Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

Stable isotopes and XRF data over the Paleocene-Eocene Thermal Maximum from IODP Sites U1403 and U1409

During the Paleocene-Eocene Thermal Maximum (PETM) about 56 million years ago, thousands of petagrams of carbon were released into the atmosphere and ocean in just a few thousand years, followed by a gradual sequestration over approximately 200,000 years. If silicate weathering is one of the key negative feedbacks that removed this carbon, a period of seawater calcium carbonate saturation greater than pre-event levels is expected during the event's recovery phase. In marine sediments, this should be recorded as a temporary deepening of the depth below which no calcite is preserved - the calcite compensation depth (CCD). Previous and new sedimentary records from sites that were above the pre-PETM calcite compensation depth show enhanced carbonate accumulation following the PETM. A new record from an abyssal site in the North Atlantic that lay below the pre-PETM calcite compensation depth shows a period of carbonate preservation beginning about 70,000 years after the onset of the PETM, providing the first direct evidence for an over-deepening of the calcite compensation depth. This record confirms an overshoot in ocean carbonate saturation during the PETM recovery. Simulations with two earth system models support scenarios for the PETM that involve both a large initial carbon release followed by prolonged low-level emissions, consistent with the timing of CCD deepening in our record. Our findings indicate that sequestration of these carbon emissions was most likely the result of both globally enhanced calcite burial above the calcite compensation depth and, at least in the North Atlantic, by a temporary over-deepening of the calcite compensation depth.

(Table 1) Organic carbon and radiogenic isotopes analysis of DSDP Hole 22-218 sediments

Modern erosion of the Himalaya, the world's largest mountain range, transfers huge dissolved and particulate loads to the ocean. It plays an important role in the long-term global carbon cycle, mostly through enhanced organic carbon burial in the Bengal Fan. To understand the role of past Himalayan erosion, the influence of changing climate and tectonic on erosion must be determined. Here we use a 12 Myr sedimentary record from the distal Bengal Fan (Deep Sea Drilling Project Site 218) to reconstruct the Mio-Pliocene history of Himalayan erosion. We use carbon stable isotopes (d13C) of bulk organic matter as paleo-environmental proxy and stratigraphic tool. Multi-isotopic - Sr, Nd and Os - data are used as proxies for the source of the sediments deposited in the Bengal Fan over time. d13C values of bulk organic matter shift dramatically towards less depleted values, revealing the widespread Late Miocene (ca. 7.4 Ma) expansion of C4 plants in the basin. Sr, Nd and Os isotopic compositions indicate a rather stable erosion pattern in the Himalaya range during the past 12 Myr. This supports the existence of a strong connection between the southern Tibetan plateau and the Bengal Fan. The tectonic evolution of the Himalaya range and Southern Tibet seems to have been unable to produce large re-organisation of the drainage system. Moreover, our data do not suggest a rapid change of the altitude of the southern Tibetan plateau during the past 12 Myr. Variations in Sr and Nd isotopic compositions around the late Miocene expansion of C4 plants are suggestive of a relative increase in the erosion of High Himalaya Crystalline rock (i.e. a simultaneous reduction of both Transhimalayan batholiths and Lesser Himalaya relative contributions). This could be related to an increase in aridity as suggested by the ecological and sedimentological changes at that time. A reversed trend in Sr and Nd isotopic compositions is observed at the Plio-Pleistocene transition that is likely related to higher precipitation and the development of glaciers in the Himalaya. These almost synchronous moderate changes in erosion pattern and climate changes during the late Miocene and at the Plio-Pleistocene transition support the notion of a dominant control of climate on Himalayan erosion during this time period. However, stable erosion regime during the Pleistocene is suggestive of a limited influence of the glacier development on Himalayan erosion.

Compilation of Mg/Ca ratios of Neogloboquadrina pachyderma (sinistral) and SST estimates from the northern North Atlantic

A map of estimated calcification temperatures of the planktic foraminifer Neogloboquadrina pachyderma sinistral (TNps) for the Nordic Seas and the northern North Atlantic for the Last Glacial Maximum was produced from oxygen isotopes with support of Mg/Ca ratios. To arrive at the reconstruction, several constraints concerning the plausible salinity and ?18O-fields were employed. The reconstruction indicates inflow of temperate waters in a wedge along the eastern border of the Nordic Seas and at least seasonally ice-free waters. The reconstruction from oxygen isotopes shows similarities with Mg/Ca based paleotemperatures in the southern and southeastern sector, while unrealistically high Mg/Ca values in the central Nordic Seas prevent the application of the method in this area. The oxygen isotope based reconstruction shows some agreement with temperature reconstructions based on the modern analogue technique, but with somewhat lower temperatures and a stronger internal gradient inside the Nordic Seas. All told, our results suggest a much more ice-free and dynamic high latitude ocean than the CLIMAP reconstruction.

delta O-18, Sr/Ca and Mg/Ca records of Porites lutea corals from Leizhou Peninsula, northern South China Sea, and their applicability as paleoclimatic indicators

Combined seasonal to monthly resolution coral skeletal delta(18)O, Sr/Ca, and Mg/Ca records are reported for one modem and two late Holocene Porites lutea corals from a fringing reef at Leizhou Peninsula, the northern coast of the South China Sea (SCS). All the profiles for the period 1989-2000 reveal annual cycles well correlated with instrumental sea surface temperatures (SST), and display broad peaks in summer and narrow troughs in winter, reflecting seasonal growth rate variations. Calibration against instrumental SST yields the following equations: delta(18)O=-0.174(+/- 0.010)xSST(degrees C)-1.02(+/- 0.27) (MSWD=5.8), Sr/Ca-(mmol/mol)=-0.0424(+/- 0.0031)xSST(degrees C)+9.836(+/- 0.082) (MSWD=8.6), and Mg/Ca-(mmol/mol)=0.110(+/- 0.009)XSST(degrees C)+ 1.32(+/- 0.23) (MSWD=55). The scatter in the Mg/Ca-SST relationship is much larger than analytical uncertainties can account for, suggesting the presence of SST-unrelated components in the Mg/Ca variation. Calculated Sr/Ca-SST values for two later Holocene Porites lutea samples (U-series ages similar to 541 BC and similar to 487 AD, respectively) from the same reef suggest that SST in the SCS at similar to 541 BC was nearly as warm as in the 1990s (the warmest decade of the last century), but at similar to 487 AD, it was significantly cooler. This observation is consistent with climatic data reported in Chinese historic documents, confirming that the Sr/Ca-SST relationship is a reliable thermometer. Removing the SST component in the delta(18)O variation based on calculated Sr/Ca-SST values, the residual delta(18)O reflects the deviation of the Holocene seawater delta(18)O from the modem value, which is also a measure of the Holocene sea surface salinity (SSS) or the summer monsoon moisture level in mainland China. Such residual delta(18)O was close to zero at similar to 541 BC and -0.3 parts per thousand at similar to 487 AD, suggesting that it was as wet as in the 1990s at similar to 541 BC but significantly drier at similar to 487 AD in mainland China, which are also consistent with independent historic records. Calculated Mg/Ca-SST values for the two late Holocene corals are significantly lower than the Sr/Ca-SST values and are also in conflict with Chinese historic records, suggesting that coral Mg/Ca is not reliable proxy for SST. At comparable Sr/Ca ranges, fossil corals always display negative Mg/Ca offsets if compared with the modem coral of the same site. We interpret this observation as due to preferential loss of Mg during meteoric dissolution of cryptic Mg-calcite-bearing microbialites in the exposed fossil corals. Microbialites (MgO up to 17%, Sr only 100-300 ppm) are ubiquitous during reef-building processes and their presence in only a trace amount will have a significant impact on coral Mg/Ca ratios without detectable influence on coral Sr/Ca ratios. (c) 2004 Elsevier B.V. All rights reserved.

Isotopes content, mineralogical composition, Uranium and Thorium contents and determined activity ratios from METEOR cruise M74/3 in 2007

Authigenic carbonate deposits have been sampled with the remotely operated vehicle 'MARUM-QUEST 4000 m' from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The delta18O carbonate values range from 1.3 to 4.2 per mil V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low delta13Ccarbonate values (as low - 54.6per mil V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by delta13C methane values ranging from - 70.3 to - 66.7per mil V-PDB, and also by back-calculations considering delta 13C methane values of carbonate and incorporated lipid biomarkers.

Mg/Ca and Sr/Ca ratios of planktonic foraminifera from North Atlantic surface sediments

Reliable temperature estimates from both surface and subsurface ocean waters are needed to reconstruct past upper water column temperature gradients and past oceanic heat content. This work examines the relationships between trace element ratios in fossil shells and seawater temperature for surface-dwelling foraminifera species, Globigerinoides ruber (white) and Globigerina bulloides, and deep-dwelling species, Globorotalia inflata, Globorotalia truncatulinoides (dextral and sinistral) and Pulleniatina obliquiloculata. Mg/Ca and Sr/Ca ratios in shells picked in 29 modern core tops from the North Atlantic Ocean are calibrated using calculated isotopic temperatures. Mg/Ca ratios on G. ruber and G. bulloides agree with published data and relationships. For deep-dwelling species, Mg/Ca calibration follows the equation Mg/Ca = 0.78 (±0.04) * exp (0.051 (±0.003) * T) with a significant correlation coefficient of R**2 = 0.74. Moreover, there is no significant difference between the different deep-dwellers analyzed. For the Sr/Ca ratio, the surface dwellers and P. obliquiloculata do not record any temperature dependence. For the Globorotalia species, the thermo dependence of Sr/Ca ratio can be described by a single linear relationship: Sr/Ca = (0.0182 (±0.001) * T) + 1.097 (±0.018), R**2 = 0.85. Temperature estimates with a 1 sigma error of ±2.0°C and ±1.3°C can be derived from the Mg/Ca and Sr/Ca ratios, respectively, as long as the Sr geochemistry in the ocean has been constant through time.

Stable isotope and Mg/Ca ratios of Globigerinoides ruber from core-top sediment samples

Seasonal changes in surface ocean temperature are increasingly recognized as an important parameter of the climate system. Here we assess the potential of analyzing single-specimen planktonic foraminifera as proxy for the seasonal temperature contrast (seasonality). Oxygen isotopes and Mg/Ca ratios were measured on single specimens of Globigerinoides ruber, extracted from surface sediment samples of the Mediterranean Sea and the adjacent Atlantic Ocean. Variability in d18O and Mg/Ca was then compared to established modern seasonal changes in temperature and salinity for both regions. The results show that (1) average d18O-derived temperatures correlate with modern annual average temperatures for most sites, (2) the range in d18O- and Mg/Ca-derived temperature estimates from single-specimen analysis resembles the range in seasonal temperature values at the sea surface (0-50 m) in the Mediterranean Sea and the Atlantic Ocean, and (3) there is no strong correlation between Mg/Ca- and d18O-derived temperatures from the same specimens in the current data set, indicating that other parameters (salinity, carbonate ion concentration, symbiont activity, ontogenesis, and natural variability) potentially affect these proxies.

Foraminifera Mg/Ca, test weight and XDX for sediment core WIND28K

A record of deep-sea calcite saturation (D[CO3**-2]), derived from X-ray computed tomography-based foraminifer dissolution index, XDX, was constructed for the past 150 ka for a core from the deep (4157 m) tropical western Indian Ocean. G. sacculifer and N. dutertrei recorded a similar dissolution history, consistent with the process of calcite compensation. Peaks in calcite saturation (~15 µmol/kg higher than the present-day value) occurred during deglaciations and early in MIS 3. Dissolution maxima coincided with transitions to colder stages. The mass record of G. sacculifer better indicated preservation than did that of N. dutertrei or G. ruber. Dissolution-corrected Mg/Ca-derived SST records, like other SST records from marginal Indian Ocean sites, showed coolest temperatures of the last 150 ka in early MIS 3, when mixed layer temperatures were ~4°C lower than present SST. Temperatures recorded by N. dutertrei showed the thermocline to be ~4°C colder in MIS 3 compared to the Holocene (8 ka B.P.).

Stable isotopes, radionuclides, and calculated sea surface temperature of two sediment cores in the Sicily Channel

The Eastern Mediterranean Transient (EMT) occurred in the Aegean Sea from 1988 to 1995 and is the most significant intermediate-to-deep Mediterranean overturning perturbation reported by instrumental records. The EMT was likely caused by accumulation of high salinity waters in the Levantine and enhanced heat loss in the Aegean Sea, coupled with surface water freshening in the Sicily Channel. It is still unknown whether similar transients occurred in the past and, if so, what their forcing processes were. In this study, sediments from the Sicily Channel document surface water freshening (SCFR) at 1910±12, 1812±18, 1725±25 and 1580±30 CE. A regional ocean hindcast links SCFR to enhanced deep-water production and in turn to strengthened Mediterranean thermohaline circulation. Independent evidence collected in the Aegean Sea supports this reconstruction, showing that enhanced bottom water ventilation in the Eastern Mediterranean was associated with each SCFR event. Comparison between the records and multi-decadal atmospheric circulation patterns and climatic external forcings indicates that Mediterranean circulation destabilisation occurs during positive North Atlantic Oscillation (NAO) and negative Atlantic Multidecadal Oscillation (AMO) phases, reduced solar activity and strong tropical volcanic eruptions. They may have recurrently produced favourable deep-water formation conditions, both increasing salinity and reducing temperature on multi-decadal time scales.

(Table 1) Sulfur and oxygen isotopes from two anhydrite samples recovered from DSDP Hole 70-504B

The first anhydrite reported from oceanic basalts occurs in altered basalts drilled during DSDP Leg 70 from Hole 504B. Anhydrite has been identified in several samples, two of which were studied in detail. Anhydrite in Sample 504B-40-3 (130-135 cm), which was acquired at 310 meters sub-basement, occurs in a dolerite at the center of a vug rimmed by saponite and calcite. Red iron-hydroxide-rich alteration halos occur from 0 to 310 meters sub-basement; primary sulfides in these halos are oxidized, and the rocks have lost large amounts of sulfur. The anhydrite in this sample has a d34S value of 18.5 per mil, and it is interpreted to have formed from a fluid containing a mixture of seawater sulfate (20.9 per mil) and basaltic sulfur (0 per mil) released during the oxidation of primary sulfides. Anhydrite in Sample 504B-48-3 (14-18 cm), which was found at 376 meters sub-basement, occurs intergrown with gyrolite at the center of a 1-cm-wide vein that is rimmed by saponite and quartz. At sub-basement depths below 310 meters to the bottom of the Leg 70 section (562 m sub-basement), the rocks exhibit the effects of anoxic alteration with common secondary pyrite. Anhydrite in Sample 504B-48-3 (14-18 cm) has a d34S value of 36.7 per mil, and it is interpreted to have formed from seawater-derived fluids enriched in 34S through sulfate reduction. Temperatures of alteration calculated from oxygen isotope data range from 60 to 100°C. Sulfate reduction may have occurred in situ, or elsewhere at higher temperature, possibly deeper in the crust. The secondary mineral paragenetic sequence indicates a progressive decrease in Mg and increase in Ca in the circulating fluids. This eventually led to anhydrite formation late in the alteration process.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.