Stable carbon isotope ratios and the formation of dolomite in ODP Leg 175 sites

We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.

Geochemistry and mineralogy of ODP Leg 107 basalts

During ODP Leg 107, the basement of the Tyrrhenian Sea was drilled at Site 650, located in the Marsili basin, and at Sites 651 and 655, both located in the Vavilov basin. In addition, a lava flow was drilled at Site 654 on the Sardinia rifted margin. Mineral and whole rock major and trace element chemistry, including rare earth element (REE) and Sr and Nd isotopic ratios, were determined in samples of these rocks. Site 654 lava was sampled within uppermost Pliocene postrift sediments. This lava is a basaltic andesite of intraplate affinity, and is analogous to some Plio-Pleistocene tholeiitic lavas from Sardinia. Site 650 basalts, drilled beneath 1.7-1.9-Ma-old basal sediment, are strongly altered and vesicular suggesting a rapid subsidence of the Marsili basin. Based on incompatible trace elements, these basalts show calc-alkaline affinity like some products of the Marsili Seamount and the Eolian arc. The basement of the two sites drilled within Vavilov basin shows contrasting petrologies. Site 655, located along the Gortani ridge in the western part of the basin, drilled a 116-m-thick sequence of basalt flows beneath 3.4-3.6-Ma-old basal sediments. These basalts are chemically relatively homogeneous and show affinity to transitional MORB. Four units consisting of slightly differentiated basaltic lavas, have been identified. Site 655 basalts are geochemically similar to the high Ti lavas from DSDP Leg 42, Site 373 (Vavilov Basin). The basement at Site 651, overlain by 40 m of metalliferous dolostone covered by fossiliferous sediments with an age of 2 Ma, consists of two basalt units separated by a dolerite-albitite intrusive body; serpentinized harzburgites were drilled for 30 m at the base of the hole. The two basalt units of Site 651 are distinct petrochemically, though both show incompatible elements affinity with high-K calc-alkaline/calc-alkaline magmas from Eolian arc. The cpx chemistry and high K/Na ratio of the lower unit lavas suggest a weak alkaline tendency of potassic lineage. Leg 107 basement rock data, together with data from DSDP Site 373 and from dredged samples, indicate that the deepest basins of the central Tyrrhenian Sea are underlain by a complex back-arc basin crust produced by magmas with incompatible element affinities to transitional MORB (Site 655 and DSDP Site 373), and to calc-alkaline and high-K calc-alkaline converging plate margin basalts (Sites 650 and 651). This petrogenetic complexity is in accordance with the back-arc setting of the Vavilov and Marsili basins. Other back-arc basin basalts, particularly those from ensialic basins such as the Bransfield Strait (Antarctica), show a comparable petrogenetic complexity (cf., Sounders and Tarney, 1984).

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

Geochemistry of interstitial gases in sedimentary deposits at DSDP Leg 64 Holes

We analyzed interstitial gases from holes at Sites 474, 477, 478, 479, and 481 in the Gulf of California, using gas chromatography and stable isotope mass spectrometry to evaluate their composition in terms of biogenic and thermogenic sources. The hydrocarbon gas (C1-C5) concentrations were comparable to the shipboard data, and no olefins could be detected. The ?13C data for the CH4 confirmed the effects of thermal stress on the sedimentary organic matter, because the values were typically biogenic near the surface and became more depleted in 12C versus depth in holes at Sites 474, 478, and 481. The CH4 at Site 477 was the heaviest, and in Hole 479 it did not show a dominant hightemperature component. The CO2 at depth in most holes was mostly thermogenic and derived from carbonates. The low concentrations of C2-C5 hydrocarbons in the headspace gas of canned sediments precluded a stable carbon-isotope analysis of their genetic origin.

Neogene magneto- and biostratigraphy of ODP Leg 104 holes

Silicoflagellate assemblages of ODP Leg 104 Neogene sequences are the basis of an interpretation of changes in the Neogene paleoenvironment of the Norwegian Sea. Fluctuations in the percentages of temperature and nutrient-sensitive taxonomic groups document major changes in sea-surface conditions. A brief, but distinct, cooling event occurred at 18.0-17.5 Ma which resulted in the disappearance of Naviculopsis. Following this early Miocene cooling a long period of increasing surface-water temperature occurred, leading up to a thermal high in the early middle Miocene (14.0 Ma). The early late Miocene (10.0-9.0 Ma) was distinctly cooler than the middle Miocene, but warmer than the remainder of the Neogene. Conditions between 13.0 and 10.0 Ma are unrecorded because of a regional hiatus, which is the earliest evidence for an end to the more temperate and stable conditions of the early to middle middle Miocene. A major plunge in temperatures occurred between 8.5 and 7.4 Ma and during the remainder of the late Miocene and Pliocene; from 7.4 to 2.65 Ma subpolar conditions prevailed. Silicoflagellates disappeared, except for sporadic occurrences, at 2.64 Ma with the beginning of dominant glacial sedimentation. Biogenic opal is absent in sediments younger than 0.76 Ma, indicating the dominance of glacial conditions with extensive sea ice.

Dinoflagellates of ODP Leg 104 holes

Dinoflagellate cysts, pollen, and spores were studied from 78 samples of the Eocene to Miocene section of ODP Site 643 at the outer Wring Plateau. Dinoflagellate cysts ranging from less than 1,000 to rarely over 30,000 per gram of sediment in the Paleogene, and generally between 50,000 and 100,000 in the Miocene were present. The shift to conspicuously higher cyst frequencies takes place in the lowermost Miocene section and appears to reflect increased cyst recruitment rather than a change in sedimentation rate. Of the 179 dinoflagellate cyst forms whose ranges were recorded, 129 are known species. Fifteen assemblage zones have been recognized, although the upper Eocene is missing and no substantial lower Eocene was recorded at Site 643. Norwegian Sea and Rockall Plateau zonations were compared with this study. Detailed correlation with existing onshore section zonations was difficult because key zonal species are inadequately represented; however, the middle to upper Miocene zonation established for Denmark is applicable. Pollen and spores occur with relatively low frequencies, and palynodebris is generally absent, in contrast to the observations from DSDP Leg 38. Thirty-nine samples from Eocene to Miocene sediments at Site 642 were studied and correlated with Site 643. A lower Eocene cyst assemblage present in Hole 642D is older than the questionably lower Eocene assemblage from Site 643. Site 642 has a lower Eocene to lower Miocene hiatus.

Sedimentological, petrographical and biostratigraphical characteristics of ODP Leg 190 volcanic ashes and siliceous claystones

Leg 190 was the first of a two-leg program across the Nankai accretionary prism and Trough, offshore Japan, aiming to evaluate existing models for prism evolution and to constrain syntectonic sedimentation, deformation styles, mechanical properties, and prism hydrology (Moore, Taira, Klaus, et al., 2001; Moore et al., 2001). More than 400 volcanic ash and siliceous claystone (altered ash) layers were penetrated and sampled during drilling of the six sites from two transects across the accretionary prism (Sites 1173-1178). In sites from the subducting Shikoku Basin (Sites 1173 and 1177) and in the trench axis (Site 1174), recognition of ash layers and diagenetically altered ashes was initially important in defining major lithostratigraphic units. However, it is clear that understanding the diagenesis of the volcanic ashes has considerable implications for prism evolution, mechanical properties, prism hydrology, geochemistry, and fluid flow in the accretionary prism and associated subducting sediments (cf. Masuda et al., 1996, doi 10.1346/CCMN.1996.0440402). Particle size, chemical composition, temperature, depth of burial, and time are all thought to be factors that may affect volcanic ash diagenesis and preservation (Kuramoto et al., 1992, doi:10.2973/odp.proc.sr.127128-2.235.1992; Underwood et al., 1993, doi:10.2973/odp.proc.sr.131.137.1993). The overall aim of this research is to evaluate factors influencing volcanic ash diagenesis in the Nankai Trough area. This data report presents just the results of the sedimentological and petrographic analysis of the volcanic ashes and siliceous claystones from Sites 1173, 1174, and 1177. It is anticipated that when the results of additional geochemical analysis of these lithologies is available a more meaningful evaluation of factors influencing volcanic ash alteration will be possible.

Organic carbon and nitrogen at DSDP Leg 58 Holes

The sediments penetrated on Leg 58 of the Deep Sea Drilling Project in the Philippine Sea represent long periods of geologic time during which depositional conditions apparently remained very constant. Organic carbon and nitrogen contents of the sediments decrease with increasing depth of burial, before leveling off at minimum values of about 0.05 to 0.10 per cent and 0.01 per cent, respectively. The depth at which the minimum values are reached varies from site to site, but ages of sediments corresponding to the minima are all about 5 m.y. We infer that slow bacterial diagenesis is responsible for the gradual depletion of organic carbon and nitrogen. It is likely that the rate of bacterial metabolism is controlled by the rate of diffusion of electron acceptors within the sediments. These results suggest that bacterial ecosystems in deep-water sediments play a much more important role in diagenesis than has previously been thought.

Calcium carbonate and organic carbon at DSDP Leg 62 Holes

Percent CaCO3 was determined in selected samples aboard the ship by the carbonate-bomb technique (Müller and Gastner, 1971). Results of these analyses are listed in Table 1 and plotted in Figures 1, 3, 4, and 5 as plus signs (+). Samples collected specifically for analyses of CaCO3 and organic carbon were analyzed at three shore-based laboratories. Concentrations of total carbon, organic carbon, and CaCO3 were determined in some samples at the DSDP sediment laboratory, using a Leco carbon analyzer, by personnel of the U.S. Geological Survey, under the supervision of T. L. Valuer. Most of these samples were collected from lithologic units containing relatively high concentrations of organic carbon. Sample procedures are outlined in Boyce and Bode (1972). Precision and accuracy are both ±0.3% absolute for total carbon, ±0.06% absolute for organic carbon, and ±3% absolute for CaCO3.

Silicoflagellate abundances in sediments of ODP Leg 207 sites

The Ocean Drilling Program (ODP) drilled at five sites in the western Atlantic Ocean during Leg 207. The objective of the drilling was to recover samples from the shallow buried Cretaceous and Paleocene sediments on the Demerara Rise off Suriname, South America. These sediments are being studied for a number of paleoceanographic studies of the low-latitude Atlantic off the coast of Suriname (this volume). For this report two sites, Sites 1257 and 1258, were selected for silicoflagellate study because shipboard results suggested these two sites as the only ones with siliceous microfossils of Paleocene-Eocene age. The Demarara Rise is a predominant submarine plateau located off the coast of Suriname and French Guyana. This plateau stretches 380 km along the coast and is 220 km wide. The depth to seafloor along the depth transect drilled during ODP Leg 207 ranges from 1000 to 4500 m, but most of the remainder of the plateau lies in shallow water of 700 m. Much of this area is covered with 2-3 km of sediments. The Demerara Rise is built on rifted Precambrian continental crust. The plateau was one of the last places to be in contact with West Africa during the opening of the Atlantic Ocean (see Shipboard Scientific Party, 2004). Site 1257 (9°27'N, 54°20'W; water depth = 2951 m) is located on a terrace on the northwestern Demerara Rise ~400 km from Suriname. This is the second deepest water depth location drilled during Leg 207. Sediments from this area range in age from Miocene to Albian. This area is part of the transform fault that separated from Central America and western Africa. Three holes were drilled at Site 1257. Site 1258 (9°26'N, 54°43'W; water depth = 3192 m) is located on the western slope of the Demerara Rise ~380 km north of Suriname. This site is the distal and deepest site of the paleoceanographic depth transect drilled across Demerara Rise during Leg 207. The area is located on a ridge of Paleocene sediments cropping out on the seafloor. Three holes were drilled at Site 1258, but only one is studied.

Accumulation rates of sediments and main sedimentary components in ODP Leg 121 holes on Broken Ridge

Broken Ridge, in the eastern Indian Ocean,is overlain by about 1600 m of middle Cretaceous to Pleistocene tuffaceous and carbonate sediments that record the oceanographic history of southern hemisphere mid-to high-latitude regions. Prior to about 42 Ma, Broken Ridge formed the northern part of the broad Kerguelen-Broken Ridge Plateau. During the middle Eocene, this feature was split by the newly forming Southeast Indian Ocean Ridge; since then, Broken Ridge has drifted north from about 55° to 31°S. The lower part of the sedimentary section is characterized by Turonian to Santonian tuffs that contain abundant glauconite and some carbonate. The tuffs record a large but apparently local volcanic input that characterized the central part of Broken Ridge into the early Tertiary. Maestrichtian shallow-water(several hundred to 1000 m depth) limestones and cherts accumulated at some of the highest rates ever documented from the open ocean, 4 to 5 g/cm**2/kyr. A complete (with all biostratigraphic zones) Cretaceous-Tertiary boundary section was recovered from site 752. The first 1.5 m.y. of the Tertiary is characterized by an order-of-magnitude reduction in the flux of biogenic sediments, indicating a period of sharply reduced biological productivity at 55°S, following which the carbonate and silica sedimentation rates almost reach the previous high values of the latest Cretaceous. We recovered a complete section through the Paleocene that contains all major fossil groups and is more than 300 m thick, perhaps the best pelagic Paleocene section encountered in ocean drilling. About 42 Ma, Broken Ridge was uplifted 2500 m in response to the intra-plateau rifting event; subsequent erosion and deposition has resulted in a prominent Eocene angular unconformity atop the ridge. An Oligocene disconformity characterized by a widespread pebble layer probably represents the 30 Ma sea-level fall. The Neogene pelagic ooze on Broken Ridge has been winnowed, and thus its grain size provides a direct physical record of the energy of the southern hemisphere drift current in the Indian Ocean for the past 30 m.y.

Component composition and benthic foraminifera in sediments of ODP Leg 112

Indicators of surface-water productivity and bottom-water oxygenation have been studied for the age interval from the latest Pleistocene to the Holocene at three holes (679D, 680B, and 68IB) located in the center and at the edges of an upwelling cell at approximately 11°S on the Peruvian continental margin. Upwelling activity was maximal at this latitude during d18O Stages 1 (lower part), 3, the upper part of 5, the lower part of 6, and 7, as documented by high diatom abundance. During these time intervals, the bottom water was poorly oxygenated, as documented by low diversity benthic foraminiferal assemblages that are dominated by B. seminuda s.l. Both surface- and bottom-water-circulation patterns appear to have changed rapidly over short time intervals. Due to changes in surface circulation, the intensity of upwelling decreased, thereby decreasing the concentration of nutrients, and reducing the supply of organic matter to the bottom. Radiolarians became more abundant in the surface waters, and the bottom-water environment was less depleted in oxygen, allowing for the establishment of more diverse benthic foraminiferal assemblages. Surface-water productivity was probably minimal during the early part of d18O Stages 5 and 9, as indicated by the increased abundance of planktonic foraminifers and pteropods and their subsequent preservation.

Relative abundances of selected radiolarian species in sediments of ODP Leg 199 sites

During Ocean Drilling Program (ODP) Leg 199, sediments were recovered from eight sites in the Central Pacific. Late Oligocene and early Miocene radiolarians are common to abundant and moderately well preserved in Cores 199-1218A-8H through 11H and 199-1219A-5H through 9H. More than 110 radiolarian species were encountered during this study. Of these species, 100 are identifiable forms and the rest are undescribed or unfamiliar forms. This report presents the relative abundances of described forms from the upper Oligocene to lower Miocene sediments.

Petrography and mineral compositions of gabbros at DSDP Leg 60 Holes

The compositions, mineralogies, and textures of gabbros recovered in polymict breccias in Hole 453 indicate that they are the cumulus assemblages of calc-alkalic crystal fractional on that occurred beneath the West Mariana Ridge. They are among a class of gabbros known only from other calc-alkalic associations (e.g., the Lesser Antilles and the Peninsular Ranges batholith of Southern California) and differ from gabbros of stratiform complexes, ophiolites, and the ocean crust. Particularly abundant in the Hole 453 breccias are olivine-bearing gabbros with extremely calcic Plagioclase (An94-97) but with fairly iron-rich olivines (Fo76-77). Other gabbros contain biotite and amphibole and occur in breccias with fairly high-grade greenschist facies (amphibole-chlorite-stilpnomelane) metabasalts. One unusual gabbro has experienced almost complete subsolidus recrystallization to an assemblage of aluminous magnesio-hornblende, anorthite, and green hercynitic spinel. This reaction, the extremely calcic Plagioclase, the occurrence of biotite and amphibole, and the association with greenschist facies metamorphic rocks suggest that crystallization of the gabbros occurred at elevated P(H2O). Comparisons with other calc-alkalic gabbro suites suggest pressures in excess of 4 kbar (about 12 km depth). The gabbros were exposed by the early stages of opening of the Mariana Trough and imply that considerable uplift may have attended rifting. They were also subjected to hydrothermal alteration after breccia formation, resulting in formation of chlorite, epidote, actinolite, and prehnite. Temperatures of at least 200°C - and probably 350°C - were reached, and most likely could not have been attained without extrusion or intrusion of magmas nearby, even though no such rocks were cored.

Chaetoceros resting spores in Quaternary sediments of ODP Leg 119 sites

During Leg 119 of the Ocean Drilling Program (ODP), Quaternary sediments of the Southern Ocean were examined for the presence and abundance of Chaetoceros resting spores. Six drill sites were occupied along the Kerguelen Plateau. An additional five drill sites were clustered within Prydz Bay, Antarctica. Chaetoceros resting spores were present at all sites examined. These resting spore assemblages were comprised primarily of Chaetoceros neglectus and several unidentified Chaetoceros species. Resting spore assemblages accounted for approximately 20% of the total diatom assemblage (ranging from 0% to 91.4% of any given sample). Quantitative estimates of resting spores demonstrated considerable downcore abundance fluctuations, ranging from 0 to 1.82*10*9 valves/g sediment. The highest spore production rates (3.75*10**12 spores/cm/yr) were found on the northern Kerguelen Plateau (Sample 119-736B-1H-3,35-37 cm). A lack of adequate chronological control at all sites prevented proper between-core comparisons. Mean resting spore abundance, however, appeared highest within the sediments of Prydz Bay and across the northern Kerguelen Plateau. Deep-water stations of the southern Kerguelen Plateau demonstrated the lower spore abundances and a reduction in the percentage contribution of spore to the total diatom assemblage.