Frequency distribution of graded turbidite cycles in DSDP sediments from the Coral Sea Basin and the Sea of Japan

At sites 390 and 392 (Deep Sea Drilling Project, Leg 44) on the Blake nose, thoroughly lithified Lower Cretaceous limestone more than 250 m thick is abruptly overlain by a condensed sequence of Barremian to Eocene pelagic carbonate ooze. The Lower Cretaceous sediments consist of three units: limestone with moldic porosity (base), oolitic limestone, and fenestral limestone. Subaerial diagenesis of the limestone section is recorded by (1) caverns with vertical dimensions of up to 10 m, (2) stalactitic intergranular cement, and (3) meniscus sediment (or cement). Compatible with these subaerial features are mud cracks, fenestral fabrics, intraclasts, and cryptalgal structures. Inasmuch as these shallow-water and tidal-flat deposits are now beneath 2,607 m of sea water (plus 99 m of younger sediments), they serve to dramatize the apparent degree of Barremian and later subsidence of this part of the Atlantic outer continental shelf. Porosity and permeability are high in vuggy samples, which are common in the skelmoldic limestone. Cementation has destroyed most of the extensive primary porosity of the two younger units.

Ba distribution in surface sediments of the Southern Ocean

We present excess Ba (Baxs) data (i.e., total Ba corrected for lithogenic Ba) for surface sediments from a north-south transect between the Polar Front Zone and the northern Weddell Gyre in the Atlantic sector and between the Polar Front Zone and the Antarctic continent in the Indian sector. Focus is on two different processes that affect excess Ba accumulation in the sediments: sediment redistribution and excess Ba dissolution. The effect of these processes needs to be corrected for in order to convert accumulation rate into vertical rain rate, the flux component that can be linked to export production. In the Southern Ocean a major process affecting Ba accumulation rate is sediment focusing, which is corrected for using excess 230Th. This correction, however, may not always be straightforward because of boundary scavenging effects. A further major process affecting excess Ba accumulation is barite dissolution during exposure at the sediment-water column interface. Export production estimates derived from excess 230Th and barite dissolution corrected Baxs accumulation rates (i.e., excess Ba vertical rain rates) are of the same magnitude but generally larger than export production estimates based on water column proxies (234Th-deficit in the upper water column; particulate excess Ba enrichment in the mesopelagic water column). We believe export production values based on excess Ba vertical rain rate might be overestimated due to inaccurate assessment of the Baxs preservation rate. Barite dissolution has, in general, been taken into account by relating it to exposure time before burial depending on the rate of sediment accumulation. However, the observed decrease of excess Ba content with increasing water column depth (or increasing hydrostatic pressure) illustrates the dependence of barite preservation on degree of saturation in the deep water column in accordance with available thermodynamic data. Therefore correction for barite dissolution would not be appropriate by considering only exposure time of the barite to some uniformly undersaturated deep water but requires also that regional differences in degree of undersatuation be taken into account.

Sediment and pore water C and N composition of ODP Holes 201-1227A and 201-1230A

This study addresses the problem of diagenetic fractionation of d15N in sedimentary organic matter by constructing isotopic mass balances for the sedimentary nitrogen and pore water ammonium at two Ocean Drilling Program (ODP) sites, 1227 and 1230. At Site 1230, ammonium production flux integrated through the sedimentary column indicates that >60% of organic matter is lost to decomposition. The d15N of pore water ammonium is <0.7 per mil different from that of the sedimentary organic matter, which implies that very little isotopic fractionation is associated with degradation of organic matter at this site. The constant d15N of the solid-phase sedimentary nitrogen through the whole profile supports this conclusion. Atomic C/N ratios (9-12) indicate that organic matter at this site is primarily of marine origin. At Site 1227, the sedimentary organic matter appears to be a mixture of terrestrial and marine components. Ammonium is ~4 heavier than the organic matter. The observed isotopic enrichment of pore water ammonium relative to the sedimentary nitrogen might indicate either the preferential decomposition of isotopically heavier marine fraction of the organic matter, or possibly, a nonsteady-state condition of the ammonium concentration and d15N profiles. Interpretation of the results at Site 1227 is further complicated by the contribution of ammonium with d15N of ~4 per mil that is diffusing upward from Miocene brines.

Calcareous-nannofossil biostratigraphy at DSDP Leg 57 Holes

As a continuation of the Japan Trench transect commenced by DSDP Leg 56, 10 holes were drilled and 273 cores were recovered while occupying Sites 438, 439, 440, and 441 during Leg 57. At Sites 438 and 439, near the top of the trench inner wall, a principal biostratigraphic objective was to establish a Neogene reference section overlying a pronounced acoustic basement thought to represent continental crust extending outward to this slope environment. At Sites 440 and 441, prime objectives were to distinguish, if present, admixtures of accreted oceanic and non-accreted slope materials, and to recognize repeated or missing sections resulting from the accretionary process. This report summarizes the nannofossil biostratigraphy of the upper lower Miocene to Pleistocene sequences of Leg 57 cores. Insufficient occurrences in the lowermost Miocene, presumed upper Oligocene, and upper Cretaceous sequences at Sites 438 and 439 precluded age determinations for these intervals based on nannoliths. All but a few samples from Site 441 were barren, and in general Leg 57 nannofossil assemblages were too modified by dissolution and diagenesis to permit meaningful paleoclimatologic or paleobiogeographic conclusions to be drawn.

Stable isotope record and age model for sapropel stratigraphy of ODP Site 160-967

Stable oxygen isotope data from four holes drilled at the Ocean Drilling Program Site 967, which is located on the lower northern slope of the Eratosthenes Seamount, provide a continuous record of Eastern Mediterranean surface-water conditions during the last 3.2 Ma. A high-resolution stratigraphy for the Pliocene-Pleistocene sequence was established by using a combination of astronomical calibration of sedimentary cycles, nannofossil stratigraphy, and stable oxygen isotope fluctuations. Sapropels and color cycles are present throughout the last 3.2 Ma at Site 967, and their ages, as determined by calibration against the precessional component of the astronomical record, are consistent with those estimated for the sapropels of the classical land-based marine sequences of the Punta Piccola, San Nicola, Singa, and Vrica sections (southern Italy). The Site 967 oxygen isotope record shows large amplitude fluctuations mainly caused by variations in surface water salinity throughout the entire period. Spectral analysis shows that fluctuations in the d18O record were predominantly influenced by orbital obliquity and precessional forcing from 3.2 to 1 Ma, and all main orbital frequencies characterize the d18O record for the last million years. The start of sapropel formation at 3.2 Ma indicates a possible link between sapropel formation and the build up of northern hemisphere ice sheets. The dominance of the obliquity cycle in the interval from 3.2-1 Ma further points to the sensitivity of Eastern Mediterranean climate to the fluctuations in the volume of Arctic ice sheets. An intensification of negative isotope anomalies at Site 967, relative to the open ocean, supports a link between high run-off (during warm periods) and sapropel formation. freshwater input would have inhibited deep-water formation, which led to stagnation of deeper waters. Comparison with the land sections also confirms that differential preservation and diagenesis play a key role in sapropel occurrence.

Planktonic foraminifers from Oligocene to Pleistocene sediments of DSDP Leg 92 sites

Leg 92 of the Deep Sea Drilling Project cored sediments containing calcareous microfossils at six sites along 19°S latitude in the South Pacific Ocean. Shipboard examination of these sediments revealed planktonic foraminifers of uppermost Oligocene through Pleistocene age that were identified and assigned to biostratigraphic zones according to the tropical zonation scheme of Blow (1969). Preservation of planktonic foraminifers in the sites from Leg 92 has been affected by the position of each site with respect to the lysocline and calcium carbonate compensation depth (CCD) at the time of deposition, depth of burial, and sediment accumulation rate (rate of burial). An additional factor may also be important, especially in the sediments deposited immediately above basement. Evidence of poor preservation in basal sediments of Holes 600C and 601, which have always been shallower than both the lysocline and the CCD, suggests that hydrothermal solutions circulating within young oceanic crust may penetrate the overlying sediments and affect the preservation of calcareous microfossils deposited there.

Chemical composition of Fe-Mn nodules and crusts from the Pacific Ocean

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.

Upper Cretaceous sediments of ODP Hole 122-762C

Well-developed Campanian to Maestrichtian pelagic cyclic sediments were recovered from Hole 762C on the Exmouth Plateau, off northwest Australia, during Ocean Drilling Program Leg 122. The cycles consist of nannofossil chalk (light beds) and clayey nannofossil chalk (dark beds). Both light and dark beds are strongly to moderately bioturbated, alternate on a decimeter scale, and exhibit gradual boundaries. Bioturbation introduces materials from a bed of one color into an underlying bed of another color, indicating that diagenesis is not responsible for the cyclicity. Differences in composition between the light and dark beds, revealed by calcium carbonate measurement and X-ray diffraction analysis, together with trace fossil evidence, indicate that the cycles in the sediments are a depositional feature. Diagenetic processes may have intensified the appearance of the cycles. Spectral analysis was applied to the upper Campanian to lower Maestrichtian cyclic sediments to examine the regularity of the cycles. Power spectra were calculated from time series using Walsh spectral analysis. The most predominant wavelengths of the color cycles are 34-41 cm and 71-84 cm. With an average sedimentation rate of 1.82 cm/k.y. in this interval, we found the time durations of the cycles to be around 41 k.y. and 21 k.y., respectively, comparable to the obliquity and precession periods of the Earth's rotation, which strongly suggests an orbital origin for the cycles. On the basis of sedimentological evidence and plate tectonic reconstruction, we propose the following mechanism for the formation of the cyclic sediments from Hole 762C. During the Late Cretaceous, when there was no large-scale continental glaciation, the cyclic variations in insolation, in response to cyclic orbital changes, controlled the alternation of two prevailing climates in the area. During the wetter, equable, and warmer climatic phases under high insolation, more clay minerals and other terrestrial materials were produced on land and supplied by higher runoff to a low bioproductivity ocean, and the dark clayey beds were deposited. During the drier and colder climatic phases under low insolation, fewer clay minerals were produced and put into the ocean, where bioproductivity was increased and the light beds were deposited.

Sulfur isotopic variations in nodular and disseminated pyrite at DSDP Hole 93-603B

Analyses of modern marine sediments have suggested that availability and type of organic matter, sedimentation rate, and openness of the sulfate system influence the degree of isotopic fractionation between seawater sulfate and sedimentary iron sulfides. Isotopic studies of ancient sulfides should, therefore, provide insights into conditions of deposition and early diagenesis. Analysis of d34S of disseminated pyrite from Cretaceous sediments of Hole 603B yielded fractionations relative to coeval seawater sulfate ranging from 40 to 55 per mil, which are within the range for modern oxic marine sediments reported by others. Sulfur/carbon ratios are similar to those found from modern marine sediments and suggest that disseminated pyrite formation was dependent upon available organic carbon. These results imply that depositional and early diagenetic conditions during the Cretaceous in Hole 603B were similar to those occurring in initially oxic marine environments today. Macroscopic (nodular) pyrite from Hole 603B is isotopically variable (d34S values = - 48 to + 33 per mil), but generally more positive than disseminated pyrite. The isotopic evidence suggests that macroscopic pyrite formed during late stages of sulfate reduction in a system closed with respect to sulfate. However, detailed analyses of large pyrite nodules did not yield a consistent pattern of isotopic variation from center to rim.

Pore water geochemistry of ODP Hole 169-1037B and Site 196-1038

Data were presented to compare pore fluids from Sites 1037 and 1038 in the Escanaba Trough, Gorda Ridge. Site 1037 constitutes the reference site, and Site 1038 is the hydrothermally affected site. The program was undertaken for two purposes: (1) to make a detailed analysis of the halide chemistry of these two sites, with the specific aim of discerning any potential differences in the generation of dissolved halides as a result of sediment diagenesis in these drill sites and (2) to investigate the geochemistry of Ba2+ and Mn2+ at these two sites to discover potential hydrothermal effects reflected in the concentration-depth distributions of these elements.

Calcareous nannofossil stratigraphy, mass accumulation rates and bulk density of sediments from ODP Leg 173 sites

Drilling on the Iberia Abyssal Plain during Ocean Drilling Program Leg 173 allowed us to recover Upper Cretaceous through Paleocene sediments at Sites 1068 and 1069 and only upper Paleocene sediments at Site 1067, which expands considerably the Upper Cretaceous to Paleocene record for this region. Of these three sites, Site 1068 recovered uppermost Cretaceous sediments as well as the most complete Paleocene record, whereas Site 1067 yielded only uppermost Paleocene sediments (Zone CP8). Site 1069 provided a rather complete upper Campanian through Maastrichtian section but a discontinuous Paleocene record. After a detailed calcareous nannofossil biostratigraphy was documented in distribution charts, we calculated mass accumulation rates for Holes 1068A and 1069A. Sediments in Hole 1068A apparently record the final stages of burial of a high basement block by turbidity flows. Accumulation rates through the Upper Cretaceous indicate relatively high rates, 0.95 g/cm**2/k.y., but may be unreliable because of the lack of datum points and/or possible hiatuses. Accumulation rates in the Paleocene section of Hole 1068A fluctuated every few million years from lower (~0.35 g/cm**2/k.y.) to higher rates (~0.85 g/cm**2/k.y.) until the latest Paleocene, when rates increased to an average of ~2.0 g/cm**2/k.y. Mass accumulation rates for the Upper Cretaceous in Hole 1069A indicate a steady rate of ~0.60 g/cm**2/k.y. from 75 to 72 Ma. There may have been one or more hiatuses between 72 and 68 Ma (combined Zone CC24 through Subzone CC25b), as indicated by the very low accumulation rate of 0.15 g/cm**2/k.y. The Paleocene section of Hole 1069A does not show the same continuous record, which may result from fluctuations in the carbonate compensation depth and poor recovery (average = 40%). Zones CP4 and CP5 are missing within a barren interval; this and numerous other barren intervals affect the precision of the nannofossil zonation and calculation of mass accumulation rates. However, in spite of these missing zones, mass accumulation rates do not seem to indicate the presence of hiatuses as the rates for this barren interval average ~1.0 g/cm**2/k.y. This study set out to test the hypothesis that a reliable biostratigraphic record could be constructed from sediments derived from turbidity flows deposited below the carbonate compensation depth. As illustrated here, not only could a reliable biostratigraphic record be determined from these sediments, but sedimentation and mass accumulation rates could also be determined, allowing inferences to be drawn concerning the sedimentary history of this passive margin. The reliability of this record is confirmed by independent verification by the establishment of a magnetostratigraphy for the same cores.

Carbohydrates in waters and sediments

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.

(Table 1) Calcite, siderite, and stable isotopes d13C and d18O at DSDP Hole 93-603B

Diagenesis of the fine-grained, feldspathic sandstones in the Lower Cretaceous submarine fan complex cored in DSDP Hole 603B can be considered to have occurred in three stages: (1) replacement of matrix and framework grains by pyrite, siderite, phillipsite (?), and particularly by ferroan calcite; (2) dissolution of ferroan calcite and feldspars to produce secondary macroporosity; and (3) development of sparse feldspar and quartz overgrowths, and authigenic modification of remnant matrix. Only ferroan calcite is a volumetrically important diagenetic mineral phase (up to 50 vol.%). Matrix in thin sandstone turbidite deposits has been extensively replaced by ferroan calcite. Carbon stable isotope data suggest that organic diagenesis had only a minor influence on calcite precipitation. Oxygen stable isotope data indicate that the minimum average calcite precipitation temperature was 40° C. Preliminary calculations show that steadystate diffusion of Ca+ + from the dissolution of nannoplankton skeletal material in the interbedded pelagic marls to the associated sandstones is a feasible transport mechanism. A thick sandstone unit from 1234-1263 m sub-bottom is extensively replaced by calcite near the upper and lower contacts. Farther into the sand body away from the contacts, the sandstone has good secondary porosity resulting from the dissolution of ferroan calcite that partially replaced matrix and framework grains. The central portion of the thick sand appears to be a channel with high-energy clean sand. We believe that the channel provided a conduit for focused flow of diagenetic compactional fluids responsible for dissolution. Focused flow may be the result of the earlier lithification of the pelagic limestones and thin-bedded sandstones which, then formed vertical permeability barriers. Calcite dissolution has occurred and may still be occurring at temperatures less than 65°C.

Geochemistry on interstitial water of 5 sediment profiles from the Persian Gulf

The landward part of the 7 km wide sabkha at Umm Said, SE Qatar, is filled with a stagnant brine virtually saturated with halite. Recent dolomite occurs in the sabkha sediments, the quantity being fully accounted for by the amount of Mg++ ions lost from the interstitial brine. The existence of a reflux system in the seaward parts of the sabkha was established. It was not, however, possible to gi ve any unequivocal demonstration of the effect of this potential system for dolomitization . Although both a reflux mechanism and Recent dolomite formation occur in this tidal flat, the first process has apparently not influenced the second sufficiently to permit the demonstration of reflux dolomitization.

Composition of native Cu, Cu isotope and mineral analysis from different samples of ODP and DSDP

Ocean drilling has revealed that, although a minor mineral phase, native Cu ubiquitously occurs in the oceanic crust. Cu isotope systematics for native Cu from a set of occurrences from volcanic basement and sediment cover of the oceanic crust drilled at several sites in the Pacific, Atlantic and Indian oceans constrains the sources of Cu and processes that produced Cu**0. We propose that both hydrothermally-released Cu and seawater were the sources of Cu at these sites. Phase stability diagrams suggest that Cu**0 precipitation is favored only under strictly anoxic, but not sulfidic conditions at circum-neutral pH even at low temperature. In the basaltic basement, dissolution of primary igneous and potentially hydrothermal Cu-sulfides leads to Cu**0 precipitation along veins. The restricted Cu-isotope variations (delta 65Cu = 0.02-0.19 per mil) similar to host volcanic rocks suggest that Cu**0 precipitation occurred under conditions where Cu+-species were dominant, precluding Cu redox fractionation. In contrast, the Cu-isotope variations observed in the Cu**0 from sedimentary layers yield larger Cu-isotope fractionation (delta 65Cu = 0.41-0.95 per mil) suggesting that Cu**0 precipitation involved redox processes during the diagenesis, with potentially seawater as the primary Cu source. We interpret that native Cu precipitation in the basaltic basement is a result of low temperature (20°-65 °C) hydrothermal processes under anoxic, but not H2S-rich conditions. Consistent with positive delta 65Cu signatures, the sediment cover receives major Cu contribution from hydrogenous (i.e., seawater) sources, although hydrothermal contribution from plume fallout cannot be entirely discarded. In this case, disseminated hydrogenous and/or hydrothermal Cu might be diagenetically remobilized and reprecipitated as Cu**0 in reducing microenvironment.