Stable foraminifer isotope composition and age of ODP Sites 184-1147 and 184-1148, South China Sea

Sites 1147 (18°50.11'N, 116°33.28'E; water depth = 3246 m) and 1148 (18°50.17'N, 116°33.94'E; water depth = 3294 m) are located on the lowermost continental slope off southern China near the continent/ocean crust boundary of the South China Sea Basin. Site 1147 is located upslope ~0.45 nmi west of Site 1148. Three advanced piston corer holes at Site 1147 and two extended core barrel holes at Site 1148 were cored and combined into a composite (spliced) stratigraphic section, which provided a relatively continuous profile for the lower Oligocene to Holocene (Wang, Prell, Blum, et al., 2000, doi:10.2973/odp.proc.ir.184.2000; Jian, et al., 2001, doi:10.1007/BF02907088) for studying stratigraphy and paleoceanography. A total of 1047 planktonic foraminifers stable isotope measurements were performed on 975 samples covering the upper 409.58 meters composite depth (mcd) at ~42-cm intervals (Tables T1, T2), and a total of 1864 benthic foraminifers measurements were performed on 1650 samples in the upper 837.11 mcd at ~51-cm intervals (Tables T3, T4). We significantly improved the time resolution of the benthic stable isotope record in the upper 476.68 mcd by reducing the average sample spacing to ~29 cm. This translates into an average sampling resolution of ~16 k.y. for the Miocene sequence and ~8 k.y. for the Pliocene-Holocene interval, assuming a change in sedimentation rates from ~1.8 to ~3.5 cm/k.y., as suggested by shipboard stratigraphy. These data sets provide the basis for upcoming studies to establish an oxygen isotope stratigraphy and examine the Neogene evolution of deep and surface water signatures (temperature, salinity, and nutrients) in the South China Sea.

Grain size analyses, Ca/Ti and other selected elemental ratios from XRF core scanning of sediment cores from the Apulian Margin

An extensive, high-resolution, sedimentological-geochemical survey was done using geo-acoustics, XRF-core scans, ICP-AES, AMS 14C-dating and grain size analyses of sediments in 11 cores from the Gulf of Taranto, the southern Adriatic Sea, and the central Ionian Sea spanning the last 16 cal. ka BP. Comparable results were obtained for cores from the Gallipoli Shelf (eastern Gulf of Taranto), and the southern Adriatic Sea suggesting that the dominant provenance of Gallipoli Shelf sediments is from the western Adriatic mud belt. The 210Pb and 14C-dated high-accumulation-rate sediments permit a detailed reconstruction of climate variability over the last 16 cal. ka BP. Although, the Glacial-Interglacial transition is generally dry and stable these conditions are interrupted by two phases of increased detrital input during the Bølling-Allerød and the late Younger Dryas. The event during the Younger Dryas period is characterized by increased sediment inputs from southern Italian sources. This suggests that run-off was higher in southern- compared to northern Italy. At approximately ~ 7 cal. ka BP, increased detrital input from the Adriatic mud belt, related to sea level rise and the onset of deep water formation in the Adriatic Sea, is observed and is coincident with the end of sapropel S1 formation in the southern Adriatic Sea. During the mid-to-late Holocene we observed millennial-scale events of increased detrital input, e.g. during the Roman Humid Period, and of decreased detrital input, e.g., Medieval Warm Period. These dry/wet spells are consistent with variability in the North Atlantic Oscillation (NAO). A negative state of the NAO and thus a more advanced penetration of the westerlies into the central Mediterranean, that result in wet conditions in the research area concord with events of high detrital input e.g., during the Roman Humid Period. In contrast, a positive state of the NAO, resulting in dry conditions in the Mediterranean, dominated during events of rapid climate change such as the Medieval Warm Period and the Bronze Age.

Oxygen isotopes and Sr/Ca ratios of fossil corals from Bonaire

Explanations for the demise of the Classic Maya civilization on the Yucatán Peninsula during the Terminal Classic Period (TCP; CE 750-1050) are controversial. Multiyear droughts are one likely cause, but the role of the Caribbean Sea, the dominant moisture source for Mesoamerica, remains largely unknown. Here we present bimonthly resolved snapshots of reconstructed sea surface temperature (SST) and salinity (SSS) variability in the southern Caribbean from precisely dated fossil corals. Our fossil coral results from Bonaire indicate strong interannual to decadal SST and SSS variability in the southern Caribbean Sea during the TCP with multiyear extremes of high SSS and high SST that coincide with droughts on the Yucatán Peninsula. The results are best explained by changed Caribbean SST gradients affecting the Caribbean low-level atmospheric jet with consequences for Mesoamerican precipitation, possibly linked to changes in Atlantic Meridional Overturning Circulation strength. Our findings provide a new perspective on the anomalous hydrological changes on the Yucatán Peninsula during the TCP that complement the often-suggested southward displacement of the Intertropical Convergence Zone. We advocate for a strong role of ocean-atmosphere interactions in the Caribbean Sea related to the multiyear variations in Caribbean Sea surface conditions as an important driver of the spatially complex pattern of hydrological anomalies during the TCP.

Sable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from DSDP Hole 31-292

This study presents new evidence of when and how the Western Pacific Warm Pool (WPWP) was established in its present form. We analyzed planktic foraminifera, oxygen isotopes, and Mg/Ca ratios in upper Miocene through Pleistocene sediments collected at Deep Sea Drilling Program (DSDP) Site 292. These data were then compared with those reported from Ocean Drilling Program (ODP) Site 806. Both drilling sites are located in the western Pacific Ocean. DSDP Site 292 is located in the northern margin of the modern WPWP and ODP Site 806 near the center of the WPWP. Three stages of development in surface-water conditions are identified in the region using planktic foraminferal data. During the initial stage, from 8.5 to 4.4 Ma, Site 806 was overlain by warm surface water but Site 292 was not, as indicated by the differences in faunal compositions and sea-surface temperature (SST) between the two sites. In addition, the vertical thermal gradient at Site 292 was weak during this period, as indicated by the small differences in the delta18O values between Globigerinoides sacculifer and Pulleniatina spp. During stage two, from 4.4 to 3.6 Ma, the SST at Site 292 rapidly increased to 27 °C, but the vertical thermal gradient had not yet be strengthened, as shown by Mg/Ca ratios and the presence of both mixed-layer dwellers and thermocline dwellers. Finally, a warm mixed layer with a high SST ca. 28 °C and a strong vertical thermal gradient were established at Site 292 by 3.6 Ma. This event is marked by the dominance of mixed-layer dwellers, a high and stable SST, and a larger differences in the delta18O values between G. sacculifer and Pulleniatina spp. Thus, evidence of surface-water evolution in the western Pacific suggests that Site 292 came under the influence of the WPWP at 3.6 Ma. The northward expansion of the WPWP from 4.4 to 3.6 Ma and the establishment of the modern WPWP by 3.6 Ma appear to be closely related to the closure of the Indonesian and Central American seaways.

Mg/Ca ratios of Cenozoic benthic foraminifera from the Indian and South Atlantic Ocean

We investigate the evolution of Cenozoic climate and ice volume as evidenced by the oxygen isotopic composition of seawater (delta18Osw) derived from benthic foraminiferal Mg/Ca ratios to constrain the temperature effect contained in foraminiferal delta18O values. We have constructed two benthic foraminiferal Mg/Ca records from intermediate water depth sites (Ocean Drilling Program sites 757 and 689 from the subtropical Indian Ocean and the Weddell Sea, respectively). Together with the previously published composite record of Lear et al. (2002, doi:10.1126/science.287.5451.269) and the Neogene record from the Southern Ocean of Billups and Schrag (2002, doi:10.1029/2000PA000567), we obtain three, almost complete representations of the delta18Osw for the past 52 Myr. We discuss the sensitivity of early Cenozoic Mg/Ca-derived paleotemperatures (and hence the delta18Osw) to assumptions about seawater Mg/Ca ratios. We find that during the middle Eocene (~ 49-40 Ma), modern seawater ratios yield Mg/Ca-derived temperatures that are in good agreement with the oxygen isotope paleothermometer assuming ice-free conditions. Intermediate waters cooled during the middle Eocene reaching minimum temperatures by 40 Ma. The corresponding delta18Osw reconstructions support ice growth on Antarctica beginning by at least 40 Ma. At the Eocene/Oligocene boundary, Mg/Ca ratios (and hence temperatures) from Weddell Sea site 689 display a well-defined maximum. We caution against a paleoclimatic significance of this result and put forth that the partitioning coefficient of Mg in benthic foraminifera may be sensitive to factors other than temperature. Throughout the remainder of the Cenozoic, the temporal variability among delta18Osw records is similar and similar to longer-term trends in the benthic foraminiferal delta18O record. An exception occurs during the Pliocene when delta18Osw minima in two of the three records suggest reductions in global ice volume that are not apparent in foraminiferal delta18O records, which provides a new perspective to the ongoing debate about the stability of the Antarctic ice sheet. Maximum delta18Osw values recorded during the Pleistocene at Southern Ocean site 747 agree well with values derived from the geochemistry of pore waters (Schrag et al., 1996, doi:10.1126/science.272.5270.1930) further highlighting the value of the new Mg/Ca calibrations of Martin et al. (2002, doi:10.1016/S0012-821X(02)00472-7) and Lear et al. (2002, doi:10.1016/S0016-7037(02)00941-9) applied in this study. We conclude that the application of foraminiferal Mg/Ca ratios allows a refined view of Cenozoic ice volume history despite uncertainties related to the geochemical cycling of Mg and Ca on long time scales.

(Table S3) Benthic foraminiferal Mg/Ca, Li/Ca and stable isotope ratios of ODP Site 122-761

The sensitivities of benthic foraminiferal Mg/Ca and Li/Ca to bottom water temperature and carbonate saturation state have recently been assessed. Here we present a new approach that uses paired Mg/Ca and Li/Ca records to calculate simultaneous changes in temperature and saturation state. Using previously published records, we first use this approach to document a cooling of deep ocean waters associated with the establishment of the Antarctic ice sheet at the Eocene-Oligocene climate transition. We then apply this approach to new records of the Middle Miocene Climate Transition from ODP Site 761 to estimate variations in bottom water temperature and the oxygen isotopic composition of seawater. We estimate that the oxygen isotopic composition of seawater varied by ~1 per mil between the deglacial extreme of the Miocene Climatic Optimum and the glacial maximum following the Middle Miocene Climate Transition, indicating large amplitude variations in ice volume. However, the longer-term change between 15.3 and 12.5 Ma is marked by a ~1°C cooling of deep waters, and an increase in the oxygen isotopic composition of seawater of ~0.6 per mil. We find that bottom water saturation state increased in the lead up to the Middle Miocene Climate Transition and decreased shortly after. This supports decreasing pCO2 as a driver for global cooling and ice sheet expansion, in agreement with existing boron isotope and leaf stomatal index CO2 records but in contrast to the published alkenone CO2 records.

Mg/Ca-temperature proxy in benthic foraminifera from the Florida Strait

Over the past decade, the ratio of Mg to Ca in foraminiferal tests has emerged as a valuable paleotemperature proxy. However, large uncertainties remain in the relationships between benthic foraminiferal Mg/Ca and temperature. Mg/Ca was measured in benthic foraminifera from 31 high-quality multicore tops collected in the Florida Straits, spanning a temperature range of 5.8° to 18.6°C. New calibrations are presented for Uvigerina peregrina, Planulina ariminensis, Planulina foveolata, and Hoeglundina elegans. The Mg/Ca values and temperature sensitivities vary among species, but all species exhibit a positive correlation that decreases in slope at higher temperatures. The decrease in the sensitivity of Mg/Ca to temperature may potentially be explained by Mg/Ca suppression at high carbonate ion concentrations. It is suggested that a carbonate ion influence on Mg/Ca may be adjusted for by dividing Mg/Ca by Li/Ca. The Mg/Li ratio displays stronger correlations to temperature, with up to 90% of variance explained, than Mg/Ca alone. These new calibrations are tested on several Last Glacial Maximum (LGM) samples from the Florida Straits. LGM temperatures reconstructed from Mg/Ca and Mg/Li are generally more scattered than core top measurements and may be contaminated by high-Mg overgrowths. The potential for Mg/Ca and Mg/Li as temperature proxies warrants further testing.

Stable oxygen and carbon isotope record of foraminifera of ODP SIte 184-1146

Ocean Drilling Program Site 1146 was drilled within a small rift basin on the midcontinental slope of the northern South China Sea. It is located at 19°27.4'N, 116°16.37'E, in 2092 m water depth. This site was drilled to recover records of Asian monsoon variability into the middle Miocene with temporal resolution sufficient for orbital-scale analyses. Here we present oxygen and carbon isotopic measurements of planktonic foraminifers (Globigerinoides ruber) and benthic foraminifers (Uvigerina peregrina and Cibicides wuellerstorfi) as well as a preliminary age model for the top 185 meters composite depth (mcd).

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.

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.

Chemical and isotopic composition of interstitial waters and hydrocarbon composition at ODP Site 184-1146

Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

Benthic foraminiferal faunas of Miocene to Holocene sediments of ODP Site 184-1143 from the southern South China Sea

Deep-sea benthic foraminiferal assemblages from Ocean Drilling Program (ODP) Site 1143 located in the southern South China Sea (SCS) were investigated to evaluate the relationship between faunal composition patterns and paleoceanographic changes during the last 6 million years (late Miocene to Holocene). We used multivariate statistics (correspondence analysis) to analyze carbon-flux-related changes in assemblage composition of benthic foraminifers. Additional proxies for carbon flux and deep-water ventilation include delta13C records of epifaunal Cibicidoides wuellerstorfi and infaunal Uvigerina peregrina var. dirupta and Melonis pompilioides, benthic foraminiferal accumulation rates (BFARs), diversity indices, and relative abundances of indicator species. We observe three significant benthic faunal changes in the southern South China Sea during the last 6 million years. Strong fluctuations in BFAR and relative abundance of productivity indicator species between glacial and interglacial stages after the mid-Pleistocene revolution (MPR) at approximately 0.9 Ma, indicating stronger seasonal carbon flux fluctuations, are accompanied by the extinction of such species as Stilostomella spp. Increases in carbon flux indicator species are coupled with an overall decrease in benthic foraminifer diversity around 3.0 Ma in the late Pliocene. This may indicate increasing carbon flux in a period of productivity maximum caused by enhanced offshore upwelling from intensified winter monsoon wind strength.

Benthic foraminiferal Cd/Ca and isotope record from the South Atlantic

A depth transect of cores from 1268 to 3909 m water depth in the western South Atlantic are ideally situated to monitor the interocean exchange of deep water and variations in the relative strength of northern and southern sources of deep water production. Benthic foraminiferal Cd/Ca and d13C data suggest that Glacial North Atlantic Intermediate Water (GNAIW) extended at least as far south as 28°S in the western South Atlantic. The core of nutrient-depleted water was situated at ~1500 m, above and below water masses with higher nutrient concentrations. When examined in conjunction with published paired Cd/Ca and d13C from intermediate depth cores from other basins, it appears that the extent of GNAIW influence on the intermediate waters of the world's oceans was less than suggested previously. Differentiating among possible pathways for the glacial deep ocean (>3 km) requires a better understanding of the controls on Cd/Ca and d13C values of benthic foraminifera.