Ion concentration and deduced chemical compounds of the GRIP and Dome Fuji ice cores, Greenland and Antarctica

We have proposed a method of deducing the chemical compounds found in deep polar ice cores by analyzing the balance between six major ions (Cl-, NO3-, SO4**2-, Na+, Mg2+, and Ca2+). The method is demonstrated for the Holocene and last glacial maximum regions of the Dome Fuji and GRIP ice cores. The dominant compounds depend only on the ion balance and the sequence of chemical reactions. In priority order, the principle salts are calcium sulfate, other sulfates, nitrate, chloride, and carbonate. The chemical abundances deduced by this method agree well with the results of Raman spectroscopy on individual salt inclusions. The abundances in the ice cores are shown to reflect differences in climatic periods (the acidic environment of the Holocene versus the reductive environment of the last glacial maximum) and regional conditions (the marine environment of Antarctica versus the continental environment of Greenland).

(Table 1) Color, Fe-C-S chemistry and carbonate content from ODP Sites 172-1062 and 172-1063

Reflectance spectra collected during ODP Leg 172 were used in concert with solid phase iron chemistry, carbonate content, and organic carbon content measurements to evaluate the agents responsible for setting the color in sediments. Factor analysis has proved a valuable and rapid technique to detect the local and regional primary factors that influence sediment color. On the western North Atlantic drifts, sediment color is the result of primary mineralogy as well as diagenetic changes. Sediment lightness is controlled by the carbonate content while the hue is primarily due to the presence of hematite and Fe2+/Fe3+ changes in clay minerals. Hematite, most likely derived from the Permo-Carboniferous red beds of the Canadian Maritimes, is differentially preserved at various sites due to differences in reductive diagenesis and dilution by other sedimentary components. Various intensities for diagenesis result from changes in organic carbon content, sedimentation rates, and H2S production via anaerobic methane oxidation. Iron monosulfides occur extensively at all high sedimentation sites especially in glacial periods suggesting increased high terrigenous flux and/or increased reactive iron flux in glacials.

Electromagnetic, rock magnetic, and geochemical properties of surficial sediments in Eckernförde Bay

Submarine groundwater discharge in coastal settings can massively modify the hydraulic and geochemical conditions of the seafloor. Resulting local anomalies in the morphology and physical properties of surface sediments are usually explored with seismo-acoustic imaging techniques. Controlled source electromagnetic imaging offers an innovative dual approach to seep characterization by its ability to detect pore-water electrical conductivity, hence salinity, as well as sediment magnetic susceptibility, hence preservation or diagenetic alteration of iron oxides. The newly developed electromagnetic (EM) profiler Neridis II successfully realized this concept for a first time with a high-resolution survey of freshwater seeps in Eckernförde Bay (SW Baltic Sea). We demonstrate that EM profiling, complemented and validated by acoustic as well as sample-based rock magnetic and geochemical methods, can create a crisp and revealing fingerprint image of freshwater seepage and related reductive alteration of near-surface sediments. Our findings imply that (1) freshwater penetrates the pore space of Holocene mud sediments by both diffuse and focused advection, (2) pockmarks are marked by focused freshwater seepage, underlying sand highs, reduced mud thickness, higher porosity, fining of grain size, and anoxic conditions, (3) depletion of Fe oxides, especially magnetite, is more pervasive within pockmarks due to higher concentrations of organic and sulfidic reaction partners, and (4) freshwater advection reduces sediment magnetic susceptibility by a combination of pore-water injection (dilution) and magnetite reduction (depletion). The conductivity vs. susceptibility biplot resolves subtle lateral litho- and hydrofacies variations.

Bulk calcite minor element composition of ODP Leg 130 samples

We investigated minor element ratios (Sr/Ca and Mg/Ca) in bulk sediment samples from Sites 803-807 using a recently optimized sample treatment protocol for calcium-carbonate-rich sediments consisting of sequential reductive and ion exchange treatments. We evaluated this protocol relative to bulk sediment leaching using samples from Sites 804 and 806, the two end-member sites in the depth transect, reporting as well Mn/Ca and Fe/Ca ratios for sediments from these two sites processed by means of both methods. The Sr/Ca ratios were only slightly affected by the sample treatment, with an average reduction of 6%-7% caused primarily by the ion exchange step. The reductive sample treatment, designed to be effective at removing Mn-rich oxyhydroxides, has a major effect on Mg/Ca ratios, with up to 50% reduction, whereas little effect occurred in ion exchange alone on Mg/Ca ratios. The Mn/Ca and Fe/Ca ratios were not consistently offset by the sample treatment, and these ratios do not appear to be representative of calcite geochemistry reflecting either ocean history or diagenetic overprinting. Celestite solubility appears to be an important control on interstitial water Sr concentrations in these sites, and it must be considered when constructing Sr mass balance models of calcite recrystallization. Calcite Sr/Ca ratios (range 1-2 mmol/mol) are similar from site to site when plotted vs. age, with a pattern comparable to that for well-preserved foraminifer tests over the past 40 Ma. Interstitial water Mg and Ca gradients appear to reflect basement character and the intensity of alteration; they can vary substantially over a small area. Calcite Mg/Ca ratios (range 1.5-4.5 mmol/mol) differ from site to site, with generally higher ratios for sites at a shallower water depth. Increasing calcite Mg/Ca ratios correlate with decreasing Sr/Ca ratios in the treated samples. No consistent pattern exists for calcite Mg/Ca ratios vs. age or depth, nor is any direct correlation to interstitial water Mg/Ca ratios present.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Sediment geochemical evidence for an early-middle Gilbert (early Pliocene) productivity peak in the North Pacific Red Clay Province

Current attempts to understand climatic variability during the early to middle Pliocene require paleoceanographic information from the Pacific and Indian Oceans that may serve to test and/or constrain future circulation models. Ocean Drilling Program (ODP) Sites 885/886 are located in the central subarctic North Pacific at water depths exceeding 5700 m. Recent studies of rock magnetic properties suggest that the fine-grained Fe oxide component in sediment at Sites 885/886 experienced reductive dissolution during the early-middle Gilbert. Because such an interval in the North Pacific Red Clay Province suggests a maximum in the sedimentary flux of organic carbon and/or a minimum in bottom water dissolved O2 concentrations (and hence, a peak change in North Pacific oceanographic conditions), a geochemical investigation was conducted to test the hypothesis. Quaternary sediment at Hole 886B was subjected to an oxyhydroxide removal procedure, and chemical analyses indicate that bulk sediment concentrations of Fe and the Fe/Sc ratio decrease significantly upon reductive dissolution. Downcore chemical analyses of untreated sediment at Hole 886B demonstrate that similar depletions also occur across the proposed interval of reduced sediment. Downcore chemical analyses also indicate that a pronounced increase in the Ba/Sc ratio occurs across the interval. These results are consistent with an interpretation that abyssal sediment of the North Pacific experienced a decrease in redox conditions during the early-middle Gilbert, and that this change in oxidation state was related to a peak in paleoproductivity. If the zenith of late Miocene to middle Pliocene enhanced productivity observed at other Indo-Pacific divergence regions similarly can be constrained to the early-middle Gilbert, there exists an oceanographic boundary condition in which to test future models concerning Pliocene warmth.

(Table 2) Chemical composition of phosphates from the Namibian and Chilean shelves

This study on phosphorites of different compositions and ages from shelf sediments and seamounts of the Pacific Ocean by means of analytical electron microscopy showed that these phosphorites contain ultra-microscopic inclusions of authigenic minerals and, more rarely, of rare earth element (REE) minerals. In some of phosphorite samples of Pleistocene-Pliocene age from the Namibian shelf both kinds of minerals were found. Uranium minerals were represented by uraninite, coffinite, and ningioite; those of REE - by monazite, xenotime, and bastnesite, which points to their potential accumulation not only as isomorphous admixtures in calcium phosphate but also as independent mineral phases. Coexistence of the minerals noted in shelf phosphorites is caused by repeated changes in redox conditions during formation and then redeposition of phosphate concretions. Presence of uranium minerals in phosphorites from seamounts shows that during an initial step of formation of these phosphorites environment was rather suboxic or reductive than oxic.

Neodymium isotope composition of planktonic foraminifera from ODP Hole 121-758A

This study presents neodymium isotope and elemental data for cleaned planktonic foraminifera from ODP site 758 in the southernmost reaches of the Bay of Bengal in the north-east Indian Ocean. Cleaning experiments using oxidative-reductive techniques suggest that diagenetic Fe-Mn oxyhydroxide coatings can be effectively removed, and that the measured Nd isotope composition reflects the composition of seawater from which the foraminiferal calcium carbonate was precipitated. Modern core-top Pulleniatina obliquiloculata and Globorotalia menardii give epsilon-Nd values of 310.12 +/- 0.16 and 310.28 +/- 0.16, respectively, indistinguishable from recent direct measurements of surface seawater in this area. A high-resolution Nd isotope record obtained from G. menardii for the past 150 kyr shows systematic variations (Delta epsilon-Nd = 3) on glacial-interglacial timescales. The timing of those variations shows a remarkable correspondence with the global oxygen isotope record, which suggests a process controlling the Nd isotope composition that responds in phase with global climate cycles. Palaeoclimate reconstruction indicates that during the last glacial maximum changes in monsoon circulation resulted in a reduction in rainfall over the Indian subcontinent, and a decrease in the flux of river water delivered to the Bay of Bengal. Thus, changes in the riverine input of Nd, a change in either flux or composition, most likely caused the isotope variations, although changes in dust source or local ocean circulation may have also played a role. These results clearly establish a link between climate change and variations in radiogenic isotopes in the oceans, and illustrate the potential of Nd isotopes in foraminifera for highresolution palaeoceanographic reconstruction.