternary sequence off eastern South Island, New Zealand, consists of ~100 m of alternating bluish gray pelagic oozes and greenish gray hemipelagic oozes that extend uninterruptedly back to the Brunhes/Matuyama boundary (0.73 m.y.). A very high resolution (~2400 yr.) record of sediment texture, calcium carbonate content, and planktonic and benthic foraminiferal oxygen and carbon isotope composition demonstrates an in-phase cyclical fluctuation between the sedimentary parameters that closely correspond to the pelagic-hemipelagic sedimentation cycles and the isotope composition. Pelagic oozes, formed during interglacial periods of high eustatic sea level, are characterized by calcareous microfossils, relative enrichment in sand and clay sizes, high carbonate contents, reduced delta18O values, and increased delta13C values. Hemipelagic oozes, associated with glacial episodes and lowered eustatic sea level, include common terrigenous material and siliceous microfossils, are enriched in silt sizes, have low carbonate contents, high delta18O values, and low delta13C values. The history of alpine glaciations and associated erosion of the South Island of New Zealand, as expressed by the appearance of hemipelagic oozes, can be correlated directly with the major fluctuations of Northern Hemisphere ice sheets as expressed by the influence of eustatic sea-level changes on the oxygen isotope composition of both planktonic and benthic foraminifers. This high-accumulation-rate record contains conspicuous intervals of highfrequency, high-amplitude isotope variability including the presence of multiple glacial/interglacial intervals within single isotope stages, and offers one of the best sections cored to date for detailed study of the evolution and history of climate change over the last 0.75 m.y.