Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.

Isotopic composition of the fine fraction of ODP Site 114-704

Ocean Drilling Program Site 704 in the subantarctic South Atlantic was drilled to investigate the response of the Southern Ocean to climatic and Oceanographic developments during the late Neogene. Stable oxygen and carbon isotopes of fine-fraction (<63 µm) carbonate were analyzed to supplement similar analyses of benthic and planktonic foraminifers. The fine fraction is generally composed primarily of coccoliths, and isotopic analyses of the fine fraction were made to complement the foraminiferal analyses. The isotopic curves thus generated suggest paleoceanographic changes not recognizable by the use of benthic and planktonic foraminifers alone. The global Chron 6 carbon isotope shift, found at 253-244 mbsf (6.39-6.0 Ma) at Site 704 in the planktonic and benthic record, is seen in the fine-fraction d13C record as a gradual decrease from 255 mbsf (6.44 Ma) to 210 mbsf (4.24 Ma). At 170 mbsf, mean d18O values of Neogloboquadrina pachyderma increase by 0.6 per mil-0.7 per mil (Hodell and Ciesielski, 1991, doi:10.2973/odp.proc.sr.114.150.1991), reflecting decreased temperature and increased continental ice volume. Accumulation rates increase by 3.3 times above this depth (which corresponds to an age of 2.5 Ma), suggesting increased upwelling and biologic productivity. Carbon isotopic values of fine-fraction carbonate decrease by about 1.5 per mil at 2.6 Ma; however, no change is recorded in the d13C of N. pachyderma. The fine-fraction d13C shift slightly precedes an average l per mil decrease in d13C in benthic foraminifers. The cause of the benthic d13C shift (most likely due to a change in deep water circulation; Hodell and Ciesielski, 1991) is probably not directly related to the fine-fraction shift. The fine-fraction shift is most likely caused by (1) a change in the upwelling to productivity ratio at this site, with increased upwelling bringing lighter carbon to surface waters, more productivity, and higher sedimentation rates and (2) a change in the particle composition of the fine fraction. The increased upwelling is probably due to a northward migration of the Antarctic Polar Front to a position nearer Site 704.

Sulfur contents and S, C and O isotopic compositions in serpentinized peridotites at ODP Site 153-920

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated d34S_sulfide (3.7 to 12.7?). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high d34S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (~400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ~300°C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5?) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 mln ton seawater S per year. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.

Color data, carbon and oxygen isotopes, and offsets from BBCP Polecat Bench cores 2A and 2B

The Earth's climate abruptly warmed by 5-8 °C during the Palaeocene-Eocene thermal maximum (PETM), about 55.5 million years ago**1,2. This warming was associated with a massive addition of carbon to the ocean-atmosphere system, but estimates of the Earth systemresponse to this perturbation are complicated by widely varying estimates of the duration of carbon release, which range from less than a year to tens of thousands of years. In addition the source of the carbon, and whether it was released as a single injection or in several pulses, remains the subject of debate**2-4. Here we present a new high-resolution carbon isotope record from terrestrial deposits in the Bighorn Basin (Wyoming, USA) spanning the PETM, and interpret the record using a carbon-cycle boxmodel of the ocean-atmosphere-biosphere system.Our record shows that the beginning of the PETMis characterized by not one but two distinct carbon release events, separated by a recovery to background values. To reproduce this pattern, our model requires two discrete pulses of carbon released directly to the atmosphere, at average rates exceeding 0.9 Pg C yr**-1, with the first pulse lasting fewer than 2,000 years.

Oxygen- and carbon-isotopes at DSDP Leg 73 Holes

We established a composite oxygen- and carbon-isotope stratigraphy for the Pliocene in the central South Atlantic. Monospecific samples of benthic and planktonic foraminifers from pelagic sediments from DSDP Sites 519, 521, 522, and 523 were analyzed isotopically. The resulting benthic oxygen-isotope stratigraphy allowed three paleoclimatic periods in the Pliocene to be distinguished. During the early Pliocene (5.2-3.3 Ma), low-amplitude climatic changes prevailed in a world that was less glaciated than during the Pleistocene. A net increase in global ice volume is documented in a 0.5 permil positive shift in the average 18O composition of the benthic foraminifers at 3.2 Ma. The middle Pliocene (3.3-2.5 Ma) is not only characterized by a more widespread glaciation of the Southern and Northern hemispheres but also by more drastic isotopic differences between glacial and interglacial times. A minor shift in the average 18O composition of the benthic foraminifers marks the beginning of the late Pliocene-early Pleistocene climatic period (2.5-1.1 Ma). Alternating cold and warm climate is documented in both the oxygen-isotope record and in the pelagic sediments. During cold periods, sediments with a lower CaCO3 content indicate more corrosive bottom-water conditions. More negative 13C signals in the benthic foraminifers from these sediments suggest that the Antarctic Bottom Water current was intensified in glacial times. The oxygen-isotope composition of the measured planktonic foraminifers suggests that the surface water in this part of the South Atlantic remained relatively warm during the growth of the Pliocene glaciers.

Stable oxygen isotope record of Globigerinoides ruber of ODP Site 133-820 off the Great Barriere Reef

Oxygen-isotope ratio measurements are presented for the planktonic species Globigerinoides ruber collected from shallow-water, upper-slope sediments from Holes 820A and 820B in 280 m of water, on the seaward edge of the Great Barrier Reef. Correlation of the Site 820 isotope curve with deep-sea reference curves of the Pacific Ocean (Core V28-238, Hole 677A, Hole 607A) permits the definition of isotope stages 1 to 19 in the top 145 m of Holes 820A and 820B. However, paleontological data indicate that stages 4 and 7 might be missing and that two hiatuses occur at a depth of 8.05 to 12.1 and 34.55 to 35.8 mbsf. Using deep-sea Hole 677A as a reference for ice-volume variations, we determine the difference in isotopic signature between it and Site 820. We propose that this difference is a regional signal representing a progressive 4°C increase in surface-water temperature at Site 820. The proposed temperature change was initiated at about 400 k.y. and corresponds to a change from high-to-low frequency variations in Pleistocene isotope signals. We postulate that these changes may have catalyzed the growth of the Great Barrier Reef. The shift also coincides with changes in seismic character and some physical and chemical sediment characteristics.

Annual-layer thickness, d18O and sodium values on Akademii Nauk ice core (AD 900-1998) based on core chronology AN 2012

Understanding recent Arctic climate change requires detailed information on past changes, in particular on a regional scale. The extension of the depth-age relation of the Akademii Nauk (AN) ice core from Severnaya Zemlya (SZ) to the last 1100 yr provides new perspectives on past climate fluctuations in the Barents and Kara seas region. Here, we present the easternmost high-resolution ice-core climate proxy records (d18O and sodium) from the Arctic. Multi-annual AN d18O data as near-surface air-temperature proxies reveal major temperature changes over the last millennium, including the absolute minimum around 1800 and the unprecedented warming to a double-peak maximum in the early 20th century. The long-term cooling trend in d18O is related to a decline in summer insolation but also to the growth of the AN ice cap as indicated by decreasing sodium concentrations. Neither a pronounced Medieval Climate Anomaly nor a Little Ice Age are detectable in the AN d18O record. In contrast, there is evidence of several abrupt warming and cooling events, such as in the 15th and 16th centuries, partly accompanied by corresponding changes in sodium concentrations. These abrupt changes are assumed to be related to sea-ice cover variability in the Barents and Kara seas region, which might be caused by shifts in atmospheric circulation patterns. Our results indicate a significant impact of internal climate variability on Arctic climate change in the last millennium.