isotopic composition of gases and interstitial fluides of ODP Site 104-644

Pleistocene- to middle Miocene-age sediment was drilled at Site 341 (67? 20.1'N, 6? 06.6'E) on the inner Voring Plateau during Leg 38 of the Deep Sea Drilling Project (DSDP). In 1985, the Ocean Drilling Program (ODP) returned to the inner Wring Plateau near Site 341 and drilled a new hole at Site 644 (66° 40.7'N, 4° 34.6'E) as part of a transect to study Norwegian Sea paleoenvironments. In Hole 341, gas expansion pockets formed in cores which were recovered from depths below 50 m. This gas was characterized as predominantly methane with delta13C values in the range of -87 to -77 per mil (Morris, 1976, doi:10.2973/dsdp.proc.38.124.1976). At Site 644, sediment gas and pore-water samples were obtained to study the geochemistry of methanogenesis. Of particular interest is the possibility that methane hydrate might be present in these sediments.

Chemical composition of sediments and interstitial waters in the Gulf of California and Eastern Pacific

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.

Chemistry of interstitial waters of ODP Leg 112 samples

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13?S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to ~20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of 87Sr/86Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to -200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

Organic geochemistry of interstitial waters at DSDP Holes 64-474 and 64-479

Studies of the nature and amount of dissolved organic matter (DOM) in pore-water solutions have been confined mostly to recent sediments (Henrichs and Farrington, 1979; Krom and Sholkovitz, 1977; Nissenbaum et al., 1972). The analyses of organic constituents in interstitial waters have not been extended to sediment depths of more than 15 meters (Starikova, 1970). Large fluctuations in organic contents of near-bottom interstitial fluids suggest that organic compounds may provide insight into the chemical and biological processes occurring in the sedimentary column. Gradients in inorganic ion concentrations have been used as indicators of diagenesis of organic matter in deep sediments and interstitial waters. Shishkina (1978) attributed the occurrence of iodine and Cl/Br ratios that deviated from the value of seawater to the breakdown of organic matter and the liberation of bromide during mineralization. Sulfate depletion and maxima in ammonia concentrations were interpreted to be a consequence of sulfate reduction reactions in pore fluids, even at depths of more than 400 meters (Miller et al., 1979; Manheim and Schug, 1978).The purpose of this chapter is to study organic carbon compounds dissolved in interstitial waters of deep sediments at Sites 474 and 479.

Sulphur geochemistry of interstitial waters and squeeze cake samples of ODP Leg 181 sites

Seventy-nine interstitial water samples from six sites (Ocean Drilling Program Sites 1119-1124) from the southwestern Pacific Ocean have been analyzed for stable isotopes of dissolved sulfate (34S), along with major and minor ions. Sulfate from the interstitial fluids (34S values between +20.7 and +57.5 vs. the Vienna-Canyon Diablo troilite standard) was enriched in 34S with respect to modern seawater (34S +20.6), indicating that differing amounts of microbial sulfate reduction took place at all investigated sites. Microbial sulfate reduction was found at all sites, the intensity depending on the availability of organic matter, which is controlled by paleosedimentation conditions (e.g., sedimentation rate and presence of turbidites). In addition, total reduced inorganic sulfur (essentially pyrite) as a product of microbial sulfate reduction was quantified in selected sediments from Site 1119.

Amino acid concentrations in interstitial waters from ODP Sites 113-689 and 113-690

Biogenic calcareous and siliceous sediments were drilled at ODP Sites 689 and 690 on the Maud Rise, Antarctic Ocean. We analyzed dissolved combined amino acids (DCAA) and dissolved free amino acids (DFAA) in interstitial waters in order to characterize the amino acids in dissolved organic matter. The DFAA was predominant over the DCAA in interstitial waters at Sites 689 and 690, which contradicted the previous results from interstitial water and seawater studies. The DCAA in the interstitial waters probably originated from calcareous biogenic debris with less amounts of siliceous debris. Although glutamic acid constituted 41% of the total concentration of DCAA, it accounted for only 1% of the total concentration of DFAA due to the adsorption and/or reaction with biogenic carbonate. Ornithine, a nonprotein amino acid, is a decomposed product of arginine and made up 17 mol% of the total DFAA and. The total hydrolyzable amino acids (=DCAA + DFAA) accounted for 5 to 28% of the dissolved organic carbon (DOC) concentration, which implied that high molecular weight organic matter was a major contributor for the DOM (dissolved organic matter) in interstitial waters. Fairly positive correlation between the dissolved manganese and the total DCAA values suggested that the redox condition plays a significant role in controlling the total DCAA content. A small decrease in the sulfate concentration in the interstitial waters from both sites suggested fairly low microbial activity by sulfate-reducing bacteria.

Interstitial water chemistry at DSDP Leg 74 Holes

Interstitial water studies from sites drilled during a transect of the Walvis Ridge indicate that concentration increases in calcium and decreases in magnesium toward and into the basement. These trends can be understood principally in terms of reactions taking place in Layer 2 of the oceanic crust. At Site 525, however, some removal of magnesium occurs within the sediment column. Concentration maxima of dissolved strontium clearly indicate that carbonate recrystallization occurs throughout the carbonate sediments, and studies of the Sr/Ca ratio in carbonates indicate that in chalks and limestones recrystallization is essentially complete. Predictions of dissolved strontium maxima generally fail; this can be understood as removal of strontium in basal sediments and/or basalts.

Interstitial-water chemistry of ODP Leg 119 sites

Ocean Drilling Program inorganic geochemistry procedures routinely overlook more than 99% of the sediment column. Present and past biogeochemical reactions alter the sediment record; however, most of these reaction zones are bypassed by the normal methods where samples are collected every 30 m. A new approach to increase resolution was introduced during Leg 119. Ten milliliters of sediment provided interstitial-water samples for ammonia, silica, sulfate, magnesium, and calcium analyses. The new method introduced some systematic differences in concentrations, as well as some decrease in precision. A number of advantages, however, may warrant using the method in some instances. In cases where routine interstitial-water data showed anomalous results, core sections were retrieved from the storage facility and resampled. The new high-resolution procedure was used to provide water samples in cases were water contents were low and routine squeezing could not recover pore water.

Composition of sediments, hydrothermal manifestations, interstitial waters, and aeolian material from the TAG Hydrothermal Field and Central Atlantic

The book is devoted to regularities of spatial distribution, mineralogy and geochemistry of hydrothermal and hydrothermal-sedimentary manifestations of the Mid-Atlantic Ridge rift zone.

Amino acids and carbohydrates in sediments and interstitial waters of ODP Site 112-681

Total organic carbon (TOC), dissolved organic carbon (DOC), total hydrolyzable amino acids (THAA), amino sugars (THAS), and carbohydrates (THCHO) were measured in sediments and interstitial waters from Site 681 (ODP Leg 112). TOC concentrations vary between 0.75% and 8.2% by weight of dry sediment and exhibit a general decrease with depth. DOC concentrations range from 6.1 to 49.5 mg/L, but do not correlate with TOC concentrations in the sediment. Amino compounds (AA and AS) and sugars account for 0.5% to 8% and 0.5% to 3% of TOC, respectively, while amino compounds make up between 2% and 27% of total nitrogen. Dissolved hydrolyzable amino acids (free and combined) and amino sugars were found in concentrations from 3.7 to 150 µM and from 0.1 to 3.7 µM, respectively, and together account for an average of 8.5% of DOC. Dissolved hydrolyzable carbohydrates are in the range of 6 to 49 µM. Amino acid spectra are dominated by glycine, alanine, leucine, and phenylalanine; nonproteinaceous amino acids (gamma-amino butyric acid, beta-alanine, and ornithine) are enriched in the deeper part of the section, gamma-amino butyric acid and beta-alanine are thought to be indicators of continued microbial degradation of TOC. Glycine, serine, glutamic acid, alanine, aspartic acid, and ornithine are the dominating amino compounds in the pore waters. Spectra of carbohydrates in sediments are dominated by glucose, galactose, and mannose, while dissolved sugars are dominated by glucose and fructose. In contrast to the lack of correlation between abundances of bulk TOC and DOC in corresponding interstitial waters, amino compounds and sugars do show some correlation between sediments and pore waters: A depth increase of aspartic acid, serine, glycine, and glutamic acid in the pore waters is reflected in a decrease in the sediment, while an enrichment in valine, iso-leucine, leucine, and phenylalanine in the sediment is mirrored by a decrease in the interstitial waters. The distribution of individual hexoseamines appears to be related to zones of bacterial decomposition of organic matter. Low glucoseamine to galactoseamine ratios coincide with zones of sulfate depletion in the interstitial waters.

87Sr/86Sr ratios of planktonic foraminifers and interstitial waters at DSDP Hole 90-593

Detailed profiles of the Sr isotopic compositions of fossil planktonic foraminifers and interstitial waters have been measured from DSDP Site 593 to determine the Sr isotopic composition of seawater during the last 40 m.y. Foraminiferal recrystallization was assessed through scanning electron microscopy (SEM) and Sr/Ca ratios. Foraminifers were shown to be well preserved. Results document that the seawater 87Sr/86Sr has increased continuously but not uniformly, since the latest Eocene.

Concentrations of phosphates and silicon in near-bottom and interstitial waters of the Baltic Sea

Fine structure of vertical distributions of phosphorus and silicon in near-bottom layers and interstitial waters is studied in different regions of the Baltic Sea (Gulf of Finland, Bornholm area, Gotland trench). Data obtained are used to calculate fluxes of mineral forms of phosphorus and silicon in exchange processes between sediments and the near-bottom water layer. Depending on sediment types, values of nutrient fluxes vary from 9.8 to 632.6 µg-at/m**2/day for phosphorus and from 232.4 to 1881.1 µg-at/m**2/day for silicon. Fluxes calculated for different regions are compared.

Amino acids in the interstitial waters from ODP Hole 113-695A

Site 695 lies on the southeast margin of the South Orkney microcontinent on the northern margin of the Weddell Sea, at 62°23.48'S, 43°27.10'W in 1305 m water depth. The inorganic properties of interstitial waters at this site, including sulfate reduction, biogenic methane production, and high concentrations of ammonia and phosphate, imply high microbial activity. However, no clear relationship between amino acid composition and concentration and the type of microbial activity (e.g., sulfate reduction or methane production) can be identified. The THAA (total hydrolyzable amino acids) values range between 2.45 and 17.31 µmol/L, averaging 7.14 µmol/L. The mean concentrations and relative abundance values of acidic, basic, neutral, aromatic, and sulfur-containing amino acids are 1.34 (18%), 1.09 (15%), 3.93 (54%), 0.50 (8%), and 0.02 (0%) µmol/L, respectively. Glycine is the most abundant amino acid residue, with serine, glutamic acid, and ornithine next. The DFAA (dissolved free amino acids) values range from 0.10 to 12.73 µmol/L, averaging 4.07 µmol/L. The acidic, basic, neutral, aromatic, and sulfurcontaining amino acids are on average 0.21, 0.79, 2.56, 0.41, and 0.01 µmol/L, respectively. The relative abundances of acidic, basic, neutral, and aromatic amino acids average 4%, 18%, 58%, and 15%, respectively. Predominance of DFAA over DCAA (dissolved combined amino acids) in interstitial waters of Lithologic Units I and II is contrary to the predominance of DCAA over DFAA in other interstitial waters and seawater. The comparison of amino acid compositions between DCAA and siliceous plankton suggests that the DCAA in interstitial waters originally comes from amino acids derived from siliceous plankton. However, other sources which are much enriched in glutamic acid contribute to the DCAA composition.