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.

Geochemistry of planktonic foraminifera from DSDP sites in the Atlantic and Pacific Ocean

The lithium content of planktonic foraminiferal calcite has been determined to evaluate temporal variability of seawater Li concentrations over the past 116 m.y. Mean foraminiferal calcite lithium/calcium in each time interval is no more than 16% greater nor 25% less than the mean Li/Ca of all samples. Li/Ca minima are observed for samples from 50-60 m.y. and 80-90 m.y., with Li/Ca about 25% lower than in adjacent time intervals. At no time during the past 40 m.y does mean Li/Ca appear to be higher than that at present. Subject to the limitations imposed by sample coverage and diagenesis, a similar conclusion holds for the past 116 m.y. Coupled with an oceanic mass balance model for Li, these data suggest that: (1) oceanic Li concentrations and, therefore, high-temperature hydrothermal circulation fluxes during the past 40 m.y. (and perhaps the past 100 m.y.) have not been more than perhaps 30-40% greater than at present for intervals any longer than a million years at most, and (2) these fluxes were not a factor of two higher 100 m.y. ago. By inference, variations in oceanic crustal generation rates over these time periods are similarly limited. Decreases in hydrothermal circulation fluxes and crustal generation rates or fluctuations up to 20% in these rates of a few million years duration are not necessarily ruled out by the Li/Ca data. The lack of variability in Li/Ca over time is not unequivocal evidence that hydrothermal fluxes have not varied because the rates of removal processes may be linked to changes in input fluxes.

Geochemistry of Eocene sediments from ODP Site 171-1052 on the Black Nose, Atlantic Ocean

We use an X-ray fluorescence (XRF) Core Scanner to obtain records of elemental concentrations in sediment cores from Ocean Drilling Program (ODP) Leg 171B, Site 1052 (Blake Nose, Atlantic margin of northern Florida).This record spans the Middle to Late Eocene, as indicated by bio- and magnetostratigraphy, and displays cyclicity that can be attributed to the orbital forcing of a combination of climate, ocean circulation, or productivity. We use the XRF counts of iron and calcium as a proxy of the relative contribution from calcium carbonate and terrestrial material to construct a new composite depth record. This new composite depth record provides the basis to extend the astronomically calibrated geological time scale into the Middle Eocene and results in revised estimates for the age and duration of magnetochrons C16 through C18. In addition, we find an apparent change in the dominance of orbitally driven changes in obliquity and climatic precession at around 36.7 Ma on our new time scale. Long term amplitude modulation patterns of eccentricity and obliquity in the data do not seem to match the current astronomical model any more, suggesting the possibility of new constraints on astronomical calculations.

Major and trace element abundances of igneous rocks from DSDP Site 37-334

REE abundances in gabbros and peridotites from Site 334 of DSDP Leg 37 show that these rocks are cumulates produced by fractional crystallization of a primitive oceanic tholeiite magma. They may be part of a layered oceanic complex. The REE distributions in the residual liquids left after such a fractionation are similar to those of incompatible element-depleted oceanic tholeiites. The REE data indicate that the basalts which overlie the gabbro-peridotite complex, are not genetically related to plutonic rocks.

Element concentrations, and Sr and Os isotope ratios of DSDP Leg 92 metalliferous carbonates

The Os concentration and isotopic composition of metalliferous carbonates deposited on the East Pacific Rise over the past 28 Ma are reported with complimentary Sr isotope data. Variations in the Os isotopic composition of these samples are interpreted as a record of past changes in the Os isotopic composition of seawater. These results are consistent with isotopic analyses of leachable Os in pelagic clays which have also been interpreted as a record of the 187Os/186Os ratio of seawater through time (Pegram et al., 1992, doi:10.1016/0012-821X(92)90132-F). The metalliferous carbonate record clearly shows that seawater Os and Sr isotope systems are partially decoupled from one another over the past 28 Ma. Accelerated weathering of ancient organic-rich sediments is suggested as a possible mechanism to account for this decoupling and the rapid increase in the 187Os//186Os ratio of seawater over the past 15 Ma. This rapid increase suggests that the seawater Os record can potentially be used as a stratigraphic tool in some Neogene marine deposits.