Chemical, and Sr and Li isotopic composition of pore fluids and sediments from ODP Leg 170 and Leg 205 sites

Pore fluid and sediment chemical and isotopic data were obtained for samples from Ocean Drilling Program (ODP) Leg 205 Sites 1253, 1254, and 1255 in the Costa Rica subduction zone. The chemical and isotopic data reported here were generated in our shore-based laboratories to complement shipboard inorganic geochemical data. Li isotopic analyses were carried out by L.-H. Chan at Louisiana State University (USA). The data reported herein include fluoride, bromide, rubidium, cesium, and barium concentrations; Li and Sr isotopic compositions in pore fluids; and Rb, Cs, and Ba concentrations in representative bulk sediments. The data also include new pore fluid fluoride and bromide concentrations from corresponding ODP Leg 170 Sites 1039, 1040, and 1043. O.M. Saether's Site 1039 and 1040 fluoride concentration data are shown for comparison. Basal sediment fluoride concentrations and Li and Sr isotope ratios at both Sites 1253 and 1039 show reversals that approach modern seawater values. Br/Cl ratios are, however, conservative throughout the sediment section at Sites 1039 and 1253. The observed sharp F and Br concentration maxima, Rb and K concentration minima, the most radiogenic 87Sr/86Sr ratios, and highest 7Li values along the décollement and fracture zone (Sites 1040, 1043, 1254, and 1255) strengthen the evidence obtained during Leg 170 that a deeply sourced fluid, originating from fluid-rock reactions at ~150°C and corresponding to between 10 and 15 km depth, is transporting solutes to the ocean.

Organic compounds in sediments and pore waters of ODP Sites 117-723 and 117-724

Total organic carbon, amino compounds, and carbohydrates were measured in pore waters and sediments of Pliocene to Pleistocene age from Sites 723 and 724 (ODP Leg 117) to evaluate (1) relationships between organic matter in the sediment and in the pore water, (2) the imprint of lithological variations on the abundance and contribution of organic substances, (3) degradation of amino compounds and carbohydrates with time and/or depth, and (4) the dependence of the ammonia concentration in the pore water on the degradation of amino compounds in the sediment. Total organic carbon concentrations (TOC) of the investigated sediment samples range from 0.9% to 8.7%, and total nitrogen concentrations (TN) from 0.1% to 0.5%. Up to 4.9% of the TOC is contributed by hydrolyzable amino acids (THAA) which are present in amounts between 1.1 and 21.3 µmol/g dry sediment and decrease strongly downhole. Hydrolyzable carbohydrates (THCHO) were found in concentrations from 1.3 to 6.6 ?mol/g sediment constituting between 0.1% and 2.0% of the TOC. Differences between the distribution patterns of monomers in Sites 723 and 724 indicate higher terrigenous influence for Site 724 and, furthermore, enhanced input of organic matter that is relatively resistant to microbial degradation. Lithologically distinct facies close to the Pliocene/Pleistocene boundary yield different organic matter compositions. Laminated horizons seem to correspond with enhanced amounts of biogenic siliceous material and minor microbiological degradation. Total amounts of dissolved organic carbon (DOC) in pore waters vary between 11 and 131 mg/L. Concentrations of DOC as well as of dissolved amino compounds and carbohydrates appear to be related to microbial activity and/or associated redox zones and not so much to the abundance of organic matter in the sediments. Distributions of amino acids and monosaccharides in pore waters show a general enrichment in relatively stable components in comparison to those of the sediments. Nevertheless, the same trend appears between amino acids present in the sediments from Sites 723 and 724 as well as between amino acids in pore waters from these two sites, indicating a direct relation between the dissolved and the sedimentary organic fractions. Different ammonia concentrations in the pore waters of Sites 723 and 724 seem to be related to enhanced release of ammonia from degradation of amino compounds in Site 723.

Mineralogy at DSDP Sites 68-502 and 68-503

Eighty-four sediment samples from four holes at Site 502 and 54 samples from three holes at Site 503 were analyzed for mineral content by semiquantitative X-ray diffraction methods. Site 502 is located in the Western Caribbean, whereas Site 503 lies in the Eastern Pacific (probably on the north flank of the Galapagos Spreading Center). Both sites were chosen to yield continuous core sections for investigations of late Neogene and Quaternary biostratigraphy and magnetostratigraphy and to study events such as the closing of the Isthmus of Panama. Our X-ray diffraction work should provide a framework for further investigations - for example, determination of climatic changes in relationship to clay mineral composition or the influx of terrigeneous sediment components from South America before and after development of the Panama landbridge.

Mineralogic, elemental, and stable isotopic composition of bulk carbonate sediments from ODP Leg 166 sites

An intensive mineralogic and geochemical investigation was conducted on sediments recovered during Ocean Drilling Program Leg 166 from the western Great Bahama Bank at Sites 1006, 1008, and 1009. Pleistocene through middle Miocene sediments recovered from Site 1006, the distal location on the Leg 166 transect, are a mixture of bank-derived and pelagic carbonates with lesser and varying amounts of siliciclastic clays. A thick sequence of Pleistocene periplatform carbonates was recovered near the platform edge at Sites 1008 and 1009. Detailed bulk mineralogic, elemental (Ca, Mg, Sr, and Na), and stable isotopic (d18O and d13C) analyses of sediments are presented from a total of 317 samples from all three sites.

Bulk sedimentology from Sites M0002 and M0004 of the ACEX (Exp302) expedition to the Arctic Ocean

Except for a few discontinuous fragments of the Late Cretaceous/Early Cenozoic climate history and depositional environment, the paleoenvironmental evolution of the pre-Neogene central Arctic Ocean was virtually unknown prior to the IODP Expedition 302 (Arctic Ocean Coring Expedition - ACEX) drilling campaign on Lomonosov Ridge in 2004. Here we present detailed organic carbon (OC) records from the entire ca. 200 m thick Paleogene OC-rich section of the ACEX drill sites. These records indicate euxinic "Black Sea-type" conditions favorable for the preservation of labile aquatic (marine algae-type) OC occur throughout the upper part of the early Eocene and the middle Eocene, explained by salinity stratification due to freshwater discharge. The superimposed short-term ("Milankovitch-type") variability in amount and composition of OC is related to changes in primary production and terrigenous input. Prominent early Eocene events of algae-type OC preservation coincide with global d13C events such as the PETM and Elmo events. The Elmo d13C Event has been identified in the Arctic Ocean for the first time.

Nannofossil biohorizons for ODP Leg 133 sites

Paleontological studies conducted subsequent to the completion of Leg 133 led to refinements of the biostratigraphy for the Leg 133 sites. These biostratigraphic refinements bear on the calculations of sedimentation rates and on the age-depth plots prepared for the Initial Reports volume for Leg 133. To make available the revised data to anyone who may wish to make use of it, the revised biostratigraphic information is presented here in tabulated form. Revised age-depth plots also are presented for all of the sites to facilitate comparison of sedimentation rate curves and to identify intervals where significant changes have been made based on post-cruise studies. The revised age-depth plots include calcareous nannofossils only, and the revised data have been taken from thechapters contributed for this volume (Gartner et al., 1993, doi:10.2973/odp.proc.sr.133.213.1993; Wei and Gartner, 1993, doi:10.2973/odp.proc.sr.133.216.1993). Planktonic foraminifer biostratigraphy revisions became available subsequently and could not be readily incorporated. The age-depth plots for Sites 812 through 818 were made with the (ADP) program provided to ODP by Dave Lazarus.

Carbon chemistry of ODP Leg 105 sites

The quantity and quality of organic carbon of Eocene to Holocene sediments from ODP Sites 645, 646, and 647 were investigated to reconstruct depositional environments. Results were based on organic-carbon and nitrogen determinations, Rock-Eval pyrolysis, and kerogen microscopy. The sediments at Site 645 in Baffin Bay are characterized by relatively high organic-carbon values, most of which range from 0.5% to almost 3%, with maximum values in the middle Miocene. Distinct maxima of organic-carbon accumulation rates occur between 18 and 12.5 Ma and between 3.4 and 0 Ma. At Sites 646 and 647 in the Labrador Sea, organic-carbon contents vary between 0.1% and 0.75%. Cyclic 'Milankovitch-type' changes in organic-carbon deposition imply climate-controlled mechanisms that cause these fluctuations. The composition of organic matter at Site 645 is dominated by terrigenous components throughout the entire sediment sequence. An increased content of marine organic carbon was recorded only in the late-middle Miocene. At Sites 646 and 647, the origin of the organic matter most probably is marine. Oceanic paleoproductivity values were estimated, based on the amount of marine organic carbon. During most of the Neogene time interval at Site 645, productivity was low, i.e., similar or less than that measured in Baffin Bay today. Higher values of up to 150 (200) gC/m**2/y may have occurred only in the Miocene. At Sites 646 and 647, mean paleoproductivity values vary between 90 and 170 gC/m**2/y; i.e., these are also similar to those measured in the Labrador Sea today. Lower values of 40 to 70 gC/m**2/y were estimated for the early Eocene and (middle) Miocene.

Age and chemical composition of apatites from five DSDP and ODP Sites in the Pacific, Atlantic and Indian Oceans

Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ~10° and 70°C over geological time scales of ~15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analyzed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30°C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 µm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30°C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ~30°C. For samples which experienced maximum temperatures between ~30 and 70°C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.

Carbonate record of ODP Leg 167 sites

One of the expected scientific results of Ocean Drilling Program Leg 167 was to reconstruct the Neogene history of biogenic calcium carbonate accumulation in the northeastern Pacific along the California margin (Lyle, Koizumi, Richter, et al., 1997). This aims to constrain inorganic carbon burial rates, deep-water hydrography in the North Pacific, and linkages between deep Atlantic and Pacific circulation and carbonate accumulation or dissolution patterns. Data are presented for four sites. Two of them are located in the California bight-East Cortez Basin (Site 1012: 32°16.970?N 118°23.024?W, 1773 m) and San Nicholas Basin (Site 1013: 32°48.040??, 118°53.992?W, 1564 m). The others are the dedicated Hole 1017E at Site 1017 (34°32.099?N, 121°6.430?W, 955 m) and Site 1019 in the Eel River Basin (41¢X40.972?N, 124°55.975?W, 977 m). Reconstruction of paleo-sea-surface temperatures (SST) by determining the alkenone unsaturation index of the extractable organic matter is an independent technique and helps to verify oxygen-isotope-based estimates. Results from the uppermost 600 cm of the dedicated Hole 1017E are expected to reveal the local temperature history of the last 30 k.y.

Radiocarbon dating, sedimentation rate, granulometry and organic carbon content of ODP Leg 182 sites

This data report presents sedimentological (grain size) and geochemical (X-ray diffraction, total organic carbon, accelerator mass spectrometry radiocarbon, and percent carbonate) information obtained from the western transect (Sites 1132, 1130, and 1134) and the eastern transect (Sites 1129, 1131, and 1127) in the Great Australian Bight during Leg 182. The purpose is to quantify changing rates of sediment accumulation and changes in sediment type from the late Pleistocene and Holocene, in order to relate these changes to the well-known sea level curve that exists for this time frame. Ultimately, these data can be used to more effectively interpret lithologic variations deeper in the Pleistocene succession, which most likely represent orbitally forced sea level events.

Mineralogy of altered whole rocks from ODP Sites 193-1188 and 193-1189, PACMANUS field

Postcruise X-ray diffraction (XRD) data for 95 whole-rock samples from Holes 1188A, 1188F, 1189A, and 1189B are presented. The samples represent alteration types recovered during Leg 193. The data set is incorporated into the shipboard XRD data set. Based on the newly obtained XRD data, distribution of alteration phases were redrawn for Ocean Drilling Program Sites 1188 and 1189.

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.