Characterization of diagenetic fluids at ODP Site 103-639

Site 639, drilled during Leg 103 of the Ocean Drilling Program, penetrated an Upper Jurassic to Lower Cretaceous carbonate platform on a tilted fault block along the Galicia margin off the northwest Iberian Peninsula. The carbonate platform is composed primarily of a sequence of dolomite overlying limestone. Samples were analyzed for mineral chemistry, stable isotope geochemistry, fluid inclusion microthermometry, and volatile contents and by dolomite pyrolysis mass spectrometry for trace sulfate minerals. The dolomite recovered from the Galicia margin at Site 639 formed during shallow burial from sulfate-bearing, hypersaline brines at slightly elevated temperatures. The light oxygen isotopic signatures of the dolomite are interpreted as the result of the evaporative loop and slightly elevated temperatures during dolomite formation or from reequilibration at higher temperatures during deeper burial. The hypersalinity is interpreted to be associated with a nearby, shallow restricted basin that formed during rifting of the Iberian margin from Newfoundland. The dolomitization of the platform is therefore a by-product of the rifting.

Stable carbon and nitrogen isotopic ratios of cores from the Bering Sea

Stable carbon and nitrogen isotopic ratios (d13C and d15N) of organic matter were measured in three sediment cores from deep basins of the Bering Sea to investigate past changes in surface nutrient conditions. For surface water reconstructions, hemipelagic layers in the cores were distinguished from turbidite layers (on the basis of their sedimentary structures and 14C ages) and analyzed for isotopic studies. Although d13C profiles may have been affected by diagenesis, both d15N and d13C values showed common positive anomalies during the last deglaciation. We explain these anomalies as reflecting suppressed vertical mixing and low nutrient concentrations in surface waters caused by injection of meltwater from alpine glaciers around the Bering Sea.

Holocene d18O diatom from ODP Hole 178-1098A

The causes for rising temperatures along the Antarctic Peninsula during the late Holocene have been debated, particularly in light of instrumental records of warming over the past decades (Russell and McGregor, 2010, doi:10.1007/s10584-009-9673-4). Suggested mechanisms range from upwelling of warm deep waters onto the continental shelf in response to variations in the westerly winds (Bentley et al., 2009, doi:10.1177/0959683608096603), to an influence of El Niño-Southern Oscillation on sea surface temperatures (Shevenell et al., 2011, doi:10.1038/nature09751). Here, we present a record of Holocene glacial ice discharge, derived from the oxygen isotope composition of marine diatoms from Palmer Deep along the west Antarctic Peninsula continental margin. We assess atmospheric versus oceanic influences on glacial discharge at this location, using analyses of diatom geochemistry to reconstruct atmospherically forced glacial ice discharge and diatom assemblage (Taylor and Sjunneskog, 2002, doi:10.1029/2000PA000564) ecology to investigate the oceanic environment. We show that two processes of atmospheric forcing-an increasing occurrence of La Niña events (Makou et al., 2010, doi:10.1130/G30366.1) and rising levels of summer insolation-had a stronger influence during the late Holocene than oceanic processes driven by southern westerly winds and upwelling of upper Circumpolar Deepwater. Given that the evolution of El Niño-Southern Oscillation under global warming is uncertain (Yeh et al., 2009, doi:10.1038/nature08316), its future impacts on the climatically sensitive system of the Antarctic Peninsula Ice Sheet remain to be established.

Radiocarbon ages, carbon and oxygen isotopes and Mg/Ca and Sr/Ca ratios of Globigerinoides in sediment core MD99-2203, Cape Hatteras

This study presents high-resolution foraminiferal-based sea surface temperature, sea surface salinity and upper water column stratification reconstructions off Cape Hatteras, a region sensitive to atmospheric and thermohaline circulation changes associated with the Gulf Stream. We focus on the last 10,000 years (10 ka) to study the surface hydrology changes under our current climate conditions and discuss the centennial to millennial time scale variability. We observed opposite evolutions between the conditions off Cape Hatteras and those south of Iceland, known today for the North Atlantic Oscillation pattern. We interpret the temperature and salinity changes in both regions as co-variation of activities of the subtropical and subpolar gyres. Around 8.3 ka and 5.2-3.5 ka, positive salinity anomalies are reconstructed off Cape Hatteras. We demonstrate, for the 5.2-3.5 ka period, that the salinity increase was caused by the cessation of the low salinity surface flow coming from the north. A northward displacement of the Gulf Stream, blocking the southbound low-salinity flow, concomitant to a reduced Meridional Overturning Circulation is the most likely scenario. Finally, wavelet transform analysis revealed a 1000-year period pacing the d18O signal over the early Holocene. This 1000-year frequency band is significantly coherent with the 1000-year frequency band of Total Solar Irradiance (TSI) between 9.5 ka and 7 ka and both signals are in phase over the rest of the studied period.

Terrigenous proxy record from ODP Site 202-1237 and sediment core RRV9702a-69PC

ODP Site 1237 and sediment core RRV9702a-69PC were investigated for siliciclastic grain-size distributions and changes in geochemical composition to reconstruct southeast trade-wind variability during the past 5 Ma. Because both, working and archive halves of all ODP Site 1237 cores were completely depleted between 3.3 and 8.1 meters composite depths, (mcd), the corresponding sections of pre-site survey core RRV9702A-69PC were sampled and investigated to fill the gap.

Chemical and isotopic compositions of authigenic carbonates from the area of the Sakhalin-Deryugin gas anomaly, Sea of Okhotsk

Features of sedimentation of carbonate mineral associations in the northeastern shelf of Sakhalin and other regions of the Sea of Okhotsk are considered. Special attention is paid to correlation between carbonate neoformations and abnormal fluxes of methane. In bottom sediments with high contents of methane carbonate-sulfide associations occur, their generation has been influenced by gas (mostly methane) fields. Joint consideration of distribution of gas and geochemical fields and mineral associations in the Sea of Okhotsk allows to understand better a mechanism of mineral generation in bottom sediments, possible formation of ore accumulations, and to use them as indicators for prognosis of mineral resources.

Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Lithium and strontium isotopic compositions of sediments and pore waters at ODP Sites 152-918 and 152-919

The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. d6Li values of pore waters at these two sites vary between -42 and -25?. At shallow depths (<100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of d6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5-10% of the total inputs from rivers and submarine hot springs.