Orbital-resolution Pliocene-Pleistocene simulations of CO2, sea level, global temperature and benthic d18O, and d11B-based proxy-CO2 data

During the past five million yrs, benthic d18O records indicate a large range of climates, from warmer than today during the Pliocene Warm Period to considerably colder during glacials. Antarctic ice cores have revealed Pleistocene glacial-interglacial CO2 variability of 60-100 ppm, while sea level fluctuations of typically 125 m are documented by proxy data. However, in the pre-ice core period, CO2 and sea level proxy data are scarce and there is disagreement between different proxies and different records of the same proxy. This hampers comprehensive understanding of the long-term relations between CO2, sea level and climate. Here, we drive a coupled climate-ice sheet model over the past five million years, inversely forced by a stacked benthic d18O record. We obtain continuous simulations of benthic d18O, sea level and CO2 that are mutually consistent. Our model shows CO2 concentrations of 300 to 470 ppm during the Early Pliocene. Furthermore, we simulate strong CO2 variability during the Pliocene and Early Pleistocene. These features are broadly supported by existing and new d11B-based proxy CO2 data, but less by alkenone-based records. The simulated concentrations and variations therein are larger than expected from global mean temperature changes. Our findings thus suggest a smaller Earth System Sensitivity than previously thought. This is explained by a more restricted role of land ice variability in the Pliocene. The largest uncertainty in our simulation arises from the mass balance formulation of East Antarctica, which governs the variability in sea level, but only modestly affects the modeled CO2 concentrations.

Chemical and isotopic compositions of samples from the Haakon Mosby mud volcano and nearby

Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active methane-bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community consists of specific methane-producing bacteria, which act as methanotrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (aver. d13C = -28.9 per mil) of CO2 produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (aver. d18O = 5 per mil) in carbonates is inherited from seawater sulfate. Rapid sulfate reduction (up to 12 mg S/dm**3/day) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this carbonates can only be formed in surface sediments near the water-bottom interface. Salinity as well as CO3/Ca and Mg/Ca ratios correspond to the field of non-magnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. Radiocarbon age of carbonates is about 10 Ka.

(Table 1) H2O and CO2 contents in submarine basaltic glasses from Ontong Java Plateau

The Ontong Java Plateau in the western Pacific is anomalous compared to other oceanic large igneous provinces in that it appears to have never formed a large subaerial plateau. Paleoeruption depths (at 122 Ma) estimated from dissolved H2O and CO2 in submarine basaltic glass pillow rims vary from ~1100 m below sea level (mbsl) on the central part of the plateau to 2200-3000 mbsl on the northeastern edge. Our results suggest maximum initial uplift for the plateau of 2500-3600 m above the surrounding seafloor and 1500+/-400 m of postemplacement subsidence since 122 Ma. Our estimates of uplift and subsidence for the plateau are significantly less than predictions from thermal models of oceanic lithosphere, and thus our results are inconsistent with formation of the plateau by a high-temperature mantle plume. Two controversial possibilities to explain the anomalous uplift and subsidence are that the plateau (1) formed as a result of a giant bolide impact, or (2) formed from a mantle plume but has a lower crust of dense garnet granulite and/or eclogite; neither of these possibilities is fully consistent with all available geological, geophysical, and geochemical data. The origin of the largest magmatic event on Earth in the past 200 m.y. thus remains an enigma.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.

Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.

Composition of marine phosphorites and phosphate-bearing sediments

The book deals with behavior of phosphorus and its concentration in oceanic phosphorites. The major stages of marine geochemical cycle of phosphorus including its supply to sedimentary basins, precipitation from sea water, distribution and speciation in bottom sediments, diagenetic redistribution, and relation to other elements are under consideration. Formation of recent phosphorites as a culmination of phosphate accumulation in marine and oceanic sediments is examined. Distribution, structure, mineral and chemical compositions of major phosphorite deposits of various age on continental margins, as well as on submarine plateaus, uplifts and seamounts and some islands are described. A summary of trace element abundances in oceanic phosphorites is presented. Problems of phosphorite origin are discussed.