Age determination and carbonate content of sediment core KH-79-3_L3

Laminated sediments deposited under anoxic bottom waters in the Japan Sea during the last glacial maximum (LGM) contain extremely well preserved calcareous microfossils and eolian carbonates. The radiocarbon age-difference between bulk sediment and monospecific planktonic foraminifera in discrete laminae from a core in the southern Japan Sea implies that ~40% of the total carbonates in the sediments at the LGM are of eolian origin. Extrapolation of this result yields a rate of supply of eolian carbonates of ~2800 tons/d to the entire Japan Sea during the LGM. The climatic significance of this flux potentially lies in its broader geographic extension, particularly in the interaction of the carbonate-bearing dust with shallow, corrosive North Pacific waters and with rain in the atmosphere. By increasing the alkalinity of such waters and by enhancing the biological pump the dust flux could have increased CO2 absorption by both the ocean and rain during the LGM.

Chemistry of interstitial waters of ODP Site 166-718

Preliminary data are presented on dissolved heavy metals in interstitial water samples collected at Site 718 of Ocean Drilling Program Leg 118. The heavy metals at this site are divided into three groups: Group I (B, K, Mn, Ni, Pb, total Si, total P, V) behaves like Mg, which decrease with depth; Group II (Ba, Cu, Sr, Ti) behaves like Ca, which increases with depth; and Group 111 (Cd, Co, Cr, Fe, Na, Mo, Zn) contains metals that are independent of depth. Mg decreases with depth from 50 mM at the seafloor to 21 mM at 900 mbsf. Mn in the sulfate reduction zone (1.0 to 2.8 ppm) is more highly concentrated than in the methane fermentation zone (0.23 to 0.50 ppm), except for Section 116-718-1H-1. A similar behavior is also observed for V and Pb. Ni, B, and K decrease non-uniformly with depth. Ca and Sr increase with depth at the same rates, indicating the dissolution of inorganic calcium carbonate by anaerobic oxidation of organic matter (Sayles, 1981, doi:10.1016/0016-7037(81)90132-0). The distribution of Ba with depth is very similar to those of Ca and Sr. Cu and Ti profiles trend to increase non-uniformly with depth. Fe is constant with depth. The sharp decrease in total silicate concentration at the seafloor probably indicates a decrease in the decomposition of siliceous biological matter (e.g., diatoms) and production of opal. The constant levels of Group 111, except for Na and Fe, may reveal equal sources of supply from surface seawater and the Himalayas over time.

Petrologic data from Site U1308 over the last three glaciations

A composite North Atlantic record from DSDP Site 609 and IODP Site U1308 spans the past 300,000 years and shows that variability within the penultimate glaciation differed substantially from that of the surrounding two glaciations. Hematite stained grains exhibit similar repetitive down-core variations within the Marine Isotope Stage (MIS) 8 and 4-2 intervals, but little cyclic variability within the MIS 6 section. There is also no petrologic evidence, in terms of detrital carbonate-rich (Heinrich) layers, for surging of the Laurentide Ice Sheet through the Hudson Strait during MIS 6. Rather, very high background concentration of ice-rafted debris (IRD) indicates near continuous glacial meltwater input that likely increased thermohaline disruption sensitivity to relatively weak forcing events, such as expanded sea ice over deepwater formation sites. Altered (sub)tropical precipitation patterns and Antarctic warming during high orbital precession and low 65° N summer insolation appears related to high abundance of Icelandic glass shards and southward sea ice expansion. Differing European and North American ice sheet configurations, perhaps aided by larger variations in eccentricity leading to cooler summers, may have contributed to the relative stability of the Laurentide Ice Sheet in the Hudson Strait region during MIS 6.

Carbonate composition of Pliocene-Pleistocene sediments of the Maledives

Ocean Drilling Program (ODP) Leg 115 post-cruise research was focused on two Maldives sites, more precisely on the top 108 m of Hole 716B (water depth, 540 m), equivalent to the past 3.5 m.y., and the top 19.5 m of Hole 714A (water depth, 2195 m), equivalent to the past 0.55 m.y. These sediments consist of mostly unaltered and undisturbed, turbidite-free, periplatform ooze. Results of our research are compared with existing data on Hole 633A (water depth, 1681 m), drilled in the Bahamas during ODP Leg 101, using age/depth models built on the basis of oxygen isotope, nannofossil, and magnetic stratigraphies. Climate-induced, long-term (roughly 0.5 m.y.) aragonite cycles, superposed on short-term (roughly 0.04 and 0.1 m.y.) aragonite cycles, have been established at least during the past 2.0 m.y., in the Maldives and the Bahamas. Our most interesting result is the clear correlation among the aragonite long-term cycles in the Maldives and the Bahamas and the carbonate-preservation, long-term cycles from the open Pacific, Indian, and North Atlantic oceans. The mid-Brunhes dissolution interval, corresponding to the youngest preservation minima of the carbonate-preservation, longterm cycles, is clearly defined by fine aragonite minimum values in the deep periplatform sites, and by maximum fragmentation of pteropod tests in the shallow sites. Aragonite and planktonic d18O records, usually in phase during the late Pleistocene, display, further back in time, discreet intervals where the two records do not match with one another. Major mismatches between both records occur synchronously in the Maldives and Bahamas periplatform sites and seem to correspond to extreme events of either carbonate-preservation or dissolution in the deep pelagic carbonate sites of the equatorial Pacific Ocean. Based on our findings, short- and long-term aragonite cycles can no longer be explained only by variations of aragonite input from the nearby shallow carbonate banks, in response to their alternate flooding and exposure through cyclic sea-level fluctuations. The aragonite long-term cycles in the periplatform environments are interpreted as carbonatepreservation cycles at intermediate-water depths. Their occurrence shows, therefore, that the carbonate chemistry of the entire water column has been influenced by long-term (0.5 m.y.) cyclic variations during the past 2.0 m.y. These major changes of the water-column carbonate chemistry are linked to the climate-induced carbon cycling among the different atmospheric, oceanic, and sedimentary carbon reservoirs.

(Table 1) Chemical composition of buried manganese noduls and host sediments of ODP Hole 138-854C

Two manganese (Mn) nodules were found in upper Miocene sediments in Hole 854C at a depth of 32.12 mbsf (Samples 138-854C-5H-1,0-2 cm, and -6H-1, 2-4 cm). In structure and composition, the lower nodule is similar to the Pleistocene surface nodules associated with radiolarian ooze from the Clarion-Clipperton Nodule Province. The upper nodule resembles those occurring on pelagic clay from the northern margin of that province.

(Appendix) Bulk inorganic chemistry at DSDP Leg 77 Holes

Clay mineralogic and inorganic geochemical investigations of Cretaceous and Cenozoic sediments of the western Gulf of Mexico lead to the following main conclusions. (1) Transition of lowermost Cretaceous continental to marine sedimentation is marked by a clay evaporitic stage, north of the Campeche Escarpment. (2) Existence of combined mineralogic and geochemical stratigraphy allows us to propose correlations between Sites 535 and 540, especially for the Albian. (3) Predominance of detrital clay assemblages is indicative of hot and variably humid continental climate until the early late Cenozoic. (4) Tectonic destabilization of the margins of Gulf of Mexico occurred at different periods, especially until the middle Cretaceous, with a mixed erosion of rocks and soils and temporary oxidized conditions of deposition. (5) Successive developments of confined perimarine basins occurred from the earliest Cretaceous until the Miocene, chiefly in the Florida area. The sources of inorganic materials were chiefly situated on the east of the studied area until the late Tertiary and after that in the Mississippi River basin. (6) Occasionally, volcanic activity influenced the clay mineralogy and mainly the geochemistry, and possibly contributed to the rather strong magnesian character of the deposition until the late Paleogene. (7) The argillaceous diagenesis is weak; variability of the carbonate diagenesis is marked by the relation Sr = f(CaO) and chiefly depends on the depth of burial, the clay content, the porosity, and the geologic age.

Seawater carbonate chemistry and zooxanthellate coral Cladocora caespitosa boron isotopic and elemental systematics during experiments, 2011

Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 > 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.