Molecular properties of gases of ODP Leg 204 sites

The recognition of finely disseminated gas hydrate in deep marine sediments heavily depends on various indirect techniques because this mineral quickly decomposes upon recovery from in situ pressure and temperature conditions. Here, we discuss molecular properties of closely spaced gas voids (formed as a result of core recovery) and gas hydrates from an area of relatively low gas flux at the flanks of the southern Hydrate Ridge offshore Oregon (ODP Sites 1244, 1245 and 1247). Within the gas hydrate occurrence zone (GHOZ), the concentration of ethane (C2) and propane (C3) in adjacent gas voids shows large variability. Sampled gas hydrates are enriched in C2 relative to void gases but do not contain C3. We suggest that the observed variations in the composition of void gases is a result of molecular fractionation during crystallization of structure I gas hydrate that contains C2 but excludes C3 from its crystal lattice. This hypothesis is used to identify discrete intervals of finely disseminated gas hydrate in cored sediments. Variations in gas composition help better constrain gas hydrate distribution near the top of the GHOZ along with variations in pore water chemistry and core temperature. Sediments near the base of the gas hydrate stability zone are relatively enriched in C2+ hydrocarbon gases. Complex and poorly understood geological and geochemical processes in these deeper sediments make the identification of gas hydrate based on molecular properties of void gases more ambiguous. The proposed technique appears to be a useful tool to better understand the distribution of gas hydrate in marine sediments and ultimately the role of gas hydrate in the global carbon cycle.

Carbon and Nitrogen concentrations and isotopic composition of ODP Site 170-1040 and Leg 205 sites

We determined the C and N concentrations and isotopic compositions of sediments in the prism sampled during Ocean Drilling Program Legs 170 and 205 offshore Costa Rica, with the goals of evaluating sediment sources and extents of diagenesis and identifying any effects of infiltrating fluids on the sedimentary C and N. The sediments from Leg 170 Site 1040 contain 0.85-1.96 wt% total organic carbon (TOC) with Vienna Peedee belemnite (VPDB) d13CVPDB from -26.3 per mil to -22.5 per mil, and 832-2221 ppm total nitrogen (TN) with d15Nair from +3.5 per mil to +6.6 per mil. Sediment TN concentrations and d15N values show dramatic downhole increases within the uppermost 130 m of the section and more gradual downhole decreases from 130 meters below seafloor (mbsf) to the base of the décollement at ~370 mbsf. Concentrations and isotopic compositions of TOC are relatively uniform within the entire section, showing some minor perturbation within the décollement zone. In the uppermost 100 m, upsection increases in TN concentrations at constant TOC concentrations produce significant increases in atomic TOC/TN ratios from ~8 to ~18. Carbonate (calcite) contents in the wedge sediments are generally low (<4 wt%), but the d13C and Vienna standard mean ocean water (VSMOW) d18OVSMOW values vary significantly from -26.1 per mil to +4.1 per mil and from +30.0 per mil to +35.3 per mil, respectively. Concentrations and isotopic compositions of TOC and TN for sediments from Leg 205 Sites 1254 and 1255 overlap well with C-N data for sediments from the same depth intervals obtained during Leg 170 at Site 1040.

Low-molecular-weight hydrocarbons in sediments at DSDP Sites 89-585 and 89-586

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 38 shipboard sealed, deep-frozen core samples of Deep Sea Drilling Project Sites 585 (East Mariana Basin) and 586 (Ontong-Java Plateau) were determined by a gas stripping-thermovaporization method. Total concentrations, which represent the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediment, vary from 20 to 630 ng/g of rock at Site 585 (sub-bottom depth range 332-868 m). Likewise, organic-carbon normalized yields range from 3*10**4 to 9*10**5 ng/g Corg, indicating that the organic matter is still in the initial, diagenetic evolutionary stage. The highest value (based on both rock weight and organic carbon) is measured in an extremely organic-carbon-poor sample of Lithologic Subunit VB (Core 585-30). In this unit (504-550 m) several samples with elevated organic-carbon contents and favorable kerogen quality including two thin "black-shale" layers deposited at the Cenomanian/Turonian boundary (not sampled for this study) were encountered. We conclude from a detailed comparison of light hydrocarbon compositions that the Core 585-30 sample is enriched in hydrocarbons of the C2-C8 molecular range, particularly in gas compounds, which probably migrated from nearby black-shale source layers. C2-C8 hydrocarbon yields in Site 586 samples (sub-bottom depth range 27-298 m) did not exceed 118 ng/g of dry sediment weight (average 56 ng/g), indicating the immaturity of these samples.

Paleomagnetism at DSDP Sites 86-576 and 86-578

The upper sections of Deep Sea Drilling Project Sites 576 (32°21.4'N, 164°16.5'E) and 578 (33°55.6'N, 151°37.7'E) both have stable detrital remanence that can be correlated with the standard reversal stratigraphy. Site 576 contains all reversals above the base of the Gilbert Epoch (5 m.y.) at about 25 m, whereas Site 578 contains a remarkable section of about 60 reversals extending to Anomaly 5B (15 m.y.) at about 150 m sub-bottom depth. In both cases, the paleomagnetic stratigraphy breaks down when accumulation rates drop below 2 m/m.y. At both sites, authigenic manganiferous clays deposited from 70 to 16 m.y. ago accumulated at about 0.4 m/m.y. Similarly, at both sites, the Pleistocene pulse of eolian debris increased accumulation rates by about 6 m/m.y.**2. From 16 to 2 m.y. ago, however, sediment accumulated at Site 578 about five times as rapidly as at Site 576, apparently because of augmented input to the western site by bottom currents.

Plio-Pleistocene age-depth points and occurrence of hiatuses in ODP sites of the Southern Ocean

Changes in Atlantic deep water circulation were reconstructed by comparing the benthic foraminiferal delta13C record at ODP Site 1090 in the South Atlantic with similar records from the North Atlantic (Sites 982, 607, 925, 929) and deep Pacific (Site 849) oceans. Important deep water circulation changes occurred in the early Pleistocene at 1.55 Myr and during the Mid-Pleistocene Transition at 0.9 Myr. At 1.55 Myr, glacial delta13C values in the Southern Ocean became significantly lower than those in the deep Pacific, establishing a pattern that persisted throughout the late Pleistocene. We propose that the lowering of delta13C values of Southern Component Water (SCW) at this time resulted from expansion of sea ice and reduced ventilation of deep water during glacial periods after marine isotope stage 52. Accompanying this change in Southern Ocean deep water circulation was enhanced interhemispheric coupling between the North and South Atlantic after 1.55 Myr. At ~0.9 Myr, the magnitude of glacial-to-interglacial variabilityin delta13C increased and shifted to a longer frequency (100 kyr) along with oceanic delta18O (ice volume). Calculation of percent Northern Component Water (NCW) using Site 1090 as the SCW end member yielded 20-30% less reduction of NCW during glacial periods of the late Pleistocene. Also, a trend toward reduced glacial suppression of NCW during the past 400 kyr is not evident. The apparent decoupling of ice volume and deep water circulation reported previously maybe an artifact of using a Pacific, rather than a Southern Ocean, carbon isotopic record to calculate past mixing ratios of NCW and SCW.

Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

Cretaceous-Paleogene biomagnetostratigraphy of ODP Leg 121 sites

Broken Ridge, in the eastern Indian Ocean, is a shallow-water volcanic platform which formed during the Early to middle Cretaceous at which time it comprised the northern portion of the Kerguelen-Heard Plateau. Rifting during the middle Eocene and subsequent seafloor spreading has moved Broken Ridge about 20?N to its present location. The sedimentary section of Broken Ridge includes Turonian-lower Eocene limestone and chalk with volcanic ash, an interval of detrital sands and gravels associated with middle Eocene rifting and uplift, and a middle-late Oligocene unconformity overlain by a thin section of Neogene-Holocene pelagic calcareous ooze. This paper summarizes the available post-cruise biostratigraphic and magnetostratigraphic data for the Cretaceous-Paleogene section on Broken Ridge. The synthesis of this information permits a more precise interpretation of the timing of events in the history of Broken Ridge, in particular the timing and duration of the middle Eocene rifting event. Paleontologic data support rapid flexural uplift of Broken Ridge in response to mechanical rather than thermal forces. Other highlights of the section include a complete Cretaceous/Tertiary boundary and an opportunity for first-order correlation of Paleogene diatom stratigraphy with that of the calcareous groups.

Argon ratios, 40Ar/39Ar datings and biostratigraphic ages of ODP Leg 165 sites

Drilling in the Caribbean Sea during Ocean Drilling Program Leg 165 has recovered a large number of silicic tephra layers and led to the discovery of three major episodes of explosive volcanism that occurred during the last 55 m.y. on the margins of this evolving ocean basin. The earliest episode is marked by Paleocene to early Eocene explosive volcanism on the Cayman Rise, associated with activity of the Cayman arc, an island arc that was the westward extension of the Sierra Maestra volcanic arc in southern Cuba. Caribbean sediments also document a major mid- to late Eocene explosive volcanic episode that is attributed to ignimbrite-forming eruptions on the Chortis Block in Central America to the west. This event is contemporaneous with the first phase of activity of the Sierra Madre volcanic episode in Mexico, the largest ignimbrite province on Earth. In the Caribbean sediments, a Miocene episode of explosive volcanism is comparable to the Eocene event, and also attributed to sources in the Central American arc to the west. Radiometric 40Ar/39Ar dates have been obtained for biotites and sanidines from 27 tephra layers, providing absolute ages for the volcanic episodes and further constraining the geochronology of Caribbean sediments. Volcanic activity of the Cayman arc is attributed to the northward subduction of the leading edge of the oceanic plate that carried the Caribbean oceanic plateau. Although the factors generating the large episodes of Central American explosive volcanism are unclear, we propose that they are related to contemporary major readjustments of plate tectonic configuration in the Pacific.

Dinoflagellate and other palynomorph abundance in sediments from ODP Leg 189 sites

At Ocean Drilling Program (ODP) Leg 189 Sites 1170-1172, the climatologically critical Eocene-Oligocene (E-O) transition is barren of any calcareous microfossils but contains rich marine organic walled dinoflagellate cyst (dinocyst) and diatom assemblages, suitable for detailed biostratigraphic and paleoenvironmental analysis. The resulting first-ever integrated dinocyst/diatom magnetostratigraphy allows confident correlation of the E-O interval between all Leg 189 sites, including Site 1168. Our correlations indicate that the (deep) opening of the Tasmanian Gateway occurred quasi-synchronously throughout the Tasmanian region, starting at ~35.5 Ma. At Sites 1170-1172, quantitatively, three distinct dinocyst assemblages may be distinguished that reflect the relatively rapid and pronounced stepwise environmental changes associated with the E-O transition in the Tasmanian region, from a pro-deltaic setting to a deep marine pelagic setting. Moreover, synchronous with the deepening of the gateway, at the southern and eastern Sites 1170-1172, typical endemic Antarctic assemblages were replaced by more cosmopolitan dinocyst communities. In marked contrast, at Site 1168 off western Tasmania, endemic Antarctic taxa are virtually absent during the E-O transition. At Sites 1170-1172, the endemic Antarctic dinocyst assemblage (Transantarctic Flora) drastically changes into a more cosmopolitan assemblage at ~35.5 Ma, with a more offshore character, reflecting the arrival of different oceanographic and environmental conditions associated with the deepening of the Tasmanian Gateway. In turn, this assemblage grades at ~34 Ma into one more typical for even more offshore and/or upwelling conditions at Site 1172. In slightly younger deposits at all sites, organic microfossils are virtually absent, reflecting winnowing and oxidation, indicative of a next step of oceanographic development. This phase may be dated as close to the Oceanic Anoxic (Oi)-1 18O (Antarctic glaciation) event (~33.3 Ma). In a single productive sample from the earliest Oligocene the northern Site 1172, a relatively warm-water cosmopolitan assemblage has been recovered. This aspect contrasts findings from coeval deposits from the Ross Sea, where endemic Antarctic species remain dominant. Somewhere between the paleogeographic positions of Site 1172 and the Ross Sea, a strong differentiation of surface waters occurred in the earliest Oligocene, possibly reflecting the onset of the Antarctic Circumpolar Current.

Phosphorus concentrations and accumulation rates of ODP Leg 130 sites

Little is known about the fluxes to and from the ocean during the Cenozoic of phosphorus (P), a limiting nutrient for oceanic primary productivity and organic carbon burial on geologic timescales. Previous studies have concluded that dissolved river fluxes increased worldwide during the Cenozoic and that organic carbon burial decreased relative to calcium carbonate burial and perhaps in absolute terms as well. To examine the apparent contradiction between increased river fluxes of P (assuming P fluxes behave like the others) expected to drive increased organic carbon burial and observations indicating decreased organic carbon burial, we determined P accumulation rates for equatorial Pacific sediments from Ocean Drilling Program leg 138 sites in the eastern equatorial Pacific and leg 130 sites on the Ontong Java Plateau in the western equatorial Pacific. Although there are site specific and depth dependent effects on P accumulation rates, there are important features common to the records at all sites. P accumulation rates declined from 50 to 20 Ma, showed some variability from 20 to 10 Ma, and had a substantial peak from 9 to 3 Ma centered at 5-6 Ma. These changes in P accumulation rates for the equatorial Pacific are equivalent to substantial changes in the P mass balance. However, the pattern resembles neither that of weathering flux indicators (87Sr/86Sr and Ge/Si ratios) nor that of the carbon isotope record reflecting changes in organic carbon burial rates. Although these P accumulation rate patterns need confirmation from other regions with sediment burial significant in global mass balances (e.g., the North Pacific and Southern Ocean), it appears that P weathering inputs to the ocean are decoupled from those of other elements and that further exploration is needed of the relationship between P burial and net organic carbon burial.

Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.