Diagenetic dolomite formation in Quaternary anoxic diatomaceous muds at DSDP Leg 64 Holes

During drilling in the Gulf of California, diagenetic carbonate rocks were recovered at 7 out of 8 sites. These are primarily dolomites which record 13C isotopic evidence of the incorporation of carbon derived from the decomposition of organic matter. In Hole 479, drilled to a sub-bottom depth of 440 meters on the Guaymas Slope, under a fertile upwelling belt, we recognized an excellent example of deep sea dolomitization in progress. This Quaternary section of organic-carbon- rich, low-carbonate, hemipelagic diatomaceous oozes contains numerous fine-grained, decimeter-thin, episodic beds of dolomite, which show sedimentologic, geochemical, and isotopic evidence of accretion by precipitation below 40 meters sub-bottom in zones of high alkalinity and low sulfate. The beds preserve original sedimentary structures. Carbon-13 varies from +3 to +14 per mil, indicating biogenic CO2 reservoirs related to active methanogenesis. In single beds, 18O values range outwardly from +5 to -7 per mil, reflecting increasing temperature with progressive accretion of dolomite with depth; the values parallel progressive trends in lithification, texture, mineralogy, and fossil preservation. We estimate slow accretion rates on the order of 0.1-0.7 mm/10**3 yr. with burial. Dolomitization does not proceed merely at the expense of nearby nannofossils. Ca and Mg ions must be derived from interstitial waters. The episodic appearance of beds in the sequence seems partly a reflection of latent climate signals. This process of deep sea dolomitization carries implications for hydrocarbon migration, as well as an interpretation of the presence of dolomite in other modern and ancient pelagic to hemipelagic sediment sequences.

Geochemistry of carbon at DSDP Legs 56-57 Holes

Forty-three core sections from Sites 434, 435, 438, 439, and 440 on the landward side and six core sections from Site 436 on the seaward side of the Japan Trench were obtained through the JOIDES Organic Geochemistry Advisory Panel for study of the origin and state of genesis of the organic matter associated with these continental slope, accretionary wedge, and outer trench slope sediments of the Japan Trench. The lipid fraction of these sediments is derived primarily from terrigenous organic matter and thus is allochthonous to the area. The associated kerogen fraction is of mixed allochthonous and autochthonous origin. The total organic carbon content seaward of the trench is less than that on the landward side. The composition of this organic matter is similar but not identical to that found in the landward side sediments. The organic matter within these sediments is in a diagenetic state in which geopolymerization of biogenic organic matter is nearly complete, but microbial alteration is still occurring.

Age models for sediment cores in the eastern tropical Pacific

We present new high-resolution N isotope records from the Gulf of Tehuantepec and the Nicaragua Basin spanning the last 50-70 ka. The Tehuantepec site is situated within the core of the north subtropical denitrification zone while the Nicaragua site is at the southern boundary. The d15N record from Nicaragua shows an 'Antarctic' timing similar to denitrification changes observed off Peru-Chile but is radically different from the northern records. We attribute this to the leakage of isotopically heavy nitrate from the South Pacific oxygen minimum zone (OMZ) into the Nicaragua Basin. The Nicaragua record leads the other eastern tropical North Pacific (ETNP) records by about 1000 years because denitrification peaks in the eastern tropical South Pacific (ETSP) before denitrification starts to increase in the Northern Hemisphere OMZ, i.e., during warming episodes in Antarctica. We find that the influence of the heavy nitrate leakage from the ETSP is still noticeable, although attenuated, in the Gulf of Tehuantepec record, particularly at the end of the Heinrich events, and tends to alter the recording of millennial timescale denitrification changes in the ETNP. This implies (1) that sedimentary d15N records from the southern parts of the ETNP cannot be used straightforwardly as a proxy for local denitrification and (2) that denitrification history in the ETNP, like in the Arabian Sea, is synchronous with Greenland temperature changes. These observations reinforce the conclusion that on millennial timescales during the last ice age, denitrification in the ETNP is strongly influenced by climatic variations that originated in the high-latitude North Atlantic region, while commensurate changes in Southern Ocean hydrography more directly, and slightly earlier, affected oxygen concentrations in the ETSP. Furthermore, the d15N records imply ongoing physical communication across the equator in the shallow subsurface continuously over the last 50-70 ka.

Geochemistry on core 202-1240A

The modern Eastern Equatorial Pacific (EEP) Ocean is a large oceanic source of carbon to the atmosphere1. Primary productivity over large areas of the EEP is limited by silicic acid and iron availability, and because of this constraint the organic carbon export to the deep ocean is unable to compensate for the outgassing of carbon dioxide that occurs through upwelling of deep waters. It has been suggested that the delivery of dust-borne iron to the glacial ocean could have increased primary productivity and enhanced deep-sea carbon export in this region, lowering atmospheric carbon dioxide concentrations during glacial periods. Such a role for the EEP is supported by higher organic carbon burial rates documented in underlying glacial sediments but lower opal accumulation rates cast doubts on the importance of the EEP as an oceanic region for significant glacial carbon dioxide drawdown. Here we present a new silicon isotope record that suggests the paradoxical decline in opal accumulation rate in the glacial EEP results from a decrease in the silicon to carbon uptake ratio of diatoms under conditions of increased iron availability from enhanced dust input. Consequently, our study supports the idea of an invigorated biological pump in this region during the last glacial period that could have contributed to glacial carbon dioxide drawdown. Additionally, using evidence from silicon and nitrogen isotope changes, we infer that, in contrast to the modern situation, the biological productivity in this region is not constrained by the availability of iron, silicon and nitrogen during the glacial period. We hypothesize that an invigorated biological carbon dioxide pump constrained perhaps only by phosphorus limitation was a more common occurrence in low-latitude areas of the glacial ocean.

1.2 Ma stacked benthic foraminiferal carbon isotope record

Pleistocene stable carbon isotope (d13C) records from surface and deep dwelling foraminifera in all major ocean basins show two distinct long-term carbon isotope fluctuations since 1.00 Ma. The first started around 1.00 Ma and was characterised by a 0.35 per mil decrease in d13C values until 0.90 Ma, followed by an increase of 0.60 per mil lasting until 0.50 Ma. The subsequent fluctuation started with a 0.40 per mil decrease between 0.50 and 0.25 Ma, followed by an increase of 0.30 per mil between 0.25 and 0.10 Ma. Here, we evaluate existing evidence and various hypotheses for these global Pleistocene d13C fluctuations and present an interpretation, where the fluctuations most likely resulted from concomitant changes in the burial fluxes of organic and inorganic carbon due to ventilation changes and/or changes in the production and export ratio. Our model indicates that to satisfy the long-term 'stability' of the Pleistocene lysocline, the ratio between the amounts of change in the organic and inorganic carbon burial fluxes would have to be close to a 1:1 ratio, as deviations from this ratio would lead to sizable variations in the depth of the lysocline. It is then apparent that the mid-Pleistocene climate transition, which, apart from the glacial cycles, represents the most fundamental change in the Pleistocene climate, was likely not associated with a fundamental change in atmospheric pCO2. While recognising that high frequency glacial/interglacial cycles are associated with relatively large (100 ppmv) changes in pCO2, our model scenario (with burial changes close to a 1:1 ratio) produces a maximum long-term variability of only 20 ppmv over the fluctuation between 1.00 and 0.50 Ma.

Mg/Ca and stable isotope record of benthic foraminifera of the Paleocene-Eocene Thermal Maximum

A rapid increase in greenhouse gas levels is thought to have fueled global warming at the Paleocene-Eocene Thermal Maximum (PETM). Foraminiferal magnesium/calcium ratios indicate that bottom waters warmed by 4° to 5°C, similar to tropical and subtropical surface ocean waters, implying no amplification of warming in high-latitude regions of deep-water formation under ice-free conditions. Intermediate waters warmed before the carbon isotope excursion, in association with downwelling in the North Pacific and reduced Southern Ocean convection, supporting changing circulation as the trigger for methane hydrate release. A switch to deep convection in the North Pacific at the PETM onset could have amplified and sustained warming.

Chemistry of siliciclastic and volcanoclastic sediments of DSDP Site 47-397

The Lower Cretaceous and Miocene sequences of the NW African passive continental margin consist of siliciclastic, volcaniclastic and hybrid sediments. These sediments contain a variety of diagenetic carbonates associated with zeolites, smectite clays and pyrite, reflecting the detrital mineralogical composition and conditions which prevailed during opening of the North Atlantic. In the Lower Cretaceous siliciclastic sediments, siderite (-6 per mil to +0.7per mil d18O PDB, -19.6 per mil to +0.6 per mil d13C PDB) was precipitated as thin layers and nodules from modified marine porewaters with input of dissolved carbon from the alteration of organic matter. Microcrystalline dolomite layers, lenses, nodules and disseminated crystals (-3.0 per mil to +2.5 per mil d18O PDB, -7.2 per mil to +4.9 per mil d13C PDB) predominate in slump and debris-flow deposits within the Lower Miocene sequence. During the opening of the Atlantic, volcanic activity in the Canary Islands area resulted in input of volcaniclastic sediments to the Middle and Upper Miocene sequences. Calcite is the dominant diagenetic carbonate in the siliciclastic-bioclastic-volcaniclastic hybrid and in the volcaniclastic sediments, which commonly contain pore-rimming smectite. Diagenetic calcite (-22 per mil to +1.6 per mil d18O PDB, -35.7 per mil to +0.8 per mil d13C PDB) was precipitated due to the interaction of volcaniclastic and bioclastic grains with marine porewaters. Phillipsite is confined to the alteration of volcaniclastic sediments, whereas clinoptilolite is widely disseminated, occurring essentially within foraminiferal chambers, and formed due to the dissolution of biogenic silica.

Measurements of stable carbon isotope ratios of CO2 over the last 24000 years and CO2 concentration measurements on Antarctic ice cores using three different methods

The stable carbon isotope ratio of atmospheric CO2 (d13Catm) is a key parameter in deciphering past carbon cycle changes. Here we present d13Catm data for the past 24,000 years derived from three independent records from two Antarctic ice cores. We conclude that a pronounced 0.3 per mil decrease in d13Catm during the early deglaciation can be best explained by upwelling of old, carbon-enriched waters in the Southern Ocean. Later in the deglaciation, regrowth of the terrestrial biosphere, changes in sea surface temperature, and ocean circulation governed the d13Catm evolution. During the Last Glacial Maximum, d13Catm and atmospheric CO2 concentration were essentially constant, which suggests that the carbon cycle was in dynamic equilibrium and that the net transfer of carbon to the deep ocean had occurred before then.