The occurrence and significance of Pleistocene and Upper Pliocene sapropels

Numerous sapropels and sapropelic strata from Upper Pliocene and Pleistocene hemipelagic sediments of the Tyrrhenian Sea show that intermittent anoxia, possibly related to strongly increased biological productivity, was not restricted to the eastern Mediterranean basins and may be a basin-wide result of Late Pliocene-Pleistocene climatic variability. Even though the sapropel assemblage of the Tyrrhenian Sea clearly originates from multiple processes such as deposition under anoxic conditions or during spikes in surface water productivity and lateral transport of organic-rich suspensates, many "pelagic sapropels" have been recognized. Stratigraphic ages calculated for the organic-rich strata recovered during ODP Leg 107 indicate that the frequency of sapropel formation increased from the lowermost Pleistocene to the base of the Jaramillo magnetic event, coinciding with a period when stable isotope records of planktonic foraminifera indicate the onset of climatic cooling in the Mediterranean. A second, very pronounced peak in sapropel formation occurred in the Middle to Late Pleistocene (0.73-0.26 Ma). Formainifers studied in three high-resolution sample sets suggest that changes in surface-water temperature may have been responsible for establishing anoxic conditions, while salinity differences were not noted in the faunal assemblage. However, comparison of sapropel occurrence at Site 653 with the oxygen isotopic record of planktonic foraminifers established by Thunell et al. (1990, doi:10.2973/odp.proc.sr.107.155.1990) indicates that sapropel occurrences coincide with negative d18O excursions in planktonic foraminifers in thirteen of eighteen sapropels recognized in Hole 653A. A variant of the meltwater hypothesis accepted for sapropel formation in the Late Pleistocene eastern Mediterranean may thus be the cause of several "anoxic events" in the Tyrrhenian as well. Model calculations indicate that the amount of oxygen advection from Western Mediterranean Deep Water exerts the dominant control on the oxygen content in deep water of the Tyrrhenian Sea. Inhibition of deep-water formation in the northern Adriatic and the Balearic Basin by increased meltwater discharge and changing storm patterns during climatic amelioration may thus be responsible for sapropel formation in the Tyrrhenian Sea.

Susceptibility, magnetization and S-ratio of ODP Sites 201-1225 and 201-1227

Samples were collected at Sites 1225 and 1227 to investigate the occurrence of fine-grained, biogenic magnetic particles (magnetosomes). Several magnetic methods, including anhysteretic remanent magnetization and isothermal remanent magnetization, were used to characterize the main magnetic carriers in the samples. Extracts were made to isolate the fine-grained fraction, which was then examined under a transmission electron microscope. Grains with the unique characteristics of magnetosomes were found in samples from regions in the core with both high and low concentrations of magnetic minerals. This suggests they have the potential to be a persistent proxy of paleoredox conditions.

Carbon and oxygen isotopic composition of benthic foraminifers from ODP Site 167-1014 and Hole 167-1020C

Benthic foraminiferal stable isotope data are presented for Sites 1014 (Tanner Basin, 1176 m) and 1020 (Gorda Ridge, 3040 m) to constrain past changes in Pacific deep- and intermediate-water nutrient chemistry associated with the onset of large-amplitude 100-k.y. climate cycles after ~900 ka. The Site 1014 data were based on analyses of separate species of Cibicidoides, whereas only Cibicidoides wuellerstorfi was used to generate the Site 1020 record. The present data span 380-920 and 620-950 ka at Sites 1014 and 1020, respectively.

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.

AMS 14C dating points, isotopic compositions, Mg/Ca ratios and sea surface temperatures of sediment cores GeoB10029-4 and GeoB10038-4

Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater d18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30'S, 100°08'E, and GeoB 10038-4, 5°56'S, 103°15'E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2-3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater d18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater ?18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling-Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

Monthly Bonaire coral Sr/Ca and oxygen isotope data from 118 kyr ago (coral BON-5-D)

The end of the last interglacial period, ~118 kyr ago, was characterized by substantial ocean circulation and climate perturbations resulting from instabilities of polar ice sheets. These perturbations are crucial for a better understanding of future climate change. The seasonal temperature changes of the tropical ocean, however, which play an important role in seasonal climate extremes such as hurricanes, floods and droughts at the present day, are not well known for this period that led into the last glacial. Here we present a monthly resolved snapshot of reconstructed sea surface temperature in the tropical North Atlantic Ocean for 117.7±0.8 kyr ago, using coral Sr/Ca and d18O records. We find that temperature seasonality was similar to today, which is consistent with the orbital insolation forcing. Our coral and climate model results suggest that temperature seasonality of the tropical surface ocean is controlled mainly by orbital insolation changes during interglacials.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.