Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

Age determination of sediment core SO75-26KL, Portuguese margin

A benthic isotope record has been measured for core SO75-26KL from the upper Portuguese margin (1099 m water depth) to monitor the response of thermohaline overturn in the North Atlantic during Heinrich events. Evaluating benthic delta18O in TS diagrams in conjunction with equilibrium deltac fractionation implies that advection of Mediterranean outflow water (MOW) to the upper Portuguese margin was significantly reduced during the last glacial (< 15% compared to 30% today). The benthic isotope record along core SO75-26KL therefore primarily monitors variability of glacial North Atlantic conveyor circulation. The 14C-accelerator mass spectrometry ages of 13.54±.07 and 20.46±.12 ka for two ice-rafted detritus (IRD) layers in the upper core section and an interpolated age of 36.1 ka for a third IRD layer deeper in the core are in the range of published 14C ages for Heinrich events H1, H2, and H4. Marked depletion of benthic delta13C by 0.7-1.1 per mil during the Heinrich events suggests reduced thermohaline overturn in the North Atlantic during these events. Close similarity between meltwater patterns (inferred from planktonic delta18O) at Site 609 and ventilation patterns (inferred from benthic delta13C) in core SO75-26KL implies coupling between thermohaline overturn and surface forcing, as is also suggested by ocean circulation models. Benthic delta13C starts to decrease 1.5-2.5 kyr before Heinrich events Hl and H4, fully increased values are reached 1.5-3 kyr after the events, indicating a successive slowdown of thermohaline circulation well before the events and resumption of the conveyor's full strength well after the events. Benthic delta13C changes in the course of the Heinrich events show subtle maxima and minima suggesting oscillatory behavior of thermohaline circulation, a distinct feature of thermohaline instability in numerical models. Inferrred gradual spin-up of thermohaline circulation after Hl and H4 is in contrast to abrupt wanning in the North Atlantic region that is indicated by sudden increases in Greenland ice core delta18O and in marine faunal records from the northern North Atlantic. From this we infer that thermohaline circulation can explain only in part the rapid climatic oscillations seen in glacial sections of the Greenland ice core record.

Rare earth element data for sediments from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Rock magnetic of serpentinite seamounts in the Mariana and Izu-Bonin regions

During Leg 125, scientists drilled two serpentinite seamounts: Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. Grain densities of the serpentinized peridotites range from 2.44 to 3.02 g/cm**3. The NRM intensity of the serpentinized peridotites ranges from 0.01 to 0.59 A/m and that of serpentine sediments ranges from 0.01 to 0.43 A/m. Volume susceptibilities of serpentinized peridotites range from 0.05 * 10**-3 SI to 9.78 * 10**-3 SI and from 0.12 * 10**-3 to 4.34 * 10**-3 SI in the sediments. Koenigsberger ratios, a measure of the relative contributions of remanent vs. induced magnetization to the magnetic anomaly, vary from 0.09 to 80.93 in the serpentinites and from 0.06 to 4.74 in the sediments. The AF demagnetization behavior of the serpentinized peridotites shows that a single component of remanence (probably a chemical remanence carried by secondary magnetite) can be isolated in many samples that have a median destructive field less than 9.5 mT. Multiple remanence components are observed in other samples. Serpentine sediments exhibit similar behavior. Comparison of the AF demagnetization of saturation isothermal remanence and NRM suggests that the serpentinized peridotites contain both single-domain and multidomain magnetite particles. The variability of the magnetic properties of serpentinized peridotites reflects the complexity of magnetization acquired during serpentinization. Serpentinized peridotites may contribute to magnetic anomalies in forearc regions.

Middle to late Miocene oxygen isotope stratigraphy of ODP site 1085 (SE Atlantic): new constrains on Miocene climate variability and sea-level fluctuations

The middle Miocene delta18O increase represents a fundamental change in earth's climate system due to a major expansion and permanent establishment of the East Antarctic Ice Sheet accompanied by some effect of deepwater cooling. The long-term cooling trend in the middle to late Miocene was superimposed by several punctuated periods of glaciations (Mi-Events) characterized by oxygen isotopic shifts that have been related to the waxing and waning of the Antarctic ice-sheet and bottom water cooling. Here, we present a high-resolution benthic stable oxygen isotope record from ODP Site 1085 located at the southwestern African continental margin that provides a detailed chronology for the middle to late Miocene (13.9-7.3 Ma) climate transition in the eastern South Atlantic. A composite Fe intensity record obtained by XRF core scanning ODP Sites 1085 and 1087 was used to construct an astronomically calibrated chronology based on orbital tuning. The oxygen isotope data exhibit four distinct delta18O excursions, which have astronomical ages of 13.8, 13.2, 11.7, and 10.4 Ma and correspond to the Mi3, Mi4, Mi5, and Mi6 events. A global climate record was extracted from the oxygen isotopic composition. Both long- and short-term variabilities in the climate record are discussed in terms of sea-level and deep-water temperature changes. The oxygen isotope data support a causal link between sequence boundaries traced from the shelf and glacioeustatic changes due to ice-sheet growth. Spectral analysis of the benthic delta18O record shows strong power in the 400-kyr and 100-kyr bands documenting a paleoceanographic response to eccentricity-modulated variations in precession. A spectral peak around 180-kyr might be related to the asymmetry of the obliquity cycle indicating that the response of the dominantly unipolar Antarctic ice-sheet to obliquityinduced variations probably controlled the middle to late Miocene climate system. Maxima in the delta18O record, interpreted as glacial periods, correspond to minima in 100-kyr eccentricity cycle and minima in the 174-kyr obliquity modulation. Strong middle to late Miocene glacial events are associated with 400-kyr eccentricity minima and obliquity modulation minima. Thus, fluctuations in the amplitude of obliquity and eccentricity seem to be the driving force for the middle to late Miocene climate variability.

Temperature and acidification variability reduce physiological performance in the intertidal zone porcelain crab Petrolisthes//cinctipes

We show here that increased variability of temperature and pH synergistically negatively affects the energetics of intertidal zone crabs. Under future climate scenarios, coastal ecosystems are projected to have increased extremes of low tide-associated thermal stress and ocean acidification-associated low pH, the individual or interactive effects of which have yet to be determined. To characterize energetic consequences of exposure to increased variability of pH and temperature, we exposed porcelain crabs, Petrolisthes cinctipes, to conditions that simulated current and future intertidal zone thermal and pH environments. During the daily low tide, specimens were exposed to no, moderate or extreme heating, and during the daily high tide experienced no, moderate or extreme acidification. Respiration rate and cardiac thermal limits were assessed following 2.5 weeks of acclimation. Thermal variation had a larger overall effect than pH variation, though there was an interactive effect between the two environmental drivers. Under the most extreme temperature and pH combination, respiration rate decreased while heat tolerance increased, indicating a smaller overall aerobic energy budget (i.e. a reduced O2 consumption rate) of which a larger portion is devoted to basal maintenance (i.e. greater thermal tolerance indicating induction of the cellular stress response). These results suggest the potential for negative long-term ecological consequences for intertidal ectotherms exposed to increased extremes in pH and temperature due to reduced energy for behavior and reproduction.

Individual foraminifera variability from the western and eastern equatorial Pacific during the Late Holocene and Last Glacial Maximum

El Niño-Southern Oscillation (ENSO) is a major source of global interannual variability, but its response to climate change is uncertain. Paleoclimate records from the Last Glacial Maximum (LGM) provide insight into ENSO behavior when global boundary conditions (ice sheet extent, atmospheric partial pressure of CO2) were different from those today. In this work, we reconstruct LGM temperature variability at equatorial Pacific sites using measurements of individual planktonic foraminifera shells. A deep equatorial thermocline altered the dynamics in the eastern equatorial cold tongue, resulting in reduced ENSO variability during the LGM compared to the Late Holocene. These results suggest that ENSO was not tied directly to the east-west temperature gradient, as previously suggested. Rather, the thermocline of the eastern equatorial Pacific played a decisive role in the ENSO response to LGM climate.

Winter sea surface temperature reconstruction from planktic foraminiferal transfer functions in the northeastern Arabian Sea over the last two millennia

The Indian monsoon system is an important climate feature of the northern Indian Ocean. Small variations of the wind and precipitation patterns have fundamental influence on the societal, agricultural, and economic development of India and its neighboring countries. To understand current trends, sensitivity to forcing, or natural variation, records beyond the instrumental period are needed. However, high-resolution archives of past winter monsoon variability are scarce. One potential archive of such records are marine sediments deposited on the continental slope in the NE Arabian Sea, an area where present-day conditions are dominated by the winter monsoon. In this region, winter monsoon conditions lead to distinctive changes in surface water properties, affecting marine plankton communities that are deposited in the sediment. Using planktic foraminifera as a sensitive and well-preserved plankton group, we first characterize the response of their species distribution on environmental gradients from a dataset of surface sediment samples in the tropical and sub-tropical Indian Ocean. Transfer functions for quantitative paleoenvironmental reconstructions were applied to a decadal-scale record of assemblage counts from the Pakistan Margin spanning the last 2000?years. The reconstructed temperature record reveals an intensification of winter monsoon intensity near the year 100 CE. Prior to this transition, winter temperatures were >1.5°C warmer than today. Conditions similar to the present seem to have established after 450 CE, interrupted by a singular event near 950 CE with warmer temperatures and accordingly weak winter monsoon. Frequency analysis revealed significant 75-, 40-, and 37-year cycles, which are known from decadal- to centennial-scale resolution records of Indian summer monsoon variability and interpreted as solar irradiance forcing. Our first independent record of Indian winter monsoon activity confirms that winter and summer monsoons were modulated on the same frequency bands and thus indicates that both monsoon systems are likely controlled by the same driving force.

Noble metal abundances in ODP Leg 115 basalts (Table 1)

A comparison of 50 basalts recovered at Sites 706, 707, 713, and 715 along the Reunion hotspot trace during Ocean Drilling Program Leg 115 in the Indian Ocean shows that seafloor alteration had little effect on noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir), determined by inductively coupled plasma-mass spectrometry (ICP-MS), which generally tend to decrease with magma evolution. Their compatible-element behavior may be related to the precipitation of Ir-Os-based alloys, chromite, sulfides, and/or olivine and clinopyroxene in some combination. The simplest explanation indicates silicate control of concentrations during differentiation. Basalts from the different sites show varying degrees of alkalinity. Noble metal abundances tend to increase with decreasing basalt alkalinity (i.e., with increasing percentages of mantle melting), indicating that the metals behave as compatible elements during mantle melting. The retention of low-melting-point Au, Pd, and Rh in mantle sulfides, which mostly dissolve before significant proportions of Ir-Os-based alloys melt, explains increasing Pd/Ir ratios with decreasing alkalinity (increasing melting percentages) in oceanic basalts. High noble metal concentrations in Indian Ocean basalts (weighted averages of Au, Pd, Rh, Pt, Ru, and Ir in Leg 115 basalts are 3.2, 8.1, 0.31, 7.3, 0.22, and 0.11 ppb, respectively), compared with basalts from some other ocean basins, may reflect fundamental primary variations in upper- mantle noble metal abundances