Stable isotope record, opal accumulation rate and geochemistry of middle Miocene sediments of IODP Site 321-U1338

During the middle Miocene, Earth's climate transitioned from a relatively warm phase (Miocene climatic optimum) into a colder mode with re-establishment of permanent ice sheets on Antarctica, thus marking a fundamental step in Cenozoic cooling. Carbon sequestration and atmospheric CO2 drawdown through increased terrestrial and/or marine productivity have been proposed as the main drivers of this fundamental transition. We integrate high-resolution (1-3 k.y.) benthic stable isotope data with XRF-scanner derived biogenic silica and carbonate accumulation estimates in an exceptionally well-preserved sedimentary archive, recovered at Integrated Ocean Drilling Program Site U1338, to reconstruct eastern equatorial Pacific productivity variations and to investigate temporal linkages between high- and low-latitude climate change over the interval 16-13 Ma. Our records show that the climatic optimum (16.8-14.7 Ma) was characterized by high amplitude climate variations, marked by intense perturbations of the carbon cycle. Episodes of peak warmth at (southern hemisphere) insolation maxima coincided with transient shoaling of the carbonate compensation depth and enhanced carbonate dissolution in the deep ocean. A switch to obliquity-paced climate variability after 14.7 Ma concurred with a general improvement in carbonate preservation and the onset of stepwise global cooling, culminating with extensive ice growth over Antarctica at ~13.8 Ma. We find that two massive increases in opal accumulation at ~14.0 and ~13.8 Ma occurred just before and during the final and most prominent cooling step, supporting the hypothesis that enhanced siliceous productivity in the eastern equatorial Pacific contributed to CO2 drawdown.

Organic carbon and nitrogen concentrations in surface waters of the North Atlantic along 20°E in July-August 1996

Redfield stoichiometry has proved a robust paradigm for the understanding of biological production and export in the ocean on a long-term and a large-scale basis. However, deviations of carbon and nitrogen uptake ratios from the Redfield ratio have been reported. A comprehensive data set including all carbon and nitrogen pools relevant to biological production in the surface ocean (DIC, DIN, DOC, DON, POC, PON) was used to calculate seasonal new production based on carbon and nitrogen uptake in summer along 20°W in the northeast Atlantic Ocean. The 20°W transect between 30 and 60°N covers different trophic states and seasonal stages of the productive surface layer, including early bloom, bloom, post-bloom and non-bloom situations. The spatial pattern has elements of a seasonal progression. We also calculated exported production, i.e., that part of seasonal new production not accumulated in particulate and dissolved pools, again separately for carbon and nitrogen. The pairs of estimates of 'seasonal new production' and 'exported production' allowed us to calculate the C : N ratios of these quantities. While suspended particulate matter in the mixed layer largely conforms to Redfield stoichiometry, marked deviations were observed in carbon and nitrogen uptake and export with progressing season or nutrient depletion. The spring system was characterized by nitrogen overconsumption and the oligotrophic summer system by a marked carbon overconsumption. The C : N ratios of seasonal new as well as exported production increase from early bloom values of 5-6 to values of 10-16 in the post-bloom/oligotrophic system. The summertime accumulation of nitrogen-poor dissolved organic matter can explain only part of this shift.

Carbon chemistry of cretaceous marine organic matter

Geochemical studies of Cretaceous strata rich in organic carbon (OC) from Deep Sea Drilling Project (DSDP) sites and several land sections reveal several consistent relationships among amount of OC, hydrocarbon generating potential of kerogen (measured by pyrolysis as the hydrogen index, HI), and the isotopic composition of the OC. First, there is a positive correlation between HI and OC in strata that contain more than about 1% OC. Second, percent OC and HI often are negatively correlated with carbon isotopic composition (delta13C) of kerogen. The relationship between HI and OC indicates that as the amount of organic matter increases, this organic matter tends to be more lipid rich reflecting the marine source of the organic matter. Cretaceous samples that contain predominantly marine organic matter tend to be isotopically lighter than those that contain predominantly terrestrial organic matter. Average delta13C values for organic matter from most Cretaceous sites are between -26 and -28 per mil, and values heavier than about -25 per mil occur at very few sites. Most of the delta13C values of Miocene to Holocene OC-rich strata and modern marine plankton are between -16 to -23 per mil. Values of delta13C of modern terrestrial organic matter are mostly between -23 and -33 per mil. The depletion of terrestial OC in 13C relative to marine planktonic OC is the basis for numerous statements in the literature that isotopically light Cretaceous organic matter is of terrestrial origin, even though other organic geochemical and(or) optical indicators show that the organic matter is mainly of marine origin. A difference of about 5 per mil in delta13C between modern and Cretaceous OC-rich marine strata suggests either that Cretaceous marine planktonic organic matter had the same isotopic signature as modern marine plankton and that signature has been changed by diagenesis, or that OC derived from Cretaceous marine plankton was isotopically lighter by about 5 per mil relative to modern plankton OC. Diagenesis does not produce a significant shift in delta13C in Miocene to Holocene sediments, and therefore probably did not produce the isotopically light Cretaceous OC. This means that Cretaceous marine plankton must have had delta13C values that were about 5 per mil lighter than modern marine plankton, and at least several per mil lighter than Cretaceous terrestrial vegetation. The reason for these lighter values, however, is not obvious. It has been proposed that concentrations of CO2 were higher during the middle Cretaceous, and this more available CO2 may be responsible for the lighter delta13C values of Cretaceous marine organic matter.

Pliocene to Pleistocene calcium carbonate and organic carbon record of ODP Hole 117-722B

Site 722 provides high resolution records of percent CaCO3, magnetic susceptibility, d18O, organic carbon, and coarse fraction for the past 3.4 m.y. from the crest of the Owen Ridge, northwestern Arabian Sea. Within this time interval, most of the carbonate percent variations can be attributed to terrigenous dilution and do not reflect changes in the carbonate system. From the late Pliocene to Present, the average rate of calcium carbonate accumulation increases from 1 to 3 g/cm**2/k.y. and the average accumulation of organic carbon decreases from 75 to 30 mg/cm**2/k.y. The carbonate component is more dissolved in the older interval. The long-term variations in carbonate accumulation may reflect a greater input of organic matter in the late Pliocene, which decomposes to produce CO2 and dissolve carbonate. Magnetic susceptibility and % noncarbonate (100 - CaCO3%) reflect changes in the amount of the lithogenic component in the sediments. The period of variation of lithogenic material is the same period as the original forcing of the regional summer monsoon, however, the timing matches global aridity patterns and global ice volume (sea level) changes. This preliminary analysis suggests that the high frequency variation of lithogenic material persists for at least the last 3.4 m.y. Within the last million years, calcium carbonate accumulation has a large amplitude signal that covaries with major changes in ice volume. Both calcium carbonate and noncarbonate (mostly terrigenous) accumulation are greatest during glacial stages. Interglacial intervals are characterized by low mass accumulation rates, increased foraminifer fragmentation, and increased opal concentration. The accumulation of organic carbon matches the high frequency changes in sedimentation rates. We attribute this high correlation to enhanced preservation of organic carbon by increased sedimentation rate. Of the three major biological components studied, only opal exhibits the variations expected for a biological productivity system forced by monsoonal upwelling driven by changes in northern hemisphere summer radiation.

Organic carbon geochemistry of ODP Leg 121 samples

Organic petrological and geochemical analyses were performed on samples cored on Broken Ridge and Ninetyeast Ridge in the Central Indian Ocean during Leg 121. Organic carbon (Corg) contents are less than 1% in each individual sample and average Corg values calculated for larger stratigraphic units are less than 0.2%. Generally, there is more organic matter in Cretaceous sediments than in Tertiary. In the Cretaceous, the bulk of the organic matter consists of terrigenous debris, but a significant contribution of marine-derived organic matter was found in some samples, especially in the early Maestrichtian on Broken Ridge (Site 754). The youngest Pliocene-Pleistocene sediments at Site 758 (northern part of Ninetyeast Ridge) contain a significant amount of clastic material transported to the site by the (distal) Bengal Fan. In these sediments, Corg contents of up to 0.9% were measured and are due to the inflow of terrigenous organic debris. Corg values are positively correlated with bulk sediment accumulation rates (i.e., sediments contain more organic matter at times of faster deposition). The size of terrigenous organic particles is generally small in all sediments. The extremely small number of particles in the Cretaceous sediments at Site 758 and their smaller grain size, compared to the Cretaceous sediments on Broken Ridge, indicate that Cretaceous surface water paleocurrents flowed from southeast to northwest in the Proto-Indian Ocean. In the central Indian Ocean, sediments deposited above the carbonate compensation depth consist of nannofossil and foraminiferal oozes. In contrast to Corg values, calcite contents in the sediments are negatively correlated with bulk sediment accumulation rates (i.e., carbonate oozes were deposited only during times of extremely slow sedimentation). Therefore, older sediments deposited in the young and still narrow Indian Ocean accumulated faster and are less carbonate-rich than Neogene sediments, although carbonate accumulation rates were higher.