Nd, Sr and Pb isotopic composition of eolian dust deposited in the central North Pacific

The silicate fractions of recent pelagic sediments in the central north Pacific Ocean are dominated by eolian dust derived from central Asia. An 11 Myr sedimentary record at ODP Sites 885/886 at 44.7°N, 168.3°W allows the evaluation of how such dust and its sources have changed in response to late Cenozoic climate and tectonics. The extracted eolian fraction contains variable amounts (>70%) of clay minerals with subordinate quartz and plagioclase. Uniform Nd isotopic compositions (epsilon-Nd =38.6 to 310.5) and Sm/Nd ratios (0.170-0.192) for most of the 11 Myr record demonstrate a well-mixed provenance in the basins north of the Tibetan Plateau and the Gobi Desert that was a source of dust long before the oldest preserved Asian loess formed. epsilon-Nd values of up to 36.5 for samples 62.9 Ma indicate <=35 wt% admixture of a young, Kamchatka-like volcanic arc component. The coherence of Pb and Nd in the erosional cycle allows us to constrain the Pb isotopic composition of Asian loess devoid of anthropogenic contamination to 206Pb/204Pb =18.97 +/- 0.06, 207Pb/204Pb =15.67 +/- 0.02, 208Pb/204Pb =39.19 +/- 0.11. 87Sr/86Sr (0.711-0.721) and Rb/Sr ratios (0.39-1.1) vary with dust mineralogy and provide an age indication of ~250 Ma. 40Ar/39Ar ages of six dust samples are uniform around 200 Ma and match the K-Ar ages of modern dust deposited on Hawaii. These data reflect the weighted age average of illite formation. Changes from illite- smectite with significant kaolinite to illite- and chlorite-rich, kaolinite-free assemblages since the late Pliocene document changes in the intensity of chemical weathering in the source region. Such weathering evidently did not disturb the K-Ar systematics, and only induced scatter in the Rb-Sr data. We propose that when smectite forms at the expense of illite, K and Ar are quantitatively lost from what becomes smectite, but are quantitatively retained in adjacent illite layers. 40Ar/39Ar age data, therefore, are insensitive to smectite formation during chemical weathering but date the diagenetic growth of illite, the major K-bearing phase in the dust. Over the past 12 Myr, the dust flux to the north Pacific increased by more than an order of magnitude, documenting a substantial drying of central Asia. This climatic change, however, did not alter the ultimate source of the dust, and neoformational products of chemical weathering always remained subordinate to assemblages reworked by mechanical erosion in dust deposited in eastern Asia and the Pacific Ocean.

A multi-proxy investigation of sediment core GeoB7165-1 and AMS 14C dating points from sediment cores off Conceptión (~ 36°S)

A high-resolution sea surface temperature and paleoproductivity reconstruction on a sedimentary record collected at 36°S off central-south Chile (GeoB 7165-1, 36°33'S, 73°40'W, 797 m water depth, core length 750 cm) indicates that paleoceanographic conditions changed abruptly between 18 and 17 ka. Comparative analysis of several cores along the Chilean continental margin (30°-41°S) suggests that the onset and the pattern of deglacial warming was not uniform off central-south Chile due to the progressive southward migration of the Southern Westerlies and local variations in upwelling. Marine productivity augmented rather abruptly at 13-14 ka, well after the oceanographic changes.We suggest that the late deglacial increase in paleoproductivity off central-south Chile reflects the onset of an active upwelling system bringing nutrient-rich, oxygen-poor Equatorial SubsurfaceWater to the euphotic zone, and a relatively higher nutrient load of the Antarctic Circumpolar Current. During the Last Glacial Maximum, when the Southern Westerlies were located further north, productivity off central-south Chile, in contrast to off northern Chile, was reduced due to direct onshore-blowing winds that prevented coastal upwelling and export production.

Paleoclimate reconstructions from sediment core MD01-2378

On the basis of the radiocarbon (14C) plateau-tuning method a new age model for Timor Sea Core MD01-2378 was established. It revealed a precise centennial-scale phasing of climate events in the ocean, cryo-, and atmosphere during the last deglacial and provides important new insights into causal linkages controlling events of global climate change. At Site MD01-2378 reservoir ages of surface waters dropped from 1600 yr prior to 20 cal ka to 250-500 yr after 18.8 cal ka. This evidence was crucial for generating a high-resolution age model for deglacial events in the Indo-Pacific Warm Pool. Sea-surface temperatures (SST) started to change near 18.8 cal ka, that is ~500 yr after the start of, presumably northern hemispheric, deglacial melt and sea level rise as shown by the benthic foraminiferal oxygen isotope ratio (d18O). However, the SST rise occurred 500-1000 yr prior to the onset of deglacial Antarctic warming and the first major rise in atmospheric carbon dioxide at about 18 ka. The increase in SST may partly reflect reduced seasonal upwelling of cold subsurface waters along the eastern margin of the Indian Ocean, which is reflected by a doubling of the thermal gradient between the sea surface and the thermocline, a halving of chlorin productivity from 19 to 18.5 cal ka, and in particular, by the strong decrease in surface water reservoir ages. Two significant increases in deglacial Timor Sea surface salinities from 19-18.5 and 15.5-14.5 cal ka, may partly reflect the deglacial increase in the distance of local river mouths, partly an inter-hemispheric millennial-scale see-saw in tropical monsoon intensity, possibly linked to a deglacial increase in the dominance of Pacific El Niño regimes over Heinrich stadial 1.

Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Stable isotope ratios of foraminifera from sediment cores off northeastern Brazil

The western South Atlantic boundary currents represent a sensitive system within the global thermohaline circulation (THC). We investigated the impact of deglacial THC changes on the western tropical Atlantic studied in six high resolution sediment cores from the upper continental slope of Brazil. The stratigraphy of the cores is mainly based on 14C AMS dating of monospecific foraminiferal samples. Changes in the upper layer tropical ocean during the deglaciation are inferred from stable oxygen isotope measurements on planktic and benthic foraminifera. Variations in the delta18O residuals are assumed to be mainly temperature related. During the Oldest and Younger Dryas cooling periods, two major deglacial THC disturbances are reported from North Atlantic sediment cores. Concomitant to the repeated THC slowdown, we observe an upper layer warming in the tropical ocean. A reduced northward heat export from the tropical areas during these periods (weak North Brazil Current) is additionally reflected by low meridional gradients in the stable oxygen records. This generally agrees with results from coupled ocean atmosphere models.

Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

Reconstruction of the provenance and distribution of terrigenous sediments off NE South America over the last 30ka

We investigate the redistribution of terrigenous materials in the northeastern (NE) South American continental margin during slowdown events of the Atlantic Meridional Overturning Circulation (AMOC). The compilation of stratigraphic data from 108 marine sediment cores collected across the western tropical Atlantic shows an extreme rise in sedimentation rates off the Parnaíba River mouth (about 2°S) during Heinrich Stadial 1 (HS1, 18-15 ka). Sediment core GeoB16206-1, raised offshore the Parnaíba River mouth, documents relatively constant 143Nd/144Nd values (expressed as epsilonNd(0)) throughout the last 30 ka. Whereas the homogeneous epsilonNd(0) data support the input of fluvial sediments by the Parnaíba River from the same source area directly onshore, the increases in Fe/Ca, Al/Si and Rb/Sr during HS1 indicate a marked intensification of fluvial erosion in the Parnaíba River drainage basin. In contrast, the epsilonNd(0) values from sediment core GeoB16224-1 collected off French Guiana (about 7°N) suggest Amazon-sourced materials within the last 30 ka. We attribute the extremely high volume of terrigenous sediments deposited offshore the Parnaíba River mouth during HS1 to (i) an enhanced precipitation in the catchment region and (ii) a reduced North Brazil Current, which are both associated with a weakened AMOC.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

(Table 1) n-alkane distribution, and stable carbon and deuterium isotope ratios of DSDP Hole 10-94

Hydrology, source region, and timing of precipitation are important controls on the climate of the Great Plains of North America and the composition of terrestrial ecosystems. Moisture delivered to the Great Plains varies seasonally and predominately derives from the Gulf of Mexico/Atlantic Ocean with minor contributions from the Pacific Ocean and Arctic region. For this work, we evaluate long-term relationships for the past ~ 35 million years between North American hydrology, climate, and floral change, using isotopic records and average carbon chain lengths of higher plant n-alkanes from Gulf of Mexico sediments (DSDP Site 94). We find that carbon isotope values (d13C) of n-alkanes, corrected for variations in the d13C value of atmospheric CO2, provide minor evidence for contributions of C4 plants prior to the Middle Miocene. A sharp spike in C4 input is identified during the Middle Miocene Climatic Optimum, and the influence of C4 plants steadily increased during the Late Miocene into the Pleistocene - consistent with other North American records. Chain-length distributions of n-alkanes, indicative of the composition of higher plant communities, remained remarkably constant from 33 to 4 Ma. However, a trend toward longer chain lengths occurred during the past 4 million years, concurrent with an increase in d13C values, indicating increased C4 plant influence and potentially aridity. The hydrogen isotope values (dD) of n-alkanes are relatively invariant between 33 and 9 Ma, and then become substantially more negative (75 per mil) from 9 to 2 Ma. Changes in the plant community and temperature of precipitation can solely account for the observed variations in dD from 33 to 5 Ma, but cannot account for Plio-Pleistocene dD variations and imply substantial changes in the source region of precipitation and seasonality of moisture delivery. We posit that hydrological changes were linked to tectonic and oceanographic processes including the shoaling and closure of the Panamanian Seaway, amplification of North Atlantic Deep Water Production and an associated increase of meridional winds. The southerly movement of the Intertropical Convergence Zone near 4 Ma allowed for the development of a near-modern pressure/storm track system, driving increased aridity and changes in seasonality within the North American interior.