Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Carbon isotopic composition of dissolved CO2, CO2 gas and methane in sediments from ODP Leg 172 sites

Carbon isotopic data of interstitial dissolved CO2 (CO2), CO2 gas, and methane show that a variety of microbial diagenetic processes produce the observed isotopic trends. Anaerobic methane oxidation (AMO) is an important process near the sulfate-methane interface (SMI) that strongly influences the isotopic composition of CO2 in the sulfate reduction and upper methanogenic zones, which in turn impacts methane isotopic composition. Dissolved CO2 and methane are maximally depleted in 13C near the SMI, where 13C values are as light as -31.8 and -101 PDB for CO2 and methane, respectively. CO2 reduction links the CO2 and methane pools in the methanogenic zone so that the carbon isotopic composition of both pools evolves in concert, generally showing increasing enrichments of 13C with increasing depth. These isotopic trends mirror those within other methane-rich continental rise sediments worldwide.

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.

Stable carbon and oxygen isotope record of diagenetic carbonates from the New Jersey shelf

Carbon cycling is an important but poorly understood process on passive continental margins. In this study, we use the ionic and stable isotopic composition of interstitial waters and the petrology, mineralogy, and stable isotopic composition of authigenic carbonates collected from Ocean Drilling Program (ODP) Leg 174A (Sites 1071 and 1072) to constrain the origin of the carbonates and the evolution of methane on the outer New Jersey shelf. The pore fluids of the New Jersey continental shelf are characterized by (1) a fresh-brackish water plume, and (2) organic matter degradation reactions, which proceed through sulfate reduction. However, only minor methanogenesis occurs. The oxygen isotopic composition of the pore fluids supports a meteoric origin of the low salinity fluids. Authigenic carbonates are found in nodules, thin (~1-cm) layers, and carbonate cemented pavements. Siderite is the most common authigenic carbonate, followed by dolomite and calcite. The oxygen isotopic composition of the authigenic carbonates, i.e. 1.3-6.5 per mil PeeDee Belemnite (PDB), indicates an origin in marine pore fluids. The carbon isotopic composition of dolomite cements range from -16.4 to -8.8 per mil PDB, consistent with formation within the zone of sulfate reduction. Siderite d13C values show a greater range (-17.67-16.4 per mil), but are largely positive (mean=2.8 per mil) and are interpreted to have formed throughout the zone of methanogenesis. In contrast, calcite d13C values are highly negative (as low as -41.7 per mil)and must have formed from waters with a large component of dissolved inorganic carbon derived from methane oxidation. Pore water data show that despite complete sulfate reduction, methanogenesis appears not to be an important process presently occurring in the upper 400 m of the outer New Jersey shelf. In contrast, the carbon isotopic composition of the siderites and calcites document an active methanogenic zone during their formation. The methane may have been either oxidized or vented from shelf sediments, perhaps during sea-level fluctuations. If this unaccounted and variable methane flux is an areally important process during Neogene sea-level fluctuations, then it likely plays an important role in long-term carbon cycling on passive continental margins

Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

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.

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.

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 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.