Ba/Ca ratios in Neogloboquadrina pachyderma of sedimet core 94B17

Down-core samples of the planktonic foraminifer Neogloboquadrina pachyderma sinistral from the Mendeleyev Ridge in the western Arctic Ocean have been analyzed for Ba/Ca and d18O. The apparent distribution coefficient for N. pachyderma sin. is estimated at DBa = 0.22 ± 0.02. A meltwater event is identified at around 11.8 14C kyr BP and is coincident with elevated Ba/Ca ratios. The barium enrichment is believed to be the result of enhanced weathering and erosion following glaciation. Additionally, barium may have desorbed from shelf sediments as sea level rose. Changes in Ba/Ca correlate with the retreat of the Laurentide Ice Sheet and the evolution of the Mackenzie River drainage basin. Therefore maximum Ba/Ca in Arctic surface waters at 11.8 ka may be indicative of an increase in the export of freshwater from the Arctic to the North Atlantic, potentially contributing to the onset of the Younger Dryas. This work suggests that Ba/Ca in planktonic foraminifera may be a useful indicator of the timing and processes associated with deglaciation.

Separating ITCZ- and ENSO-related rainfall changes in the Galápagos over the last 3 kyr using D/H ratios of multiple lipid biomarkers

We present a 3000-yr rainfall reconstruction from the Galápagos Islands that is based on paired biomarker records from the sediment of El Junco Lake. Located in the eastern equatorial Pacific, the climate of the Galápagos Islands is governed by movements of the Intertropical Convergence Zone (ITCZ) and the El Niño-Southern Oscillation (ENSO). We use a novel method for reconstructing past ENSO- and ITCZ-related rainfall changes through analysis of molecular and isotopic biomarker records representing several types of plants and algae that grow under differing climatic conditions. We propose that ?D values of dinosterol, a sterol produced by dinoflagellates, record changes in mean rainfall in El Junco Lake, while dD values of C34 botryococcene, a hydrocarbon unique to the green alga Botryococcus braunii, record changes in rainfall associated with moderate-to-strong El Niño events. We use these proxies to infer changes in mean rainfall and El Niño-related rainfall over the past 3000 yr. During periods in which the inferred change in El Niño-related rainfall opposed the change in mean rainfall, we infer changes in the amount of ITCZ-related rainfall. Simulations with an idealized isotope hydrology model of El Junco Lake help illustrate the interpretation of these proxy reconstructions. Opposing changes in El Niño- and ITCZ-related rainfall appear to account for several of the largest inferred hydrologic changes in El Junco Lake. We propose that these reconstructions can be used to infer changes in frequency and/or intensity of El Niño events and changes in the position of the ITCZ in the eastern equatorial Pacific over the past 3000 yr. Comparison with El Junco Lake sediment grain size records indicates general agreement of inferred rainfall changes over the late Holocene.

Age model and Plio-Pleistocene benthic stable oxygen isotope ratios of ODP Site 184-1143 in the Sourh China Sea

Based on benthic foraminiferal delta18O from ODP Site 1143, a 5-Myr astronomical timescale for the West Pacific Plio-Pleistocene was established using an automatic orbital tuning method. The tuned Brunhes/Matuyama paleomagnetic polarity reversal age agrees well with the previously published age of 0.78 Ma. The tuned ages for several planktonic foraminifer bio-events also agree well with published dates, and new ages for some other bio-events in the South China Sea were also estimated. The benthic delta18O from Site 1143 is highly coherent with the Earth's orbit (ETP) both at the obliquity and precession bands for the last 5 Myr, and at the eccentricity band for the last 2 Myr. In general, the 41-kyr cycle was dominant through the Plio-Pleistocene although the 23-kyr cycle was also very strong. The 100-kyr cycle became dominant only during the last 1 Myr. A comparison of the benthic delta18O between the Atlantic (ODP 659) and the East and West Pacific (846 and 1143) reveals that the Atlantic-Pacific benthic oxygen isotope difference ratio (Delta delta18OAtl-Pac) displays an increasing trend in three time intervals: 3.6-2.7 Ma, 2.7-2.1 Ma and 1.5-0.25 Ma. Each of the intervals begins with a rapid negative shift in Delta delta18OAtl-Pac, followed by a long period with an increasing trend, corresponding to the growth of the Northern Hemisphere ice sheet. This means that all three intervals of ice sheet growth in the Northern Hemisphere were accompanied at the beginning by a rapid relative warming of deep water in the Atlantic as compared to that of the Pacific, followed by its gradual relative cooling. This general trend, superimposed on the frequent fluctuations with glacial cycles, should yield insights into the processes leading to the boreal glaciation. Cross-spectral analyses of the Delta delta18OAtl-Pac with the Earth's orbit suggests that after the initiation of Northern Hemisphere glaciation at about 2.5 Ma, obliquity rather than precession had become the dominant force controlling the vertical structure or thermohaline circulation in the paleo-ocean.

Planktic foraminiferal abundance and stable oxygen isotope ratios of sediment cores from the Southern California Borderlands

A variety of evidence suggests that average sea surface temperatures (SSTs) during the last glacial maximum in the California Borderlands region were significantly colder than during the Holocene. Planktonic foraminiferal delta18O evidence and average SST estimates derived by the modern analog technique indicate that temperatures were 6°-10°C cooler during the last glacial relative to the present. The glacial plankton assemblage is dominated by the planktonic foraminifer Neogloboquadrina pachyderma (sinistral coiling) and the coccolith Coccolithus pelagicus, both of which are currently restricted to subpolar regions of the North Pacific. The glacial-interglacial average SST change determined in this study is considerably larger than the 2°C change estimated by Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) [1981]. We propose that a strengthened California Current flow was associated with the advance of subpolar surface waters into the Borderlands region during the last glacial.

Mg/Ca ratios in planktonic foraminifera

The primary Mg/Ca ratio of foraminiferal shells is a potentially valuable paleoproxy for sea surface temperature (SST) reconstructions. However, the reliable extraction of this ratio from sedimentary calcite assumes that we can overcome artifacts related to foraminiferal ecology and partial dissolution, as well as contamination by secondary calcite and clay. The standard batch method for Mg/Ca analysis involves cracking, sonicating, and rinsing the tests to remove clay, followed by chemical cleaning, and finally acid-digestion and single-point measurement. This laborious procedure often results in substantial loss of sample (typically 30-60%). We find that even the earliest steps of this procedure can fractionate Mg from Ca, thus biasing the result toward a more variable and often anomalously low Mg/Ca ratio. Moreover, the more rigorous the cleaning, the more calcite is lost, and the more likely it becomes that any residual clay that has not been removed by physical cleaning will increase the ratio. These potentially significant sources of error can be overcome with a flow-through (FT) sequential leaching method that makes time- and labor-intensive pretreatments unnecessary. When combined with time-resolved analysis (FT-TRA) flow-through, performed with a gradually increasing and highly regulated acid strength, produces continuous records of Mg, Sr, Al, and Ca concentrations in the leachate sorted by dissolution susceptibility of the reacting material. Flow-through separates secondary calcite from less susceptible biogenic calcite and clay, and further resolves the biogenic component into primary and more resistant fractions. FT-TRA reliably separates secondary calcite (which is not representative of original life habitats) from the more resistant biogenic calcite (the desired signal) and clay (a contaminant of high Mg/Ca, which also contains Al), and further resolves the biogenic component into primary and more resistant fractions that may reflect habitat or other changes during ontogeny. We find that the most susceptible fraction of biogenic calcite in surface dwelling foraminifera gives the most accurate value for SST and therefore best represents primary calcite. Sequential dissolution curves can be used to correct the primary Mg/Ca ratio for clay, if necessary. However, the temporal separation of calcite from clay in FT-TRA is so complete that this correction is typically <=2%, even in clay-rich sediments. Unlike hands-on batch methods, that are difficult to reproduce exactly, flow-through lends itself to automation, providing precise replication of treatment for every sample. Our automated flow-through system can process 22 samples, two system blanks, and 48 mixed standards in <12 hours of unattended operation. FT-TRA thus represents a faster, cheaper, and better way to determine Mg/Ca ratios in foraminiferal calcite.

Stable oxygen isotope ratios in zircons from oceanic crust

Lower ocean crust is primarily gabbroic, although 1-2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater-rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform d18O with an average value of 5.2 ± 0.5 per mil (2SD). The average d18O(Zrc) would be in magmatic equilibrium with unaltered MORB [d18O(WR) ~5.6-5.7 per mil], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured d18O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like d18O(Zrc) requires melting and zircon crystallization prior to significant amounts of water-rock interactions that alter the protolith d18O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal environments. Many of the >3.9 Ga zircons have mildly elevated d18O (6.0-7.5 per mil), but such values have not been identified in any zircons from the large sample suite examined here. The difference in d18O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.

Hydrogen, carbon, and oxygen isotope ratios of interstitial fluides of ODP Leg 104 holes

Carbon, hydrogen, and oxygen isotope ratios determined on 32 squeezed interstitial fluid samples show remarkable variations with depth. For the most part these variations are related to diagenetic and alteration reactions taking place in the sediments, and in the underlying basalts. delta13C SumCO2 depth distributions at Sites 642 and 643 are the result of mixing of original SumCO2 of the paleo bottom water with SumCO2 released by remineralization of organic matter. At Site 644, where sulfate exhaustion occurs, the processes of methanogenesis by CO2 reduction and anaerobic methanotrophy strongly influence the delta13C SumCO2 distribution. Hydrogen and oxygen isotopes roughly covary, and become enriched in 16O and1H with depth. This effect is most pronounced at Sites 642 and 643, possibly due to the influence of the directly underlying basalts. Isotope depletions at Site 644 are much lower, corresponding to the greater sediment depth to basement. The alternative, that the O, H isotope shifts are due primarily to autochthonous diagenetic and exchange reactions, is not supported by the data available.

Stable isotope ratios measured on carbonate tests from the Kara Sea

River discharge of Ob and Yenisei to the Kara Sea is highly variable on seasonal and interannual time scales. River water dominates the shallow bottom water near the river mouths, making it warmer and less saline but seasonally and interannually more changeable than bottom water on the deeper shelf. This hydrographic pattern shows up in measurements and modelling, and in stable isotope records (delta18O, delta13C) along the growth axis of bivalve shells and in multiple analyses of single benthic foraminiferal shells. Average isotope ratios increase, but sample-internal variability decreases with water depth and distance from river mouths. However, isotope records of bivalves and foraminifera of a sediment core from a former submarine channel of Yenisei River reveal a different pattern. The retreat of the river mouth from this site due to early Holocene sea level rise led to increasing average isotope values up core, but not to the expected decrease of the in-sample isotope variability. Southward advection of cold saline water along the palaeo-river channel probably obscured the hydrographic variability during the early Holocene. Later, when sediment filled the channel, the hydrographic variability at the core location remained low, because the shallowing proceeded synchronously with the retreat of the river mouth.

Strontium isotopic ratios in selected microfossils from ODP Holes 119-738C and 120-747A

The Maastrichtian and Danian intervals of Ocean Drilling Program (ODP) Hole 738C contain numerous microfossils above the level of their putative extinction, suggesting either (1) persistence of local communities long after species turnover occurred across the rest of the globe or (2) large-scale reworking. These interpretations have very different paleoenvironmental implications, but discriminating between them has proved difficult. To test the competing hypotheses, we measured the 87Sr/86Sr ratios of taxon-specific separates from a number of samples and compared these values both to each other and to expected seawater values at the time of deposition. Our results indicate extensive and pervasive reworking throughout Maastrichtian and lower Danian strata in ODP Hole 738C. We estimate that up to 30% of the mass of foraminifers in any sample can be contributed by individuals that have been reworked.

Stable carbon and oxygen isotope ratios across the Cretaceous/Tertiary boundray on the Walvish Ridge

The isotopic composition and diversity of nannofossils were studied in cores from the Deep Sea Drilling Project (DSDP) Sites 525A, 527, 528, and 529 from the Walvis Ridge, South Atlantic to better understand the changes which occurred across the Cretaceous/Tertiary boundary (K/T boundary). The stratigraphic range of the samples is from the Arkhangelskiella cymbiformis Zone in the Maastrichtian to the Heliolithus kleinpelli Zone in the Danian. Nannofossil diversity was high (Shannon-Weaver diversity index, 'H= 2.5-3) in the late Cretaceous, but decreased sharply (H c. 1 ) across the K/T boundary. The delta13C values also decrease across the K/T boundary at the four sites, suggesting a reduction in surface productivity in the South Atlantic concomitant with the reduction in diversity. During the Danian, nannofossil diversity and delta13C show some recovery approximately 500-700 k.y. after the boundary event. However, not until 2.5 Ma after the boundary event did diversity become constant. Diversity values similar to those for the late Cretaceous were not attained again in the early Paleocene interval studied. Carbon isotopic compositions similar to those from the Cretaceous were not attained until 4.5 Ma after the K/T event.