Organic matter C and N composition and N. pachyderma stable isotope ratios of ODP Hole 188-1166A sediments

We report the results of downhole stable isotopic (d13Corg [organic carbon] and d15N) and elemental measurements (total organic carbon [TOC], total nitrogen [TN], and carbon/nitrogen [C/N]) of sedimentary organic matter (SOM) along with stable isotopic measurements (d18O and d13C) of left-coiling Neogloboquadrina pachyderma planktonic foraminifers from Ocean Drilling Program Site 1166. TOC and TN measurements indicate a large change from organic-rich preglacial sediments with primary organic matter to organic-poor early glacial and glacial sediments, with mainly recycled organic matter. Results of the stable isotopic measurements of SOM show a range of values that are typical of both marine and terrestrial organic matter, probably reflecting a mixture of the two. However, C/N values are mostly high (>15), suggesting greater input and/or preservation of terrestrial organic matter. Foraminifers are only present in glacial/glaciomarine sediments of latest Pliocene to Pleistocene age at Site 1166 (lithostratigraphic Unit I). The majority of this unit has d13Corg and TOC values that are similar to those of glacial sediments recovered at Site 1167 (lithostratigraphic Unit II) on the slope and may have the same source(s). Although the low resolution of the N. pachyderma (s.) d18O and d13C data set precludes any specific paleoclimatic interpretation, downcore variations in foraminifer d18O and d13C values of 0.5 per mil to 1 per mil amplitude may indicate glacial-interglacial changes in ice volume/temperature in the Prydz Bay region.

Late Neogene sediment composition and accumulation rates of ODP Hole 120-751A

Through scanning electron microscope analysis of sediment microfabric, we have evaluated variations in high-resolution shipboard physical properties (index properties and shear strength), sediment components (smear slide determinations), and shore-based calcium carbonate and biogenic silica data from Site 751 (Kerguelen Plateau). The stratigraphic section at this site records a change in biogenic ooze composition from predominantly calcareous (nannofossil) to siliceous (diatom) ooze from ~23 Ma to the present, reflecting expansion of Antarctic water masses during the late Neogene. The profound change in physical properties and sediment character at 40.1 mbsf (~5-6 Ma) evidently records the northward movement of the Polar Front and a change in absolute accumulation rates of sediment at this site. Trends in geotechnical properties with depth at Site 751 allowed us to subdivide the sedimentary column into a number of geotechnical units that reflect changes in depositional and postdepositional processes with time. Geotechnical properties are sensitive to changing sedimentary inputs of primarily siliceous and calcareous microfossils. This allows us to study the physical nature of biostratigraphically-identified hiatuses and variations in environmental conditions linked to the migration of the Polar Front across this region. The analysis of geotechnical properties permits a more detailed division of the sedimentary column than is possible from shipboard lithologic descriptions alone. Our study of the sedimentary microfabric indicates that randomly oriented, elongate pennate diatom valves compose the sediments with highest porosity and water content values, and the lowest density values (wet bulk, dry bulk, and grain density). Conversely, sediments composed of nannofossils and disassociated nannofossil crystallites and little or no siliceous remains have the lowest porosity and water content values, and the highest density values. Samples of mixed siliceous/calcareous composition have intermediate physical property values, but these vary according to the nature of the sedimentary matrix and the state of preservation of individual skeletal elements.

Geochemistry of black shales from Breitbach Creek

Lower Cretaceous sediments are frequently characterized by a well expressed cyclicity. While the processes influencing environments above the carbonate compensation depth (CCD) are reasonably well understood, almost nothing is known about the deep ocean. Cretaceous sub-CCD sediments from the Tethys and Atlantic Oceans typically show rhythmic black/green shale successions. To gain insight into the nature of these black/green shale cycles, we performed detailed geochemical analyses (X-ray fluorescence, Rock-Eval and reactive iron analysis) on a 3 m long section of latest Aptian age. The major-element distribution of the analyzed shale sequence indicates a periodic change from a high-productivity and well-oxygenated green shale mode to a low-productivity oxygen-deficient black shale mode. It is proposed here that the preservation of organic matter was dependent on the strength of salinity-driven deepwater generation. Furthermore, the data show that the Corg content covaries with changes in the detrital composition. Therefore we hypothesize that Tethyan deepwater circulation was sensitive to changes in the monsoonal system. Time series analysis suggests that these changes are periodic in nature, although we are currently unable to prove that the dominant periodicity is related to the precession component of the Milankovitch frequencies.

(Table 1) Summary of accelerator mass spectrometer (AMS) radiocarbon ages in ODP Sites 169-1033 and 169-1034

Continuous coring in Saanich Inlet (Ocean Drilling Program, ODP Leg 169S), British Columbia, Canada, yielded a detailed record of Late Quaternary climate, oceanography, marine productivity, and terrestrial vegetation. Two sites (1033 and 1034) were drilled to maximum depths of 105 and 118 m, recovering sediments ranging in age from 13,300 to less than 300 14C yr. Earliest sediments consist of dense, largely massive, gray glaciomarine muds with dropstones and sand and silt laminae deposited during the waning stages of glaciation. Deposition of organic-rich olive gray sediments began in the fjord about 12,000 14C yr ago, under well-oxygenated conditions as reflected by the presence of bioturbation and a diverse infaunal bivalve community. At about 10,500 14C yr, a massive, gray unit, 40-50 cm thick, was emplaced in a very short span of time. The unit is marked by a sharp lower contact, a gradational upper contact and an abundance of reworked Tertiary microfossils. It has been interpreted as resulting from massive flood events caused by the collapse of glacial dams in the Fraser Valley of mainland British Columbia. Progressively greater anoxia in bottom waters of Saanich Inlet began about 7000 14C yr ago. This is reflected in the preservation of varved sediments consisting of diatomaceous spring-summer laminae and terrigenous winter laminae. Correlation of the sediments was based on: marked lithologic changes, the presence of massive intervals (reflecting localized sediment gravity flow events), the Mazama Ash, occasional thin gray laminae (indicative of abnormal flood events in nearby watersheds), varve counts between marker horizons, and 71 accelerator mass spectrometry (AMS) radiocarbon dates.

Geochemistry and physics on sediment cores from the Peru Basin

We studied preservation/dissolution cycles and paleoproductivity in eight sediment cores from the Peru Basin south of the highly productive surface waters of the eastern equatorial Pacific. Stratigraphy is based on stable oxygen isotopes and on combined magnetostratigraphy and biostratigraphy. Sediment cores which span the last 8 m.y., were retrieved during cruise 79 with RV SONNE close to the carbonate compensation depth (CCD). In general, sediments show Pacific-type carbonate cycles. We interpret a pronounced carbonate peak between 6 and 7 Ma as the result of a western and northern extension of the highly productive Peru Current. Decreased carbonate contents from the late Miocene to the late Pliocene might be associated with a slow contraction of the latitudinal extent of the high-productivity belt north of the study areas. During the Pliocene, carbonate variations showed 400 kyr cycles indicating the growth and decay of ice sheets, which should have been associated with pulsations of the Antarctic ice cap. An abrupt collapse of the carbonate system occurred at 2.4 Ma. Higher frequency variations of the carbonate record indicate the major increase of the northern hemisphere glaciation. During the Quaternary, carbonate fluxes are high during glacials and low during interglacials. Large amplitude variations with long broad minima and maxima, associated with small migrations of the lysocline and the CCD (< 200 m), are indicative of the preservation/dissolution history in the Peru Basin. During the early Pleistocene, climatic forcing by the 41 kyr obliquity cycle is not observed in the carbonate record. During the last 800 kyr, variability in the carbonate record was dominated by the 100 kyr eccentricity cycle. Fluxes of biogenic material (calcium carbonate, organic carbon, opal, and barium) were greatest during glacials, which imply higher productivity and export production of the Peru Current during cold climatic periods. Dissolution was greatest during interglacials as inferred from the relatively poor preservation of planktonic foraminifera and from the low accumulation rate of carbonate. After the Mid-Brunhes Event (400 ka), we observe a plateaulike shift to enhanced dissolution and to intensified productivity.

Pliocene and Pleistocene abundance of siliceous microfossil assemblages in ODP Leg 127 sites

A close examination of the siliceous microfossil assemblages from the sediments of ODP Leg 127, Japan Sea Sites 794, 795, and 797, reveals that upper Pliocene and Pleistocene assemblages have been subjected to more dissolution than have lower Pliocene assemblages. This conclusion is based on semiquantitative observations of samples processed for diatoms and radiolarians. Although preservation of opaline microfossils in some upper Pliocene and Pleistocene samples is better than others, in general, the poorly preserved state of these assemblages supports the notion that opal dissolution, in response to lowered productivity, is responsible for the paucity of siliceous microfossils in upper Pliocene and Pleistocene sediments. The lithological transition from diatomaceous oozes to silts and clays corresponds to a change between dominantly well preserved to more poorly preserved siliceous assemblages, and is termed the late Pliocene Japan Sea opal dissolution transition zone (ODTZ). The base of the ODTZ is defined as the uppermost occurrence of high abundances of moderately to well preserved valves of the diatom Coscinodiscus marginatus. The dissolution transition zone is characterized by partially dissolved refractory assemblages of radiolarians, the presence of C. marginatus girdles, C. marginatus fragments, siliceous sponge spicules, and a general decrease in weakly silicified, less solution resistant diatoms upward in the section. The top of the dissolution transition zone marks the level where whole C. marginatus valves and C. marginatus fragments are no longer present in significant numbers. Dissolution of the late Pliocene and Pleistocene opaline assemblages is attributed mainly to changes in paleoceanographic circulation patterns and decreased nutrient (dissolved silicon) contents of the water column, and possibly dissolution at the sediment/water interface, rather than to post-depositional dissolution or diagenesis. We suggest that the transition from silica-rich to silica-poor conditions in the Japan Sea was due to fluctuations of deep-water exchange with the Pacific through the Tsugaru Strait between 2.9 and 2.3 Ma.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Median grain size and distribution of sand in ODP Hole 108-660A (Fig. 5)

50 m of Middle Eocene pure radiolarian ooze were drilled at ODP Site 660 in the equatorial East Atlantic, 80 km northeast of the Kane Gap. The oozes comprise a 10 m high and 2 km broad mound of seismic reverberations, covered by manganese-rich sediment, and contain trace amounts of sponge spicules and diatoms, negligible organic carbon (0.15%), clay, and variable amounts of pyrite. The yellow to pale brown silty sediments are relatively coarse-grained (30-45% coarser than 6 µm), little bioturbated, and commonly massive or laminated on a cm-scale. The unlithified radiolarian ooze may indicate an interval of high oceanic productivity, probably linked to a palaeoposition of Site 660 close to the equatorial upwelling belt during Middle Eocene time. The absence of organic matter, however, and both the laminated bedding and the mound-like structure of the deposit on the lower slope of a continental rise indicate deposition by relatively intense contour currents of oxygen-rich deep water, which passed through the Kane Gap, winnowed the fine clay fraction, and prevented the preservation of organic carbon. The ooze may be either a contourite-lag deposit, or a contourite accumulation of displaced radiolarians, originating south of the Kane Gap and being deposited in its northern lee, thus documenting the passage of a strong cross-equatorial bottom-water current formed near Antarctica. These Eocene contourites may be an analogue for ancient radiolarites in the Tethyan Ocean.

Geochemistry and soil characteristics of sediment core GeoB4234

Stable isotopes of sedimentary nitrogen and organic carbon are widely used as proxy variables for biogeochemical parameters and processes in the water column. In order to investigate alterations of the primary isotopic signal by sedimentary diagenetic processes, we determined concentrations and isotopic compositions of inorganic nitrogen (IN), organic nitrogen (ON), total nitrogen (TN), and total organic carbon (TOC) on one short core recovered from sediments of the eastern subtropical Atlantic, between the Canary Islands and the Moroccan coast. Changes with depth in concentration and isotopic composition of the different fractions were related to early diagenetic conditions indicated by pore water concentrations of oxygen, nitrate, and ammonium. Additionally, the nature of the organic matter was investigated by Rock-Eval pyrolysis and microscopic analysis. A decrease in ON during aerobic organic matter degradation is accompanied by an increase of the 15N/14N ratio. Changes in the isotopic composition of ON can be described by Rayleigh fractionation kinetics which are probably related to microbial metabolism. The influence of IN depleted in 15N on the bulk sedimentary (TN) isotope signal increases due to organic matter degradation, compensating partly the isotopic changes in ON. In anoxic sediments, fixation of ammonium between clay lattices results in a decrease of stable nitrogen isotope ratio of IN and TN. Changes in the carbon isotopic composition of TOC have to be explained by Rayleigh fractionation in combination with different remineralization kinetics of organic compounds with different isotopic composition. We have found no evidence for preferential preservation of terrestrial organic carbon. Instead, both TOC and refractory organic carbon are dominated by marine organic matter. Refractory organic carbon is depleted in 13C compared to TOC.

Sedimentology and stable isotope record of DSDP Hole 68-503B

Samples from the upper portion of a cyclic pelagic carbonate sediment sequence in Deep-Sea Drilling Project (DSDP) hole 503B (4.0°N, 95.6°W) are the first group to be analyzed for paleoceanographic and paleoclimatic proxy-indicators of ice volume, deep ocean and surface water circulation, and atmospheric circulation in order to resolve the complex origin of the cyclicity. Temporal resolution is taken from the delta18O time scale, most other parameters are calculated in terms of their mass flux to the seafloor. CaCO3 percent in the sediments fluctuates in the well-known Pacific pattern and is higher during glacial times. The fluxes of opal and organic carbon have patterns similar to each other and show a variability of a factor of 2.5 to 4. The longer organic carbon record shows flux maxima during both glacial and interglacial times. The accumulation patterns of both opal and organic carbon suggest that the variability in surface water productivity and/or seafloor preservation of those materials is not simply correlated to glacial or interglacial periods. Eolian dust fluxes are greater during interglacial periods by factors of 2 to 5, indicating that eolian source regions in central and northern South America were more arid during interglacial periods. The record of eolian grain size provides a semiquantitative estimation of the intensity of the transporting winds. The eolian data suggest more intense atmospheric circulation during interglacial periods, opposite to the anticipated results. We interpret this observation as recording the southerly shift of the intertropical convergence zone to the latitude of hole 503B during glaciations.

Radiolaria abundance and faunal indices of ODP Hole 183-1138A, Kerguelen Plateau

Three sites from Ocean Drilling Program (ODP) Leg 183 (Kerguelen Plateau) have been analyzed to document faunal change in high-latitude radiolarians and to compare the faunal change to Eocene-Oligocene climatic deterioration. Radiolarians are not preserved in Eocene sediments. In Oligocene sediments, radiolarian preservation improves in a stepwise manner toward the Miocene. A total of 115 species were found in lower Oligocene samples from Site 1138; all are documented herein. Radiolarian preservation is presumably linked to productivity triggered by climatic cooling during the early Oligocene. Similar patterns of improving preservation through the Eocene/Oligocene boundary are documented from several Deep Sea Drilling Project and ODP sites in the Southern Ocean, indicating a general pattern. In contrast to the Southern Kerguelen Plateau, however, proxies for productivity are more divergent at Site 1138 (Central Kerguelen Plateau). Whereas carbonate dissolution, as indicated by poor preservation of foraminifers and common hiatuses, is very pronounced in the upper Eocene-lowermost Oligocene, the quality of radiolarian and diatom preservation does not significantly increase until the uppermost lower Oligocene. Multiple measures of radiolarian diversity in the Oligocene from Site 1138 closely parallel radiolarian preservation, indicating that preserved radiolarian diversity is controlled by productivity.

Geochemistry, fluxes and nitrogen isotopic composition data of traps LP1 and EBC2-1 and cores GeoB4242-4 and Geo4301-1

We compare total and biogenic particle fluxes and stable nitrogen isotope ratios (d15N) at three mooring sites along a productivity gradient in the Canary Islands region with surface sediment accumulation rates and sedimentary d15N. Higher particle fluxes and sediment accumulation rates, and lower d15N were observed in the upwelling influenced eastern boundary region (EBC) compared to the oligotrophic sites north of Gran Canaria [European Station for Time-Series in the Ocean, Canary Islands (ESTOC]] and north of La Palma (LP). The impact of organic matter degradation and lateral particle advection on sediment accumulation was quantified with respect to the multi-year flux record at the ESTOC. Remineralisation of organic matter in the water column and at the sediment surface resulted in an organic carbon preservation of about 0.8% and total nitrogen preservation of about 0.4% of the estimated export production. Higher total and carbonate fluxes and accumulation rates in the lower traps and surface sediment compared to the upper traps indicated that at least 50% of the particulate matter at the ESTOC was derived from allochthonous sources. Low d15N values in the lower traps of the ESTOC and LP point to a source region influenced by coastal upwelling. We conclude from this study that the reconstruction of export production or nutrient regimes from sedimentary records in regions with strong productivity gradients might be biased due to the mixture of particles originating from autochthonous and allochthonous sources. This could result in an imprint of high productivity signatures on sedimentation processes in oligotrophic regions.

Nannofossil bioevents and biozones of ODP Holes 197-1203A and 197-1204A on Detroit Seamount

Calcareous nannofossils were studied in sedimentary successions recovered from two holes on the Detroit Seamount in the northwestern Pacific Ocean. Preservation of calcareous nannoflora assemblages varies from poor to good throughout the sediments recovered from both Holes 1203A and 1204A. Biostratigraphic investigation allowed the identification of 19 nannofossil zones in Hole 1203A and 7 in Hole 1204A. The sedimentary cover in Hole 1203A ranges from lower Eocene (Zone NP12) to upper Miocene (Zone NN9). The sedimentary interval investigated directly overlying the basalt recovered at Hole 1204A is late Campanian in age (Zones CC22-CC23), and the top of the section is middle Eocene (Zone NP15) in age. Major unconformities were observed in Hole 1204A between upper Campanian (Zones CC22-CC23) and lower Thanetian (Zone NP7) sediments and between upper Thanetian (Zone NP8) and upper Ypresian (Zone NP12) sediments.

Chemistry of upper Eocene microtektites

Late Eocene microtektites and crystal-bearing microkrystites extracted from DSDP and ODP cores from the Atlantic, Pacific, and Indian oceans have been analyzed to address their provenance. A new analysis of Nd and Sr isotopic compositions confirms previous work and the assignment of the uppermost microtektite layer to the North American tektites, which are associated with the 35.5 Ma, 85 km diameter Chesapeake impact structure of Virginia, USA. Extensive major element and Nd and Sr isotopic analyses of the microkrystites from the lowermost layer were obtained. The melanocratic microkrystites from Sites 216 and 462 in the Indian and Pacific oceans possess major element chemistries, Sr and Nd isotopic signatures and Sm-Nd, T CHUR, model ages similar to those of tagamite melt rocks in the Popigai impact structure. They also possess Rb-Sr, T UR, model ages that are younger than the tagamite TCHUR ages by up to ~1 Ga, which require a process, as yet undefined, of Rb/Sr enrichment. These melanocratic microkrystites are consistent with a provenance from the 35.7 Ma, 100 km diameter Popigai impact structure of Siberia, Russia, while ruling out other contemporaneous structures as a source. Melanocratic microkrystites from other sites and leucocratic microkrystites from all sites possess a wide range of isotopic compositions (epsilon (143Nd) values of -16 to -27.7 and epsilon (87Sr) values of 4.1-354.0), making the association with Popigai tagamites less clear. These microkrystites may have been derived by the melting of target rocks of mixed composition, which were ejected without homogenization. Dark glass and felsic inclusions extracted from Popigai tagamites possess epsilon (143Nd) and epsilon (87Sr) values of -26.7 to -27.8 and 374.7 and 432.4, respectively, and T CHUR and T UR model ages of 1640-1870 Ma and 240-1830 Ma, respectively, which require the preservation of initially present heterogeneity in the source materials. The leucocratic microkrystites possess diverse isotopic compositions that may reflect the melting of supra-basement sedimentary rocks from Popigai, or early basement melts that were ejected prior to homogenization of the Popigai tagamites. The ejection of melt rocks with chemistries consistent with a basement provenance, rather than the surface ~1 km of sedimentary cover rocks, atypically indicates a non-surficial source to some of the ejecta. Microkrystites from two adjacent biozones possess statistically indistinguishable major element compositions, suggesting they have a single source. The occurrence of microkrystites derived from a single impact event, but in different biozones, can be explained by: (1) diachronous biozone boundaries; (2) post-accumulation sedimentary reworking; or (3) erroneous biozonation.