(Table 1) Oxygen and carbon isotope compositions of altered carbonates from DSDP Hole 6-53 from the western Pacific Ocean

In the lower part of DSDP core 53.0, partly recrystallized carbonate sediments and well recrystallized limestone breccias of Oligo-Miocene age are associated with altered volcanic flows, lithified tuffs, and tuff breccias, suggesting that carbonate alteration was the result of thermal metamorphism. However, the oxygen isotope compositions of these carbonates (-3.4 to +0.6 per mil rel. PDB) are not compatible with recrystallization and isotope exchange with sea water at high temperatures. Evaluating the effects of the composition of the water which exchanged with the carbonates and of carbonate-water isotope exchange in closed systems yields the following approximate maximum temperature of recrystallization: limestone breccias, 100°C; calcite veins rimming breccia clasts, 30°C; and unconsolidated sediments overlying the breccias, 20°C. Therefore, the volcanics at site 53.0 must have been emplaced into the primary carbonate sediments at relatively low temperatures. Subsequent carbonate alteration was probably a consequence of chemical changes in ambient pore waters resulting from the submarine weathering of volcanic material.

(Table 1) Oxygen and carbon isotopes and calcium carbonte of bulk carbonate at DSDP Hole 72-516F

A detailed oxygen and carbon isotope study of the upper Maestrichtian-lower Paleocene section of Hole 516F from the Rio Grande Rise reveals that large isotopic anomalies are clearly associated with the Cretaceous/Tertiary boundary. Across the Cretaceous/Tertiary boundary, the total carbonate content reaches a maximum exceeding 80% before rapidly decreasing in covariance with the carbon isotope record. This strong covariance between d13C and percent CaCO3 suggests either a significant reduction in primary productivity or a rapid shoaling of the calcium carbonate compensation depth. Importantly, the d13C record 2 Ma after the Cretaceous/Tertiary boundary remained depleted in 13C by at least 0.5 per mil compared to the late Maestrichtian.

Geochemical data from the USGS #1 Portland core, Canon City, Colorado

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events-the Coniacian to Santonian OAE 3-resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high-resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon-rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in d13C indicate that redox-controlled early diagenesis can also significantly alter d13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, d18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.

The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Mg/Ca and stable oxygen measurement of the past 27 Ma of ODP Hole 120-747A

We explore the applicability of paired Mg/Ca and 18O/16O measurements on benthic foraminifera from Southern Ocean site 747 to paleoceanographic reconstructions on pre-Pleistocene timescales. We focus on the late Oligocene through Pleistocene (27-0 Ma) history of paleotemperatures and the evolution of the d18O values of seawater (d18Osw) at a temporal resolution of ~100-200 kyr. Absolute paleotemperature estimates depend on assumptions of how Mg/Ca ratios of seawater have changed over the past 27 Myr, but relative changes that occur on geologically brief timescales are robust. Results indicate that at the Oligocene to Miocene boundary (23.8 Ma), temperatures lag the increase in global ice-volume deduced from benthic foraminiferal d18O values, but the smaller-scale Miocene glaciations are accompanied by ocean cooling of -1°C. During the mid-Miocene phase of Antarctic ice sheet growth (~15-13 Ma), water temperatures cool by ~3°C. Unlike the benthic foraminiferal d18O values, which remain relatively constant thereafter, temperatures vary (by 3°C) and reach maxima at ~12 and ~8.5 Ma. The onset of significant Northern Hemisphere glaciation during the late Pliocene is synchronous with an ~4°C cooling at site 747. A comparison of our d18Osw curve to the Haq et al. (1987, doi:10.1126/science.235.4793.1156 ) sea level curve yields excellent agreement between sequence boundaries and times of increasing seawater 18O/16O ratios. At ~12-11 Ma in particular, when benthic foraminiferal d18O values do not support a further increase in ice volume, the d18Osw curve comes to a maximum that corresponds to a major mid-Miocene sea level regression. The agreement between the character of our Mg/Ca-based d18Osw curve and sequence stratigraphy demonstrates that benthic foramaniferal Mg/Ca ratios can be used to trace the d18Osw on pre-Pleistocene timescales despite a number of uncertainties related to poorly constrained temperature calibrations and paleoseawater Mg/Ca ratios. The Mg/Ca record also highlights that deep ocean temperatures can vary independently and unexpectedly from ice volume changes, which can lead to misinterpretations of the d18O record.

Core alignment and composite depth scale of DSDP Site 86-577

Deep Sea Drilling Project Site 577 on Shatsky Rise (North Pacific Ocean) recovered a series of cores at three holes that contain calcareous nannofossil ooze of latest Cretaceous (late Maastrichtian) through early Eocene age. Several important records have been generated using samples from these cores, but the stratigraphy has remained outdated and confusing. Here we revise the stratigraphy at Site 577. This includes refining several age datums, realigning cores in the depth domain, and placing all stratigraphic markers on a current time scale. The work provides a template for appropriately bringing latest Cretaceous and Paleogene data sets at old drill sites into current paleoceanographic literature for this time interval. While the Paleocene Eocene Thermal Maximum (PETM) lies within core gaps at Holes 577* and 577A, the sedimentary record at the site holds other important events and remains crucially relevant to understanding changes in oceanographic conditions from the latest Cretaceous through early Paleogene.

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.