Geochemistry and isotopes at DSDP Hole 79-546

At Site 546, below the Mazagan Escarpment at a water depth of 4 km, 36 m of salt rock was cored from the top of one of a field of salt domes. The core was studied by thin section and a variety of geochemical procedures. The salt rock contains 0.1 to 3% carnallite and lesser amounts of sylvite and polyhalite, which with the corresponding high level of bromide place it within the potash evaporite facies. The bromide profile is of a dominantly marine evaporite deposited in moderately shallow brine which, however, was not repeatedly desiccated. A mineralogical argument suggests that the brine surface was not below sea level. An average of about 5% elastics, with dispersed anhydrite, darken the salt rock to deep shades of red, brown, and gray green. Most of the included materials are in highly deformed boudins or dispersions in the salt rock that has also undergone cataclasis in a subsequent, probably tectonic, deformation. The salt rock is slightly deficient in anhydrite, and the usual separate beds and laminae of anhydrite are virtually absent. Stable isotope ratios of sulfur and oxygen in the sulfate are clearly derived from sea water of Permian to Scythian age, in contrast to the late Triassic or Early Jurassic age of evaporites onshore in Morocco and Portugal and the corresponding evaporites offshore Maritime Canada. In contrast to those evaporites off the axis of Atlantic rifting, the salt at Site 546 may have been deposited in a very early central rift fed by marine waters from Tethys through the Gibraltar or South Atlas fracture zones.

Organic carbon content, stable isotopes and planktonic foraminifera in sediments of tghe norther Arabian Sea oxygen minimum zone

The northern Arabian Sea is one of the few regions in the open ocean where thermocline water is severely depleted in oxygen. The intensity of this oxygen minimum zone (OMZ) has been reconstructed over the past 225,000 years using proxies for surface water productivity, water column denitrification, winter mixing, and the aragonite compensation depth (ACD). Changes in OMZ intensity occurred on orbital and suborbital timescales. Lowest O2 levels correlate with productivity maxima and shallow winter mixing. Precession-related productivity maxima lag early summer insolation maxima by ~6 kyr, which we attribute to a prolonged summer monsoon season related to higher insolation at the end of the summer. Periods with a weakened or even non-existent OMZ are characterized by low productivity conditions and deep winter mixing attributed to strong and cold winter monsoonal winds. The timing of deep winter mixing events corresponds with that of periods of climatic cooling in the North Atlantic region.

Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Oxygen and carbon isotope data from late calcite and zeolite pore-fill cements at DSDP Site 445

Oxygen isotopic composition of zeolite pore-fill cements in andesitic volcaniclastic sandstones recovered from DSDP Site 445 ranges from +30.1 to +17.8? (SMOW) downhole. This change is controlled by large heat flow from the basement which caused early diagenetic emplacement of zeolites during early basin rifting. d18O-values of late calcite cements range from +25.1 to +27.4? (SMOW); their petrographic relation and inferred temperature of formation suggest that calcite cements were formed during late stages of diagenesis. Isotopic composition in these sandstones is in agreement with mineral paragenesis determined microscopically.

Stable carbon and oxygen isotopes from samples of the Anaximander seamounts in the eastern Mediterranean Sea

Porous seep-carbonates are exposed at mud volcanoes in the eastern Mediterranean Sea. The 13C-depleted aragonitic carbonates formed as a consequence of the anaerobic oxidation of methane in a shallow sub-surface environment. Besides the macroscopically visible cavernous fabric, extensive carbonate corrosion was revealed by detailed analysis. After erosion of the background sediments, the carbonates became exposed to oxygenated bottom waters that are periodically influenced by the release of methane and upward diffusion of hydrogen sulphide. We suggest that carbonate corrosion resulted from acidity locally produced by aerobic oxidation of methane and hydrogen sulphide in the otherwise, with respect to aragonite, oversaturated bottom waters. Although it remains to be tested whether the mechanisms of carbonate dissolution suggested herein are valid, this study reveals that a better estimate of the significance of corrosion is required to assess the amount of methane-derived carbon that is permanently fixed in seep-carbonates.

Carbon sources in the North Sea evaluated by means of carbon isotope tracers

A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sedi- ments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the d13C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration. In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indi- cates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes (224Ra and 228Ra). 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of meta- bolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, long- term pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.

Bulk stable carbon and oxygen isotopes from ODP Site 1258, and Fe intensities from ODP Site 1262, and minimal tuning age model options for ODP Site 1258 and 1262

Timing is crucial to understanding the causes and consequences of events in Earth history. The calibration of geological time relies heavily on the accuracy of radioisotopic and astronomical dating. Uncertainties in the computations of Earth's orbital parameters and in radioisotopic dating have hampered the construction of a reliable astronomically calibrated time scale beyond 40 Ma. Attempts to construct a robust astronomically tuned time scale for the early Paleogene by integrating radioisotopic and astronomical dating are only partially consistent. Here, using the new La2010 and La2011 orbital solutions, we present the first accurate astronomically calibrated time scale for the early Paleogene (47-65 Ma) uniquely based on astronomical tuning and thus independent of the radioisotopic determination of the Fish Canyon standard. Comparison with geological data confirms the stability of the new La2011 solution back to ~54 Ma. Subsequent anchoring of floating chronologies to the La2011 solution using the very long eccentricity nodes provides an absolute age of 55.530 {plus minus} 0.05 Ma for the onset of the Paleocene/Eocene Thermal Maximum (PETM), 54.850 {plus minus} 0.05 Ma for the early Eocene ash -17, and 65.250 {plus minus} 0.06 Ma for the K/Pg boundary. The new astrochronology presented here indicates that the intercalibration and synchronization of U/Pb and 40Ar/39Ar radiometric geochronology is much more challenging than previously thought.