(Table 1) Concentrations of CaCO3 and organic carbon, organic matter atomic C/N ratios and delta13C values of sediment samples from Site DSDP 594

CaCO3 and total organic carbon concentrations, organic matter C/N and carbon isotope ratios, and sediment accumulation rates in late Quaternary sediments from DSDP Site 594 provide information about glacial-interglacial variations in the delivery of organic matter to the Chatham Rise offshore of southeastern New Zealand. Low C/N ratios and nearly constant organic delta13C values of ?23? indicate that marine production dominates organic matter supply in both glacial and interglacial times during oxygen isotope stages 1 through 6 (0-140 ka) and 17 through 19 (660-790 ka). Increased organic carbon mass accumulation rates in isotope stages 2, 4, 6, and 18 record enhanced marine productivity during glacial maxima. Excursions of organic delta13C values to ca. ?29? in portions of isotope stage 2 suggest that the local concentration of dissolved CO2 was occasionally elevated during the last glacial maximum, probably as a result of short periods of lowered sea-surface temperature. Dilution of carbonates by clastic continental sediment generally increases at this location during glacial maxima, but enhanced delivery of land-derived organic matter does not accompany the increased accumulation of clastic sediments.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

Uvigerina spp. d18O and Mg/Ca measurements from sediment cores JR244-GC528 and MD07-3076

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected d18O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer d13C and foraminifer/coral 14C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.

Planktonic foraminiferal stratigraphy, datum levels and ages of ODP Sites 184-1146 and 184-1148, South China Sea

Over 30 first and last occurrence (FO and LO, respectively) planktonic foraminifer datums were recognized from the Oligocene-Miocene section of Ocean Drilling Program (ODP) Site 1148. Most datum levels occur in similar order as, and are by correlation as probably synchronous with, their open-ocean records. Several datum levels represent local bioevents resulting from dissolution and Site 1148's unique paleoceanographic setting in the northern South China Sea. An age of 9.5-9.8 Ma is estimated for the local LO of Globoquadrina dehiscens (257 meters composite depth [mcd]), whereas the local LO of Globorotalia fohsi s.l. (301 mcd) is projected to be at ~13.0 Ma and the local FO of Globigerinatella insueta (367 mcd) is projected to be at ~18.0 Ma. The combined planktonic foraminifer and nannofossil results indicate that the Oligocene-Miocene section at Site 1148 is not complete. Unconformities up to 2-3 m.y. in duration, occurring at and before the Oligocene/Miocene boundary (OHS1, OHS2, OHS3, and OHS4 = MHS1), are associated with slump deposits between 457 and 495 mcd that signal tectonic instability during the transition from rifting to spreading in the South China Sea. Shorter unconformities of <0.5 m.y. duration that truncate the Miocene section were more likely to have been caused by sea-bottom erosion as well as dissolution. A total of 12 Miocene unconformities, MHS1 through MHS12, are mainly affected by dissolution and an elevated carbonate compensation depth (CCD) during Miocene third-order glaciations recorded in deep-sea positive oxygen isotope Mi glaciation events. Respectively, they fall at ~457 mcd (MHS1 = Mi-1), 407 mcd (MHS2 = Mi-1a), 385 mcd (MHS3 = Mi-1aa), 366 mcd (MHS4 = Mi-1b), 358 mcd (MHS5 = MLi-1), 333 mcd (MHS6 = Mi-2), 318 mcd (MHS7 = MSi-1), 308 mcd (MHS8 = Mi-3), 295 mcd (MHS9 = Mi-4), 288 mcd (MHS10 = Mi-5), 256 mcd (MHS11 = Mi-6), and 250 mcd (MHS12 = Mi-7). The correlation of these unconformities with Mi events indicates that some related driving mechanisms have been operating, causing deepwater circulation changes concomitantly in world oceans and in the marginal South China Sea.

Abundance of palynomorphs and dinoflagellate stratigraphy of ODP Hole 184-1148A, South China Sea

Dinoflagellate stratigraphy is described for the section from 364.75 to 843.85 meters below seafloor (mbsf) at Site 1148 (Sections 184-1148A-40X-1 through 76X-6 and 184-1148B-39X-CC through 56X-1) in the South China Sea. Two assemblage zones and two subzones are defined, based on characteristics of the assemblages and lowest/highest occurrences of some key species. These are the Cleistosphaeridium diversispinosum Assemblage Zone (Zone A; Oligocene), with the Enneadocysta pectiniformis Subzone (Subzone A-1) and the Cordosphaeridium gracile Subzone (Subzone A-2), and the Polysphaeridium zoharyi Assemblage Zone (Zone B; early Miocene). The highest concurrent occurrence of Enneadocysta arcuata, Eneadocysta multicornuta, Homotryblium plectilum, and Homotryblium tenuispinosum delineates the upper boundary of Zone A, which appears to mark a hiatus. Subzone A-1 is of early Oligocene age, as evidenced by the highest occurrences of E. pectiniformis and Phthanoperidinium amoenum at the upper boundary of the subzone. Subzone A-2 is of late Oligocene age based on the highest occurrences of C. gracile and Wetzeliella gochtii close to the upper boundary of the subzone and the occurrence of Distatodinium ellipticum and Membranophoridium aspinatum within the subzone. Zone B is dated as early Miocene based on the lowest occurrences of Cerebrocysta satchelliae, Hystrichosphaeropsis obscura, Melitasphaeridium choanophorum, Membranilarnacia? picena, and Tuberculodinium vancampoae within the zone. The present assemblage zones/subzones are correlative to various degrees with coeval zones/assemblages from areas of high to low latitudes in terms of common key species. We have compared the species content of the assemblage Zones A and B, and the subzones A-1 and A-2, with coeval assemblage(s)/zone(s) described from many, often widely distant, high- and low-latitude regions of the world. These comparisons show that, to various degrees and aside from a number of key species, the coordinated presence of certain important species may also help to assign an age to a given assemblage.

Age model of ODP Site 184-1146 (Table 1)

Clay mineral assemblages at ODP Site 1146 in the northern South China Sea are used to investigate sediment source and transport processes and to evaluate the evolution of the East Asian monsoon over the past 2 Myr. Clay minerals consist mainly of illite (22-43%) and smectite (12-48%), with associated chlorite (10-30%), kaolinite (2-18%), and random mixed-layer clays (5-22%). Hydrodynamic and mineralogical studies indicate that illite and chlorite sources include Taiwan and the Yangtze River, that smectite and mixed-layer clays originate predominantly from Luzon and Indonesia, and that kaolinite is primarily derived from the Pearl River. Mineral assemblages indicate strong glacial-interglacial cyclicity, with high illite, chlorite, and kaolinite content during glacials and high smectite and mixed-layer clay content during interglacials. During interglacials, summer enhanced monsoon (southwesterly) currents transport more smectite and mixed-layer clays to Site 1146 whereas during glacials, enhanced winter monsoon (northerly) currents transport more illite and chlorite from Taiwan and the Yangtze River. The ratio (smectite+mixed layers)/(illite+chlorite) was adopted as a proxy for East Asian monsoon variability. Higher ratios indicate strengthened summer-monsoon winds and weakened winter-monsoon winds during interglacials. In contrast, lower ratios indicate a strongly intensified winter monsoon and weakened summer monsoon during glacials. Spectral analysis indicates the mineral ratio was dominantly forced by monsoon variability prior to the development of large-scale glaciation at 1.2 Myr and by both monsoon variability and the effects of changing sea level in the interval 1.2 Myr to present.

(Table 2) Age model of ODP Site 184-1146

Orbital tuning of benthic d18O is a common approach for assigning ages to ocean sediment records. Similar environmental forcing of the northern South China Sea and the southeast Asian cave regions allows for transfer of the speleothem d18O radiometric chronology to the planktonic and benthic d18O records from Ocean Drilling Program Site 1146, yielding a new chronology with 41 radiometrically calibrated datums, spanning the past 350 kyr. This approach also provides for an independent assessment of the accuracy of the orbitally tuned benthic d18O chronology for the last 350 kyr. The largest differences relative to the latest chronology occur in marine isotope stages (MIS) 5.4, 5.5, 6, 7, and 9.3. Prominent suborbital-scale structure believed to be global in nature is identified within MIS 5.4 and MIS 7.2. On the basis of the radiometrically calibrated chronology, the time constant of the ice sheet is found to be 5.4 kyr at the precession band (light d18O lags precession minima by -55.4°) and 10.4 kyr at the obliquity band (light d18O lags obliquity maxima by 57.4°). These values are significantly shorter than the single 17 kyr time constant originally estimated by Imbrie et al. (1984), based primarily on the timing of terminations I and II and the 15 kyr time constant used by Lisiecki and Raymo (2005, doi:10.1029/2004PA001071).

(Table 1) Element concentrations in detrital sediments of ODP Site 184-1148

The chemical index of alteration (CIA) and elemental ratios that are sensitive to chemical weathering, such as Ca/Ti, Na/Ti, Al/Ti, Al/Na, Al/K, and La/Sm, were analyzed for detrital sediments at Ocean Drilling Program Site 1148 from the northern South China Sea to reveal information of chemical weathering in the source regions during the early Miocene. High CIA values of ~80, coupled with high Al/Ti and Al/Na and low Na/Ti and Ca/Ti, are observed for the sediments at ~23 Ma, indicating a high chemical weathering intensity in the north source region, i.e., south China. This was followed by gradual decreases in Al/Ti, Al/Na, La/Sm, and Al/K ratios, as well as the CIA values, and increases in Ca/Ti and Na/Ti ratios. These records together with other paleoclimate proxies, such as black carbon d13C and benthic foraminifer d18O, give reliable information on the climate changes in south China. Our results show that the climate in south China was warm and humid in the early Miocene (~23 Ma) according to the chemical weathering records. The humidity in south China decreased from the early Miocene to Present with several fluctuations centering at approximately 15.7 Ma, 8.4 Ma, and 2.5 Ma, coincident with the global cooling since the middle Miocene. These climate changes implied that the summer east Asian monsoon has dramatically affected south China in the early Miocene, whereas the influence of the summer monsoon on this region has decreased continuously since that time, probably because of the intensification of the winter monsoon. Such an evolution for the east Asian monsoon is different from that for the Indian monsoon.

Stable isotope and Mg/Ca ratio of sediment core GeoB12610-2

To reconstruct the still poorly understood thermocline fluctuations in the western tropical Indian Ocean, a sediment core located off Tanzania (GeoB12610-2; 04°49.00'S, 39°25.42'E, 399?m water depth) covering the last 35 ka was analysed. Mg/Ca-derived temperatures from the planktonic foraminifera Globigerinoides ruber (white) and Neogloboquadrina dutertrei indicate that the last glacial was ~2.5 °C colder in the surface waters and ~3.5 °C colder in the thermocline compared with the present day. The depth of the thermocline and thus the stratification of the water column were shallower during glacial periods and deepened during the deglaciation and Holocene. The increased inflow of Southern Ocean Intermediate Waters via 'ocean tunnels' appears to cool the thermocline from below, leading to a similarity between the thermocline record of GeoB12610-2 with the Antarctic EDML temperature curve during the glacial. With rising sea level and the corresponding greater inflow of Red Sea Waters and Indonesian Intermediate Waters, the proportion of Southern Ocean Intermediate Water within the South Equatorial Current is reduced and, by Holocene time, the correlation to Antarctica is barely traceable. Comparison with the eastern Indian Ocean reveals that the thermocline depth reverses from the last glacial to present.

(Table S1) Stable carbon and oxygen isotopes and Mg/Ca ratios of planktonic foraminifera from ODP Hole 198-1209B

The Paleocene-Eocene Thermal Maximum (PETM) has been attributed to a rapid rise in greenhouse gas levels. If so, warming should have occurred at all latitudes, although amplified toward the poles. Existing records reveal an increase in high-latitude sea surface temperatures (SSTs) (8° to 10°C) and in bottom water temperatures (4° to 5°C). To date, however, the character of the tropical SST response during this event remains unconstrained. Here we address this deficiency by using paired oxygen isotope and minor element (magnesium/calcium) ratios of planktonic foraminifera from a tropical Pacific core to estimate changes in SST. Using mixed-layer foraminifera, we found that the combined proxies imply a 4° to 5°C rise in Pacific SST during the PETM. These results would necessitate a rise in atmospheric pCO2 to levels three to four times as high as those estimated for the late Paleocene.

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