Nature, origin, and petroleum source potential of organic matter at DSDP Leg 56-57 Holes

As part of a continuing program of organic-geochemistry studies of sediments recovered by the Deep Sea Drilling Project, we have analyzed the types, amounts, and thermal-alteration indices of organic matter in samples collected from the landward wall of the Japan Trench on Legs 56 and 57. The samples were canned aboard ship, enabling us to measure also their gas contents. In addition, we analyzed the heavy C15+ hydrocarbons, NSO compounds, and asphaltenes extracted from selected samples. Our samples form a transect down the trench wall, from Holes 438 and 438A (water depth 1558 m), through Holes 435 and 435A (water depth 3401 m), and 440 (water depth 4507 m), to Holes 434 and 434B (water depth 5986 m). The trench wall is the continental slope of Japan. Its sediments are Cenozoic hemipelagic diatomaceous muds that were deposited where they are found or have slumped from farther up the slope. Their terrigenous components probably were deposited from near-bottom nepheloid layers transported by bottom currents or in low density flows (Arthur et al., 1978). Our objective was to find out what types of organic matter exist in the sediment and to estimate their potential for generation of hydrocarbons.

(Table 1) Geochemical and geothermometry data from fibrous calcite vein fills in the Dabashan Fold Belt, China

Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). d13CPDB and d18OPDB values of the fibrous calcite range from - 4.8 to -1.9 to per mil and - 12.8 to - 8.4 per mil respectively, which is lighter than that of associated carbonate host rocks ranging from - 1.7 to + 3.1 per mil and - 8.7 to - 4.5 per mil. A linear relationship between d13CPDB and d18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196° with an average of 179°. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic bearing fluids from the DBF during the Yanshan orogeny.

Holocene corals from the South China Sea

The South China Sea (SCS) is well connected with the western Pacific and influenced by the East Asian monsoon. We have examined temporal variations in radiocarbon marine reservoir ages (R) and regional marine reservoir corrections (DeltaR) of the SCS during the Holocene using paired measurements of AMS 14C and TIMS 230Th on 20 pristine corals. The results show large fluctuations in both R and DeltaR values over the past 7500 years (yrs) with two distinct plateaus during 7.5-5.6 and 3.5-2.5 thousand calendar years before present (cal ka BP). The respective weighted mean DeltaR values of these plateaus are 151 ± 85 and 89 ± 59 yrs, which are significantly higher than its modern value of -23 ± 52 yrs. This suggests that using a constant modern DeltaR value to calibrate 14C dates of the SCS marine samples will introduce additional errors to the calibrated ages. Our results provide the first database for the Holocene R and DeltaR values of the SCS for improved radiocarbon calibration of marine samples. We interpret the two DeltaR plateaus as being related to two intervals with weakened El Niño - Southern Oscillation (ENSO) and intensified East Asian summer monsoon (EASM). This is because the 14C content of the SCS surface water is controlled by both the 14C concentration of the Pacific North Equatorial Current (NEC) which is in turn influenced by ENSO-induced upwelling along the Pacific equator and vertical upwelling within the SCS as a result of moisture transportation to midlatitude region to supply the EASM rainfall.

Geochemistry of Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian-Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, d13Corg values lie mostly between -30 per mil and -27 per mil, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low d13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian-Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.

High resolution color reflectance and hematite and goethite record of ODP Hole 184-1143A in the South China Sea

Precipitation has a larger variability than temperature in tropical monsoon regions, thus it is an important climate variable. However, reconstructions of long-term rainfall histories are scarce because of the lack of reliable proxies. Here we document that iron oxide minerals, specifically the ratio of hematite to goethite (Hm/Gt), is a reasonable precipitation proxy. Using diffuse reflectance spectrophotometry, we measured samples from Ocean Drilling Program (ODP) 1143 drilling site (9°21.72'N, 113°17.11'E, 2777 m water depth) for hematite and goethite, whose formation processes are favored by opposing climate conditions. In order to determine the content of hematite and goethite we produced a set of calibration samples by removing the iron oxides to generate the natural matrix to which hematite and goethite in known percentages were added. From these calibration samples we developed a transfer function for determining hematite and goethite concentration from a sample's spectral reflectance. Applying this method to ODP 1143 sediments (top 34 m of a 510 m core with sampling interval of 10 cm) we were able to reconstruct a continuous precipitation history for SE Asia of the past 600 kyr using the Hm/Gt ratio as a proxy of the precipitation variability of Asian monsoon. The reliability of this Hm/Gt proxy is corroborated by its consistency with the stalagmite delta18O data from South China. Comparing long-term Hm/Gt records with the surface temperature gradient of equatorial Pacific Ocean, we found that monsoon precipitation and El Niño are correlated for the last 600 kyr. The development of El Niño-like conditions decreased SE Asia precipitation, whereas precipitation increases in response to La Niña intensification

Strontium measurements and sea surface temperatures of corals from Xisha Island, South China Sea

A Porites coral collected from Xisha Island, South China Sea, represents a skeleton secreted in the period from 1906 to 1994. The Sr contents of the coral vary linearly with the instrument-measured sea-surface temperature (SST), giving a Sr thermometer: SST = -1.9658 x Sr + 193.26. The reconstructed SST data show that the late 20th century was warmer (about 1°C) than the early 20th century and that two cooling (1915/1916 and 1947/1948) and three warming (1935/1936, 1960/1961, and 1976/1977) shifts occurred in the century. The temperature shifts are more pronounced for winters, implying a close effect of the west Pacific warm pool and Asian monsoon and suggesting that the former is a primary force controlling the climatic system of the region. Results of this study and previously published data indicate a close link of temperature shifts between the boreal summer and the austral winter or the boreal winter and the austral summer. The annual SST anomalies in the South China Sea and the South Pacific reveal the existence of harmonic but opposite SST variations between the two regions. On the decadal scale the comparative annual SST anomalies for the South China Sea and for the equatorial west Pacific show a similarity in temperature variations, implying that the South China Sea climate is coherent with climatic regime of the tropical west Pacific.

Magnetic and gravity measurements on North-South profiles across the Grosse Meteor Bank, North Atlantic

During the first section of the "Meteor" cruise No. 2 a profile was run from the Azores to the south across the flanks of the Mid-Atlantic Ridge with a chain of seamounts. The profile extended between the Cruiser (living) and the Hyeres seamounts, which, according to our soundings, form a connected massif, and across the centre of the Grosse Meteor Bank (30°N, 28.5 °W). These seamounts rise from a depth of more than 4000 m up till close to the surface of the sea forming there a large almost flat plateau. In the case of the Grosse Meteor Bank, this plateau has a N-S extension of approx. 30 nautical miles and an E-W extension of approx. 20 nautical miles and reaches a height of 275 m in water depth. The gravity measurements yielded a density of the topographic masses of 2.6 g/cm**3 for the Grosse Meteor Bank. Magnitude and shape of the measured free-air anomaly are very well shown in a model computation with this density. The theoretical gravity effects of the seismically detected swell of cristalline rock and of the Moho depression (mountain root) are not indicated by the observational data. It can, therefore, be assumed that the latter two neutralize each other. It seems, accordingly, that there is no local isostatic compensation of the topographic masses. Hence, the density of 2.6 g/cm**3 obtained would be about the true density of rock. In connection with the mean velocity of P waves (Aric et al., 1968) obtained by seismic refraction methods it must be concluded that the material of the 1200-4000 m thick surface layer of the Grosse Meteor Bank consists of consolidated sediments. This finding is supported by the total intensity of the Earth's magnetic field over the Grosse Meteor Bank. On the assumption of a homogeneous magnetization in the direction of the present Earth's field, the computed anomaly of the massif deviates considerably from the measured anomaly while the magnetic field of the seismically detected crystalline body is capable of interpreting the observed data. Deviating from the prevailing interpretation of the seamounts' plateau as a volcanic cone with submarine abrasion, the Grosse Meteor Bank and the seamounts in the vicinity are assumed to be of continental origin. The questions whether these seamounts submerged later on or whether the sealevel has risen subsequently are, therefore, largely nonexistent.

Neodymium isotopes in benthic foraminifera from the South Atlantic

Records of the past neodymium (Nd) isotope composition of the deep ocean can resolve ambiguities in the interpretation of other tracers. We present the first Nd isotope data for sedimentary benthic foraminifera. Comparison of the epsilon-Nd of core-top foraminifera from a depth transect on the Cape Basin side of the Walvis Ridge to published seawater data, and to the modern dissolved SiO2- epsilon-Nd trend of the deep Atlantic, suggests that benthic foraminifera represent a reliable archive of the deep water Nd isotope composition. Neodymium isotope values of benthic foraminifera from ODP Site 1264A (Angola Basin side of the Walvis Ridge) from the last 8 Ma agree with Fe-Mn oxide coatings from the same samples and are also broadly consistent with existing fish teeth data for the deep South Atlantic, yielding confidence in the preservation of the marine Nd isotope signal in all these archives. The marine origin of the Nd in the coatings is confirmed by their marine Sr isotope values. These important results allow application of the technique to down-core samples. The new epsilon-Nd datasets, along with ancillary Cd/Ca and Nd/Ca ratios from the same foraminiferal samples, are interpreted in the context of debates on the Neogene history of North Atlantic Deep Water (NADW) export to the South Atlantic. In general, the epsilon-Nd and delta13C records are closely correlated over the past 4.5 Ma. The Nd isotope data suggest strong NADW export from 8 to 5 Ma, consistent with one interpretation of published delta13C gradients. Where the epsilon-Nd record differs from the nutrient-based records, changes in the pre-formed delta13C or Cd/Ca of southern-derived deep water might account for the difference. Maximum NADW-export for the entire record is suggested by all proxies at 3.5-4 Ma. Chemical conditions from 3 to 1 Ma are totally different, showing, on average, the lowest NADW export of the record. Modern-day values again imply NADW export that is about as strong as at any stage over the past 8 Ma.

Mid-Pleistocene Mg/Ca, temperature and stable isotopes from Globigerinoides ruber white and Globorotalia inflata of sediment core GeoB3801-6 from the subtropical South Atlantic

The glacial marine isotope stage 14 (MIS 14) appears in many climate records as an unusually warm glacial. During this period an almost monospecific, up to 1.5 m thick, laminated layer of the giant diatom Ethmodiscus rex has been deposited below the South Atlantic Subtropical Gyre. This oligotrophic region is today less favorable for diatom growth with sediments typically consisting of calcareous nannofossil oozes. We have reconstructed temperatures and the stable oxygen isotopic compositions of sea surface and thermocline water (d18Ow) from planktonic foraminiferal (Globigerinoides ruber and Globorotalia inflata) Mg/Ca and stable oxygen isotopes to test whether perturbations in surface ocean conditions contributed to the deposition of the diatom layer at ~530 kyr B.P. Temperatures and d18Ow values reconstructed from this diatom ooze interval are highly variable, with maxima similar to interglacial values. Since the area of the Ethmodiscus oozes resembles the region where Agulhas rings are present, we interpret these hydrographic changes to reflect the varying influence of warm and saline water of Indian Ocean origin that entered the Subtropical Gyre trapped in Agulhas rings. The formation of the Ethmodiscus oozes is associated with a period of maximum Agulhas leakage and a maximum frequency of Agulhas ring formation caused by a termination-type position of the Subtropical Front during the unusual warm MIS 14. The input of silica through the Agulhas rings enabled the shift in primary production from calcareous nannoplankton to diatoms, leading to the deposition of the massive diatom oozes.