Biogenic silica in the coastal plume of the Mississippi River

The surface distributions of dissolved silicic acid, chlorophyll and diatom abundance were measured in the plume of the Mississippi River and adjacent waters during spring (late April and early May 1993) and summer (July 1992). In spring, the time of maximum river flow, there was an intense diatom bloom with a mean diatom abundance of 1.5 x 10**7 cells/l, more than an order of magnitude higher than in summer. Mixing curves of silicic acid concentration ([Si(OH)4]) versus salinity indicate that biological uptake within the river plume removed >99% of the Si(OH)4 supplied by the river in spring and 80 to 95% in summer. In spring [Si(OH)4] was occasionally depleted to <0.2 µM-among the lowest values ever reported from the ocean-with extensive depletion to >=0.5 µM over the shelf. In summer [Si(OH)4] was less severely depleted; the lowest measured was 0.93 µM and all others were >=2.4 µM. 30Si kinetic experiments were performed during both spring and summer to measure the degree to which the rate of Si uptake by the natural diatom assemblages was limited in situ by substrate availability. In spring the dependence of the specific uptake rate (V) on extracellular [Si(OH)4] conformed much more closely to the Michaelis-Menten saturation function than has been observed in past studies. Strong dependence of V on [Si(OH)4] was observed throughout the most Si(OH)4-depleted (<0.5 µM) region, where V was limited to 12 to 45% of the diatom assemblages' maximum uptake rate (Vmax). Half-saturation concentrations for Si uptake (Ks) averaged 0.85 uM (range = 0.48 to 1.71; n = 7) in spring, with the lowest values equal to the lowest previously reported for natural diatom assemblages. There was only 1 station in summer where V was limited by [Si(OH)4], and at that station Ks was 5.3 µM-quite high in comparison with previous studies. At stations where V was limited by [Si(OH)4], in both spring and summer, Chaetoceros spp. were numerically dominant; where there was no Si limitation other diatoms, usually Skeletonema costatum, dominated. The data thus indicate strong Si limitation in spring, with diatom assemblages well adapted to low [Si(OH)4], but little or no Si limitation in summer. Historical data suggest that coastal Si(OH)4 depletion and Si limitation may be recent phenomena in the northern Gulf of Mexico, resulting from increasing [NO3-] and decreasing [Si(OH)4] in the Mississippi River during the past 30 to 50 yr.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.

Mineralogy and incipient diagenesis of Pigmy Basin sediments, DSDP Hole 96-619

Pigmy Basin sediments cored in Hole 619 of Deep Sea Drilling Project Leg 96 are silty clays composed, on the average, of < 1% sand, 37% silt, 48% clay, and 14% carbonate minerals. Except for minor grain dissolution in some silt grains, there is no distinctive variation with depth in either composition or texture of the sand- and silt-sized minerals. This suggests a constant source of sediment supply and little diagenetic alteration of these size fractions. Clay minerals are dominated by smectite or, more precisely, montmorillonite. On the average, the clay-sized fraction consists of 48% smectite and mixed layer minerals, 30% illite, and 23% total kaolinite and chlorite. There appears to be a slight decrease in smectite and concomitant increases in other clay minerals with depth. These changes are further substantiated by the variations of ammonium acetate exchangeable K+, Mg2+, and Na+ in bulk samples. Thus, incipient diagenesis of Pigmy Basin sediments is evidenced in the mineralogical and associated chemical characteristics of the clay fractions.

Geochemistry and petrography of organic matter at DSDP Hole 77-535

Organic geochemical and organic petrographic methods were used to study three Lower to middle Cretaceous sediment samples from Hole 535 in the southeastern Gulf of Mexico for organic matter contents and origin and level of maturation. All three samples contain mixed kerogen Type II/III organic matter with a maturity corresponding to about 0.4% vitrinite reflectance. The marine component increases with stratigraphic age, and microbial reworking of the organic matter is significant in each age. The lower two samples of Hauterivian to Valanginian age appear to be impregnated (or contaminated) with soluble polar organic compounds, but there is only a weak indication for the presence of more mature, nonindigenous hydrocarbons.

Organic geochemistry of lower Cretaceous sediments at DSDP Hole 77-535

At Site 535, the four lithologic units of Cretaceous age are controlled by two types of sedimentologic facies: (1) the massive light-colored limestones or marly limestones in which the total organic carbon (TOC) content is low and the organic matter more or less oxidized and (2) laminated dark facies in which the TOC content is higher and associated with a well-preserved organic matter of Type II origin. Very little typical Type III organic matter occurs in the whole series from late Berriasian to Aptian and Cenomanian. Fluctuations from oxidizing to reducing environments of deposition are proposed to account for the variations in properties of the Type II organic matter between the different facies. Dark laminated layers are good but immature potential source rocks: petroleum potential is often higher than 2 kg HC/t of rock.

Magnetic viscosity and paleomagnetism of the basement complex at DSDP Hole 77-538A

The basement at Catoche Knoll consists of Paleozoic gneiss and amphibolite intruded by several generations of early Jurassic diabase dikes. Upon exposure to a 1-oersted field for 9 days, the diabase and amphibolite acquire a viscous remanent magnetization (VRM) which ranges from 42 to 2047% of their natural remanent magnetization (NRM). A magnetic field of similar intensity is observed in the paleomagnetic facility of the Glomar Challenger, and it is therefore doubtful if accurate measurements of magnetic moments in such rocks can be made on board unless the facility is magnetically shielded. The significant VRM also indicates the futility of attempting to discern magnetic lineations from an ocean floor composed of such rocks. No strong correlation exists between the Königsberger ratio, which is usually less than 1, and the tendency to acquire a VRM. The VRM decay is typical of a Richter aftereffect, but the relaxation times vary widely among the samples studied. A stable remanence is observed after alternating field demagnetization to 200 Oe. The range of magnetic inclinations in the diabase dikes is consistent with 40Ar/39Ar dates of 190 and 160 Ma. The inclinations suggest that the Catoche Knoll block tilted more than 20° to the north after the final dike intrusion.

Pleistocene and late Miocene Calcareous nannofossil biostratigraphy of ODP Hole 150-905A

Continental rise Site 905 yielded upper Miocene and Pliocene uniform hemipelagic mud (a contourite) from approximately 215 to 540 meters below seafloor. The nannofossil biostratigraphy of this interval was reexamined using closely spaced samples from core interiors. Additionally, total nannofossil abundances and dominant species and species group abundances were determined to evaluate the potential of this section for extracting sequence stratigraphic information. The data indicate that the putative hiatuses at the end of the late Pliocene (Zones NN17 and NN18) and in the early Pliocene (Zones NN13 and NN14) probably are condensed intervals, but the base of the late Miocene is almost certainly marked by an unconformity. Judging from carbonate content and sedimentation rate both, nannofossil abundance may be governed by carbonate dissolution or by siliciclastic dilution. Consequently, condensed sections cannot be identified by the abundance of pelagic component in the sediment alone, as is possible in equivalent age Gulf of Mexico sediments. Where nannofossil preservation is adequate in consecutive samples, as in the early Pliocene and latest late Miocene, total nannofossil abundance fluctuates regularly and with a periodicity of less than 105 yr, which suggests that dilution of the pelagic component occurred with a frequency probably related to astronomical forcing.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Age determination and median grain size of sediment core EN31-PC2

Hemipelagic muds deposited during the past 5.3 cal kyr in the northern Gulf of Mexico (Orca Basin) contain seven intervals punctuated by relatively coarse siliciclastic grain-size peaks, planktonic faunal turnovers, and negative d13C excursions. We believe these episodes represent megaflood deposits reflecting historically unprecedented outfall of North American floodwater and terrigenous mud plumes into the gulf, resulting in collapse of the open-ocean pelagic ecosystem. The deposits record multidecadal episodes of high continental precipitation and large Mississippi River floods at ~4.7, 3.5, 3.0, 2.5, 2.0, 1.2, and 0.3 cal ka (500-1200-year recurrence interval). Variations in tropical plankton frequencies define submillenial warming intervals that culminate in these fluvial episodes. Strengthened tropical currents in the gulf at these times appear to have increased sea surface temperatures and associated flow of moist gulf air to the midwest. Terrestrial paleohydrologic records support the marine evidence for millennial-scale changes in recurrence of large midwest flood episodes.

Chemical composition of bottom sediments along the Transpacific section

Distribution of Fe, Mn, Ti, Cu, Ni, Co, V, Cr, Mo, As in bottom sediments of a section from the Hawaiian Islands to the coast of Mexico. In the surface layer and isochronic layers of sediments from biogenic-terrigenous sediments of the Mexico coast to pelagic red clays of the Northeast Basin contents of all studied elements increase, and more sharply for mobile ones - Mn, Mo, Cu, Ni, Co, As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basalt composition enriched in Ti, Fe, Cr, V, P contents of these elements in surface sediments and in sediment mass increase and contents of Mn, Mo, Ni, Co, Cu, As (for the same reason) decrease compared to red clays. An area of hemipelagic and transition sediments is identified; these sediments have much higher contents of Mn, Fe, Cu, Ni, Mo, As, (Ba) than red clays and similar sediments of the Northwest Pacific Ocean. This is due to hydrothermal activity in the tectonically active zone at the northern extension of the East Pacific Rise. Similar character of distribution of the elements in the surface layer and in the isochrone layers of bottom sediments along the most part of the section is shown. Similarity between distribution of the elements in sediments of the western and the eastern parts of the Transpacific section is established.

Occurrence of hiatuses PH and NH 1 through NH 7 in DSDP holes

Miocene paleoceanographic evolution exhibits major changes resulting from the opening and closing of passages, the subsequent changes in oceanic circulation, and development of major Antarctic glaciation. The consequences and timing of these events can be observed in variations in the distribution of deep-sea hiatuses, sedimentation patterns, and biogeographic distribution of planktic organisms. The opening of the Drake Passage in the latest Oligocene to early Miocene (25-20 Ma) resulted in the establishment of the deep circumpolar current, which led to thermal isolation of Antarctica and increased global cooling. This development was associated with a major turnover in planktic organisms, resulting in the evolution of Neogene assemblages and the eventual extinction of Paleogene assemblages. The erosive patterns of two widespread hiatuses (PH, 23.0-22.5 Ma; and NH 1, 20-18 Ma) indicate that a deep circumequatorial circulation existed at this time, characterized by a broad band of carbonate-ooze deposition. Siliceous sedimentation was restricted to the North Atlantic and a narrow band around Antarctica. A major reorganization in deep-sea sedimentation and hiatus distribution patterns occurred near the early/middle Miocene boundary, apparently resulting from changes in oceanic circulation. Beginning at this time, deep-sea erosion occurred throughout the Caribbean (hiatus NH 2, 16-15 Ma), suggesting disruption of the deep circumequatorial circulation and northward deflection of deep currents, and/or intensification of the Gulf Stream. Sediment distribution patterns changed dramatically with the sudden appearance of siliceous-ooze deposition in the marginal and east equatorial North Pacific by 16.0 to 15.5 Ma, coincident with the decline of siliceous sedimentation in the North Atlantic. This silica switch may have been caused by the introduction of Norwegian Overflow Water into the North Atlantic acting as a barrier to outcropping of silica-rich Antarctic Bottom Water. The main aspects of the present oceanic circulation system and sediment distribution pattern were established by 13.5 to 12.5 Ma (hiatus NH 3), coincident with the establishment of a major East Antarctic ice cap. Antarctic glaciation resulted in a broadening belt of siliceous-ooze deposition around Antarctica, increased siliceous sedimentation in the marginal and east equatorial North Pacific and Indian Oceans, and further northward restriction of siliceous sediments in the North Atlantic. Periodic cool climatic events were accompanied by lower eustatic sea levels and widespread deep-sea erosion at 12 to 11 Ma (NH 4), 10 to 9 Ma (NH 5), 7.5 to 6.2 Ma (NH 6), and 5.2 to 4.7 Ma (NH 7).