Stable carbon isotope record and geochemistry of late Miocene-early Pliocene sediments from DSDP Site 90-590 in the Tasman Sea

Biogenic components of sediment accumulated at high rates beneath frontal zones of the Indian and Pacific oceans during the late Miocene and early Pliocene. The delta13C of bulk and foraminiferal carbonate also decreased during this time interval. Although the two observations may be causally linked, and signify a major perturbation in global biogeochemical cycling, no site beneath a frontal zone has independent records of export production and delta13C on multiple carbonate phases across the critical interval of interest. Deep Sea Drilling Project (DSDP) site 590 lies beneath the Tasman Front (TF), an eddy-generating jetstream in the southwest Pacific Ocean. To complement previous delta13C records of planktic and benthic foraminifera at this location, late Neogene records of CaCO3 mass accumulation rate (MAR), Ca/Ti, Ba/Ti, Al/Ti, and of bulk carbonate and foraminiferal delta13C were constructed at site 590. The delta13C records include bulk sediment, bulk sediment fractions (<63 µm and 5-25 µm), and the planktic foraminifera Globigerina bulloides, Globigerinoides sacculifer (with and without sac), and Orbulina universa. Using current time scales, CaCO3 MARs, Ca/Ti, Al/Ti and Ba/Ti ratios are two to three times higher in upper Miocene and lower Pliocene sediment relative to overlying and underlying units. A significant decrease also occurs in all delta13C records. All evidence indicates that enhanced export production - the 'biogenic bloom' - extended to the southwest Pacific Ocean between ca. 9 and 3.8 Ma, and this phenomenon is coupled with changes in delta13C - the 'Chron C3AR carbon shift'. However, CaCO3 MARs peak ca. 5 Ma whereas elemental ratios are highest ca. 6.5 Ma; foraminiferal delta13C starts to decrease ca. 8 Ma whereas bulk carbonate delta13C begins to drop ca. 5.6 Ma. Temporal discrepancies between the records can be explained by changes in the upwelling regime at the TF, perhaps signifying a link between changes in ocean-atmosphere circulation change and widespread primary productivity.

Stable isotope record and composition of planktonic foraminifera from ODP Site 172-1056

The stable isotopic composition of two planktonic foraminifer species (Globigerinoides sacculifer and Neogloboquadrina dutertrei) and two benthic foraminifer species (Cibicidoides wuellerstorfi and Uvigerina peregrina) was measured at sub-orbital resolution through the marine isotope stages (MISs) 10, 11, and 12 (345-460 ka) at Site 1056 on the Blake-Bahama Outer Ridge. Planktonic foraminifers were counted for the interval 405-450 ka at 2-4-kyr resolution. Site 1056 (32°29'N, 76°20'W) is located on the continental slope (water depth: 2167 m) beneath the Gulf Stream. The average rate of sediment accumulation through the interval is 11.4 cm/kyr, but sediment accumulation is much more rapid during glacial intervals (15-17 cm/kyr). The decline in percent carbonate during glacial intervals, and its rise during interglacials, indicates that the increased sediment supply is of terrigenous origin. Low carbonate values and low benthic delta13C, which are both associated with a weak Western Boundary Undercurrent and low North Atlantic Deep Water production, persist for 6 kyr after the benthic delta18O record indicates that ice volume has begun to decrease. Recovery of carbonate and benthic delta13C values is abrupt and rapid. Millennial-scale variation (~3-4 kyr) is apparent in the glacial intervals of the planktonic delta18O records and is more pronounced in a Delta delta18O record, which represents the temperature range in the photic zone. Semi-precessional (10-12-kyr) cycles are apparent in the planktonic deltadelta13C record. The millennial-scale cycles are largely caused by an increase in G. sacculifer delta18O and represent surface warming. They are interpreted as representing periodic increases in westward intensification of the gyre. The semi-precessional cycles are driven by changes in the N. dutertrei delta13C and represent fluctuations in the Gulf Stream itself and therefore likely have a tropical origin. Planktonic foraminifer census counts did not show an expected response to one of the largest glacial/interglacial transitions of the late Pleistocene. The most obvious change was an increase in faunal diversity during MIS 12.2, the interval of maximum delta18O values. This suggests that cool slope water and warm subtropical gyre water penetrated a more sluggish Gulf Stream with greater frequency at this time. The millennial-scale maxima in the Delta delta18O record are accompanied by decreases in diversity, which is consistent with the interpretation of surface warming during these events.

Stable carbon and oxygen isotope ratios of foraminifera from North Atlantic sediments

Oxygen-18 records of benthic foraminifera from the Atlantic Ocean are significantly different from those of the Pacific and Indian Oceans indicating that the Glacial North Atlantic Deep Water was about 1.3°C cooler than today because different deep water sources appeared in the North Atlantic Ocean during glacial times. The present study seeks to interprete carbon-13 records of planktonic and benthic foraminifera as a tracer of the cycle of the CO2 dissolved in surface and deep water of the ocean during the last climatic cycle. Carbon-13 records of planktonic foraminifera indicate that the delta13C of atmospheric CO2 and total CO2 dissolved in surface water did not vary noticeably (-0.2 +/- 0.3 per mil) during glacial times. Carbon-13 records of benthic foraminifera indicate that the eastern North Atlantic Ocean was an area of deep water formation dying isotopic stage 2, but not during most of stage 3. Moreover, large delta13C differences in the NADW between 20°N and 50°N show that the residence time of the glacial NADW was about 4 times that of today.

Stable carbon and oxygen isotope ratios of bulk sediment from DSDP Hole 62-463 (Appendix A)

In order to elucidate early Aptian marine paleotemperature evolution across the period of enhanced organic carbon (Corg)-burial [Oceanic Anoxic Event (OAE) 1a], stable isotope analyses were performed on pelagic limestones at Deep Sea Drilling Project Site 463, central Pacific Ocean. The delta18O data exhibit a distinct anomaly by ~-2? spanning the OAE 1a interval (i.e., a ~6 m-thick, phytoplanktonic Corg-rich unit constrained by magneto-, bio- and delta13C stratigraphy). Elucidation of paleotemperature significance of the delta18O shift is made by taking account of recent Sr/Ca evidence at the same section, which revealed that geochemical signals in carbonate-poor lithologies are relatively unaltered against burial diagenesis. By discriminating delta18O values from carbonate-poor samples (CaCO3 contents=5-30 wt.%), it appears that an abrupt rise in seasurface temperatures (SSTs) by 8 °C (=-1.7? shift in delta18O) occurred immediately before OAE 1a, whereas a cooling mode likely prevailed during the peak Corg-burial. In terms of its stratigraphic relationship as to the Corg-rich interval and to a pronounced negative delta13C excursion, as well as its timescale, the observed SST rise resembles those associated with the Paleocene-Eocene thermal maximum and, more strikingly, Jurassic Toarcian OAE. This observation is consistent with the hypothesis that these paleoenvironmental events were driven by a common causal mechanism, which was likely initiated by the greenhouse effect via massive release of CH4 or CO2 from the isotopically-light carbon reservoir and terminated by a negative productivity feedback.

Oxygen and carbon isotope ratios for six planktonic foraminifer species from different water depth, Ontong-Java Plateau, Pacific (Table 2)

Stable isotope analyses and scanning electron micrographs have been carried out on six planktonic forminifera species, Pulleniatina obliquiloculata, Globorotalia tumida, Sphaeroidinella dehiscens, Globigerinoides ruber, Globigerinoides sacculifer and Globigerinoides quadrilobatus from eleven box-cores taken at increasing depths in the equatorial Ontong-Java Plateau (Pacific). This allows us to describe the way dissolution affects the microstructures of the tests of the different species and to quantify the changes of isotopic composition. We may conclude that: 1) dissolution effects on test morphology and stable isotope compositions are species dependent, species with a similar habitat showing a similar trend; 2) the shallow water, thin-shelled species are the first to disappear: scanning electron microscope (SEM) work shows alteration of outer layers. Deep water, thick-shelled species are present in all samples: SEM work shows breakdown and disparition of inner layers; 3) for all species there is a similar trend towards increasing delta18O values with increasing water depths and increasing dissolution. This effect may be as high as 0.6 ? per thousand meters for Globorotalia tumida; 4) below the lysocline, around 3500 m, it appears that 13C/12C ratios slightly increase towards equilibrium values for thick shelled species: G. tumida, P. obliquiloculata and S. dehiscens. 14C dates and isotope stratigraphy of two box-cores show that all samples are recent in age, and exclude upward mixing of glacial deposits as an important factor.

Geographic provenancing of unprocessed cotton using elemental analysis and stable isotope ratios

Cotton is the most abundant natural fiber in the world. Many countries are involved in the growing, importation, exportation and production of this commodity. Paper documentation claiming geographic origin is the current method employed at U.S. ports for identifying cotton sources and enforcing tariffs. Because customs documentation can be easily falsified, it is necessary to develop a robust method for authenticating or refuting the source of the cotton commodities. This work presents, for the first time, a comprehensive approach to the chemical characterization of unprocessed cotton in order to provide an independent tool to establish geographic origin. Elemental and stable isotope ratio analysis of unprocessed cotton provides a means to increase the ability to distinguish cotton in addition to any physical and morphological examinations that could be, and are currently performed. Elemental analysis has been conducted using LA-ICP-MS, LA-ICP-OES and LIBS in order to offer a direct comparison of the analytical performance of each technique and determine the utility of each technique for this purpose. Multivariate predictive modeling approaches are used to determine the potential of elemental and stable isotopic information to aide in the geographic provenancing of unprocessed cotton of both domestic and foreign origin. These approaches assess the stability of the profiles to temporal and spatial variation to determine the feasibility of this application. This dissertation also evaluates plasma conditions and ablation processes so as to improve the quality of analytical measurements made using atomic emission spectroscopy techniques. These interactions, in LIBS particularly, are assessed to determine any potential simplification of the instrumental design and method development phases. This is accomplished through the analysis of several matrices representing different physical substrates to determine the potential of adopting universal LIBS parameters for 532 nm and 1064 nm LIBS for some important operating parameters. A novel approach to evaluate both ablation processes and plasma conditions using a single measurement was developed and utilized to determine the "useful ablation efficiency" for different materials. The work presented here demonstrates the potential for an a priori prediction of some probable laser parameters important in analytical LIBS measurement.

(Table S1) Calcium isotope ratios of Pacific Ocean sediments

Multiple lines of evidence have shown that the isotopic composition and concentration of calcium in seawater have changed over the past 28 million years. A high-resolution, continuous seawater calcium isotope ratio curve from marine (pelagic) barite reveals distinct features in the evolution of the seawater calcium isotopic ratio suggesting changes in seawater calcium concentrations. The most pronounced increase in the d44/40Ca value of seawater (of 0.3 per mil) occurred over roughly 4 million years following a period of low values around 13 million years ago. The major change in marine calcium corresponds to a climatic transition and global change in the carbon cycle and suggests a reorganization of the global biogeochemical system.

Stable isotope ratios and paleoceanaographic reconstructions from sediment cores 80-548 and 161-978A

Largely continuous millennial-scale records of benthic d18O, Mg/Ca-based temperature, and salinity variations in bottom waters were obtained from Deep Sea Drilling Project Site 548 (eastern Atlantic continental margin south of Ireland, 1250 m water depth) for the period between 3.7 and 3.0 million years ago. This site monitored mid-Pliocene changes in Mediterranean Outflow Water (MOW) documented by continuously high Nd values between -10.7 and -9. Site 978 (Alboran Sea, 1930 m water depth) provides a complementary record of bottom water variability in the westernmost Mediterranean Sea, which is taken to represent MOW composition at its source. Both sites are marked by a singular and persistent rise in bottom water salinities by 0.7-1.4 psu and in densities by ~1 kg m-3 from 3.5 to 3.3 Ma, which is matched by an average 3 °C increase in bottom water temperatures at Site 548. This event suggests the onset of strongly enhanced deep-water convection in the Mediterranean Sea and a related strengthened MOW flow, which implies a major aridification of the Mediterranean source region. In harmony with model suggestions, the enhanced MOW flow has possibly intensified Upper North Atlantic Deep Water formation.

Stable carbon and oxygen isotope ratios of benthic foraminifera

Carbon isotopic measurements on the benthic foraminiferal genus Cibicidoides document that mean deep ocean delta13C values were 0.46 per mil lower during the last glacial maximum than during the Late Holocene. The geographic distribution of delta13C was altered by changes in the production rate of nutrient-depleted deep water in the North Atlantic. During the Late Holocene, North Atlantic Deep Water, with high delta13C values and low nutrient values, can be found throughout the Atlantic Ocean, and its effects can be traced into the southern ocean where it mixes with recirculated Pacific deep water. During the glaciation, decreased production of North Atlantic Deep Water allowed southern ocean deep water to penetrate farther into the North Atlantic and across low-latitude fracture zones into the eastern Atlantic. Mean southern ocean delta13C values during the glaciation are lower than both North Atlantic and Pacific delta13C values, suggesting that production of nutrient-depleted water occurred in both oceans during the glaciation. Enriched 13C values in shallow cores within the Atlantic Ocean indicate the existence of a nutrient-depleted water mass above 2000 m in this ocean.

Isotope and Mg/Ca measurements from Cores ME0005A-43JC and 202-1242 of tropical Pacific

Multiproxy geologic records of d18O and Mg/Ca in fossil foraminifera from sediments under the Eastern Pacific Warm Pool (EPWP) region west of Central America document variations in upper ocean temperature, pycnocline strength, and salinity (i.e., net precipitation) over the past 30 kyr. Although evident in the paleotemperature record, there is no glacial-interglacial difference in paleosalinity, suggesting that tropical hydrologic changes do not respond passively to high-latitude ice sheets and oceans. Millennial variations in paleosalinity with amplitudes as high as 4 practical salinity units occur with a dominant period of 3-5 ky during the glacial/deglacial interval and 1.0-1.5 ky during the Holocene. The amplitude of the EPWP paleosalinity changes greatly exceeds that of published Caribbean and western tropical Pacific paleosalinity records. EPWP paleosalinity changes correspond to millennial-scale climate changes in the surface and deep Atlantic and the high northern latitudes, with generally higher (lower) paleosalinity during cold (warm) events. In addition to Intertropical Convergence Zone (ITCZ) dynamics, which play an important role in tropical hydrologic variability, changes in Atlantic-Pacific moisture transport, which is closely linked to ITCZ dynamics, may also contribute to hydrologic variations in the EPWP. Calculations of interbasin salinity average and interbasin salinity contrast between the EPWP and the Caribbean help differentiate long-term changes in mean ITCZ position and Atlantic-Pacific moisture transport, respectively.

Stable carbon and oxygen isotope ratios of planktonic foraminifera from the equatorial Atlantic

Carbon isotopic records of nutrient-depleted surface water place constraints on the past fertility of the oceans and on past atmospheric pCO2 levels. The best records of nutrient-depleted delta13C are obtained from planktonic foraminifera living in the thick mixed layers of the western equatorial and tropical Atlantic Ocean. We have produced a composite, stacked Globigerinoides sacculifer delta13C record from the equatorial Atlantic, which exhibits significant spectral power at the 100,000- and 41,000-year Milankovitch periods, but no power at the 23,000-year period. Similar to the record presented by Shackleton and Pisias [1985], surface-deep ocean Delta delta13C produced with the G. sacculifer record leads the delta18O ice volume record. However, the glacial-interglacial amplitudes of Delta delta13C differ between our record and Shackleton and Pisias [1985] record. Although large changes in Delta delta13C occur in the equatorial Atlantic during early stages of the last three glacial cycles, surface-deep Delta delta13C at glacial maxima (18O stage 2, late stage 6, and late stage 8) was only about 0.2? greater than during the subsequent interglacial. Our results imply that nutrient-driven pCO2 changes account for about one third of the pCO2 decrease observed in ice cores, and consequently, Delta delta13C should not be used as a proxy pCO2 index. Enough variance in the ice core pCO2 records remains to be explained that conclusions about pCO2 and ice volume phase relationships should also be reexamined. As much as 40 ppm pCO2 change still has not been accounted for by models of past physics and chemistry of the ocean.