Consolidation tests, elastic properties and grain size measurements at the consolidations samples from different Holes of IODP Expedition 302

The Integrated OceanDrilling Program's Expedition 302, the Arctic Coring Expedition (ACEX), recovered the first Cenozoic sedimentary sequence from the central Arctic Ocean. ACEX provided ground truth for basin scale geophysical interpretations and for guiding future exploration targets in this largely unexplored ocean basin. Here, we present results from a series of consolidation tests used to characterize sediment compressibility and permeability and integrate these with high-resolution measurements of bulk density, porosity and shear strength to investigate the stress history and the nature of prominent lithostratigraphic and seismostratigraphic boundaries in the ACEX record. Despite moderate sedimentation rates (10-30 m/Myr) and high permeability values (10**-15 -10**-18 m**2), consolidation and shear strength measurements both suggest an overall state of underconsolidation or overpressure. One-dimensional compaction modelling shows that to maintain such excess pore pressures, an in situ fluid source is required that exceeds the rate of fluid expulsion generated by mechanical compaction alone. Geochemical and sedimentological evidence is presented that identifes the Opal A-C/T transformation of biosiliceous rich sediments as a potential additional in situ fluid source.However, the combined rat of chemical and mechanical compaction remain too low to fully account for the observed pore pressure gradients, implying an additional diagenetic fluid source from within or below the recovered Cenozoic sediments from ACEX. Recognition of the Opal A-C/T reaction front in the ACEX record has broad reaching regional implications on slope stability and subsurface pressure evolution, and provides an important consideration for interpreting and correlating the spatially limited seismic data from the Arctic Ocean.

Seawater carbonate chemistry and silica during an experiment with a marine diatom Thalassiosira weissflogii, 2004

Opal accumulation rates in sediments have been used as a proxy for carbon flux, but there is poor understanding of the factors that regulate the Si quota of diatoms. Natural variation in silicon isotopes (delta.lc.gif - 54 Bytes30Si) in diatom frustules recovered from sediment cores are an alternative to opal mass for reconstructing diatom Si use and potential C export over geological timescales. Understanding the physiological factors that may influence the Si quota and the delta.lc.gif - 54 Bytes30Si isotopic signal is vital for interpreting biogenic silica as a paleoproxy. We investigated the influence of pCO2 on the Si quota, fluxes across the cell membrane, and frustule dissolution in the marine diatom Thalassiosira weissflogii and determined the effect that pCO2 has on the isotopic fractionation of Si. We found that our Si flux estimates mass balance and, for the first time, describe the Si budget of a diatom. The Si quota rose in cells grown with low pCO2 (100 ppm) compared with controls (370 ppm), and the increased quota was the result of greater retention of Si (i.e., lower losses of Si through efflux and dissolution). The ratio of efflux : influx decreased twofold as pCO2 decreased from 750 to 100 ppm. The efflux of silicon is shown to significantly bias measurements of silica dissolution rates determined by isotope dilution, but no effect on the Si isotopic enrichment factor (epsilon.lc.gif - 51 Bytes) was observed. The latter effect suggests that silicon isotopic discrimination in diatoms is set by the Si transport step rather than by the polymerization step. This observation supports the use of the v signal of biogenic silica as an indicator of the percentage utilization of silicic acid.

(Table 1) Summary of coral geochemical data and reconstructed SST

We analyzed strontium/calcium ratios (Sr/Ca) in four colonies of the Atlantic coral genus Montastrea with growth rates ranging from 2.3 to 12.6 mm/a. Derived Sr/Ca-sea surface temperature (SST) calibrations exhibit significant differences among the four colonies that cannot be explained by variations in SST or seawater Sr/Ca. For a single coral Sr/Ca ratio of 8.8 mmol/mol, the four calibrations predict SSTs ranging from 24.0° to 30.9°C. We find that differences in the Sr/Ca-SST relationships are correlated systematically with the average annual extension rate (ext) of each colony such that Sr/Ca (mmol/mol) = 11.82 (±0.13) - 0.058 (±0.004) * ext (mm/a) - 0.092 (±0.005) * SST (°C). This observation is consistent with previous reports of a link between coral Sr/Ca and growth rate. Verification of our growth-dependent Sr/Ca-SST calibration using a coral excluded from the calibration reconstructs the mean and seasonal amplitude of the actual recorded SST to within 0.3°C. Applying a traditional, nongrowth-dependent Sr/Ca-SST calibration derived from a modern Montastrea to the Sr/Ca ratios of a conspecific coral that grew during the early Little Ice Age (LIA) (400 years B.P.) suggests that Caribbean SSTs were >5°C cooler than today. Conversely, application of our growth-dependent Sr/Ca-SST calibration to Sr/Ca ratios derived from the LIA coral indicates that SSTs during the 5-year period analyzed were within error (±1.4°C) of modern values.

Seawater carbonate chemistry and biological processes of foraminifera, Globigerinoides ruber and Globigerinella siphonifera during experiments, 2011

Specimens of two species of planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera, were grown under controlled laboratory conditions at a range of temperatures (18-31 °C), salinities (32-44 psu) and pH levels (7.9-8.4). The shells were examined for their calcium isotope compositions (d44/40Ca) and strontium to calcium ratios (Sr/Ca) using Thermal Ionization Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. Although the total variation in d44/40Ca (~0.3 per mill) in the studied species is on the same order as the external reproducibility, the data set reveals some apparent trends that are controlled by more than one environmental parameter. There is a well-defined inverse linear relationship between d44/40Ca and Sr/Ca in all experiments, suggesting similar controls on these proxies in foraminiferal calcite independent of species. Analogous to recent results from inorganically precipitated calcite, we suggest that Ca isotope fractionation and Sr partitioning in planktic foraminifera are mainly controlled by precipitation kinetics. This postulation provides us with a unique tool to calculate precipitation rates and draws support from the observation that Sr/Ca ratios are positively correlated with average growth rates. At 25 °C water temperature, precipitation rates in G. siphonifera and G. ruber are calculated to be on the order of 2000 and 3000 µmol/m**2/h, respectively. The lower d44/40Ca observed at 29 °C in both species is consistent with increased precipitation rates at high water temperatures. Salinity response of d44/40Ca (and Sr/Ca) in G. siphonifera implies that this species has the highest precipitation rates at the salinity of its natural habitat, whereas increasing salinities appear to trigger higher precipitation rates in G. ruber. Isotope effects that cannot be explained by precipitation rate in planktic foraminifera can be explained by a biological control, related to a vacuolar pathway for supply of ions during biomineralization and a pH regulation mechanism in these vacuoles. In case of an additional pathway via cross-membrane transport, supplying light Ca for calcification, the d44/40Ca of the reservoir is constrained as -0.2 per mill relative to seawater. Using a Rayleigh distillation model, we calculate that calcification occurs in a semi-open system, where less than half of the Ca supplied by vacuolization is utilized for calcite precipitation. Our findings are relevant for interpreting paleo-proxy data on d44/40Ca and Sr/Ca in foraminifera as well as understanding their biomineralization processes.

Composite depth scales, ash layer correlations and splice tie points of ODP Site 186-1151

We present composite depth scales for the multiply cored intervals from Sites 1150 and 1151. These new depth scales place coeval strata recovered in cores from different holes at a single site into a common stratigraphic framework. At Site 1150, double coring between Holes 1150A and 1150B occurred over only a short interval between ~703 and 713 meters below seafloor (mbsf), but this is sufficient to tie the upper portion of the stratigraphic section cored in Hole 1150A to the lower portion cored in Hole 1150B. The upper ~100 m of the sedimentary section at Site 1151 was double cored with the advanced piston corer and partially cored with the rotary core barrel, resulting in the complete recovery of this interval. The composite depth scales were constructed using Splicer software to vertically adjust the relative depths of various cores from one hole to the depths from another hole so as to align distinct physical properties measured on cores. The magnetic susceptibility data was the physical property most easily correlated between holes, and therefore primarily used to create a composite depth scale and spliced stratigraphic section. The spliced section is a continuous stratigraphic section constructed from representative cored intervals from the holes at a site. Both the splice and the composite depth scale can be applied to other data sets from Site 1151 to provide a stratigraphically continuous and laterally consistent basis for interpreting lithologic features or data sets. The resulting composite scale showed a 30% improvement in correlation of the magnetic susceptibility data relative to the original mbsf depth scale, and comparable improvement when applied to the other data sets.

Calcium isotope ratios from marine barite and carbonate over Paleocene-Eocene Boundary (ODP Sites 1212 and 1221)

Carbonates are invaluable archives of the past, and have been used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. Such archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the importance of diagenesis on proxy fidelity, the effects of diagenesis on the calcium isotopic composition (d44Ca) of carbonates are unclear. Accordingly, bulk carbonate d44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene-Eocene Thermal Maximum (PETM, ~55 Ma). The d44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large (~0.8 per mil) variations in bulk carbonate d44Ca occur in the deeper site near the peak carbon isotope excursion, and are correlated with a large drop in carbonate weight percent. Such an effect is seen in neither the 1221 barite record nor the bulk carbonate record at the shallower, less dissolved Site 1212. We contend that ocean chemical changes associated with the abrupt and massive carbon release into the ocean-atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate d44Ca record via diagenesis in the sedimentary column. Such changes are considerable, and need to be taken into account when interpreting and modeling Ca isotope data over extreme climatic events associated with ocean chemical evolution.

Chemical composition of manganese nodules and crusts from the Pacific and Indian Ocean and Loch Fyne, Scotland

The first part of this thesis includes some topics of a non-geochemical nature but which are of importance in interpreting the geochemistry of nodules. The points covered include their distribution, petrography, structure, mineralogy and internal compositional variations. Part Two includes the geochemistry of both nodules and that of their surrounding sediments, This geochemical study has been divided into firstly, a general geochemical study of both nodules and sediments using a statistical approach to the interpretation of the data, secondly, the regional geochemistry of Pacific and Indian Ocean nodules and sediments, the latter entirely uninvestigated in the past, and thirdly, local variations in the composition of nodules. Throughout, emphasis has been placed on the geochemistry of nodules in terms of their environment of formation.