Composition of swamp waters from the lower Tom' River Basin

New data on chemical and trace component compositions of acidic and low acidic swamp waters and other types of low mineralized waters are reported in the paper. Special attention is paid to dissolved organic compounds: fulvic and humic acids, bitumen, and hydrocarbons. For the first time detailed data on organic trace components (alkanes, pentacyclic terpenoids, steranes, alkylbenzenes, naphthalenes, phenanthrenes, tetraarenes, etc.) in the swamp waters of the Western Siberia: are reported.

Geochemistry and isotopes at DSDP Site 76-533

Concentrations and d34S and d13C values were determined on SO4, HCO3, CO2, and CH4 in interstitial water and gas samples from the uppermost 400 m of sediment on the Blake Outer Ridge. These measurements provide the basis for detailed interpretation of diagenetic processes associated with anaerobic respiration of electrons generated by organic- matter decomposition. The sediments are anaerobic at very shallow depths (<1 m) below the seafloor. Sulfate reduction is confined to the uppermost 15 m of sediment and results in a significant outflux of oxidized carbon from the sediments. At the base of the sulfate reduction zone, upward-diffusing CH4 is being oxidized, apparently in conjunction with SO4 reduction. CH4 generation by CO2 reduction is the most important metabolic process below the 15-m depth. CO2 removal is more rapid than CO2 input over the depth interval from 15 to 100 m, and results in a slight decrease in HCO3 concentration accompanied by a 40 per mil positive shift in d13C. The differences among coexisting CH4, CO2, and HCO3 are consistent with kinetic fractionation between CH4 and dissolved CO2, and equilibrium fractionation between CO2 and HCO3. At depths greater than 100 m, the rate of input of CO2 (d13C = -25 per mil) exceeds by 2 times the rate of removal of CO2 by conversion to CH4 (d13C of -60 to -65 per mil). This results in an increase of dissolved HCO3 concentration while maintaining d13C of HCO3 relatively constant at +10 per mil. Non-steady-state deposition has resulted in significantly higher organic carbon contents and unusually high (70 meq/l) pore-water alkalinities below 150 m. These high alkalinities are believed to be related more to spontaneous decarboxylation reactions than to biological processes. The general decrease in HCO3 concentration with constant d13C over the depth interval of 200 to 400 m probably reflects increased precipitation of authigenic carbonate. Input-output carbon isotope-mass balance calculations, and carbonate system equilibria in conjunction with observed CO2-CH4 ratios in the gas phase, independently suggest that CH4 concentrations on the order of 100 mmol/kg are present in the pore waters of Blake Outer Ridge sediments. This quantity of CH4 is believed to be insufficient to saturate pore waters and stabilize the CH4*6H2O gas hydrate. Results of these calculations are in conflict with the physical recovery of gas hydrate from 238 m, and with the indirect evidence (seismic reflectors, sediment frothing, slightly decreasing salinity and chlorinity with depth, and pressure core barrel observations) of gas-hydrate occurrence in these sediments. Resolution of this apparent conflict would be possible if CH4 generation were restricted to relatively thin (1-10 m) depth intervals, and did not occur uniformly at all depths throughout the sediment column, or if another methanogenic process (e.g., acetate fermentation) were a major contributor of gas.

Oxygen contents, sulfate concentrations, and changes of IPLs under different storage conditions of samples from ODP Leg 204 and IODP Expedition 311

We have studied the effects of slow infiltration of oxygen on microbial communities in refrigerated legacy samples from ocean drilling expeditions. Storage was in heat-sealed, laminated foil bags with a N2 headspace for geomicrobiological studies. Analysis of microbial lipids suggests that Bacteria were barely detectable in situ but increased remarkably during storage. Detailed molecular examination of a methane-rich sediment horizon showed that refrigeration triggered selective growth of ANME-2 archaea and a drastic change in the bacterial community. Subsequent enrichment targeting methanogens yielded exclusively methylotrophs, which were probably selected for by high sulfate levels caused by oxidation of reduced sulfur species. We provide recommendations for sample storage in future ocean drilling expeditions.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.

Water chemistry and sediment age of lake Terrasovoje, Amery Oasis, East Antarctica

The late Quaternary palaeoenvironmental history of the southern Windmill Islands, East Antarctica, has been reconstructed using diatom assemblages from two long, well-dated sediment cores taken in two marine bays. The diatom assemblage of the lowest sediment layers suggests a warm climate with mostly open water conditions during the late Pleistocene. During the following glacial, the Windmill Islands were covered by grounded ice preventing any in situ bioproductivity. Following deglaciation, a sapropel with a well-preserved diatom assemblage was deposited from ~10?500 cal yr BP. Between ~10?500 and ~4000 cal yr BP, total organic carbon (Corg) and total diatom valve concentrations as well as the diatom species composition suggest relatively cool summer temperatures. Hydrological conditions in coastal bays were characterised by combined winter sea-ice and open water conditions. This extensive period of glacial retreat was followed by the Holocene optimum (~4000 to ~1000 cal yr BP), which occurred later in the southern Windmill Islands than in most other Antarctic coastal regions. Diatom assemblages in this period suggest ice-free conditions and meltwater-stratified waters in the marine bays during summer, which is also reflected in high proportions of freshwater diatoms in the sediments. The diatom assemblage in the upper sediments of both cores indicates Neoglacial cooling from ~1000 cal yr BP, which again led to seasonally persistent sea-ice on the bays. The Holocene optimum and cooling trends in the Windmill Islands did not occur contemporaneously with other Antarctic coastal regions, showing that the here presented record reflects partly local environmental conditions rather than global climatic trends.

Sulfur concentrations and isotopic composition of serpentinized oceanic peridotites

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of <1 Ma peridotites at Hess Deep occurred at high temperatures (200°-400°C) and low water/rock ratios. Oxidation of ferrous iron to magnetite maintained low fO2 and produced a reduced, low-sulfur assemblage including NiFe alloy. Small amounts of sulfate reduction by thermophilic microbes occurred as the system cooled, producing low-delta34S sulfide (1.5? to -23.7?). In contrast, serpentinization of Iberian Margin peridotites occurred at low temperatures(~20°-200°C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-delta34S sulfide (~15 to ~43?) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high delta34S of total sulfur (mean ~8?). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in delta34S of total sulfur (mean ~ -5?). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 * 10**12 g S/yr from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Biogeochemical measurements of cold seep sediments inhabit by vesicomyid clams in the Japan Deep Sea Trench

Vesicomyidae clams harbor sulfide-oxidizing endosymbionts and are typical members of cold seep communities associated with tectonic faults where active venting of fluids and gases takes place. We investigated the central biogeochemical processes that supported a vesicomyid clam colony as part of a locally restricted seep community in the Japan Trench at 5346 m water depth, one of the deepest seep settings studied to date. An integrated approach of biogeochemical and molecular ecological techniques was used combining in situ and ex situ measurements. During the cruise YK06-05 in 2006 with the RV Yokosuka to the Japan Trench, we investigated a clam colony inhabited by Abyssogena phaseoliformis (former known as Calyptogena phaseoliformis) and Isorropodon fossajaponicum (former known as Calyptogena fossajaponica). The targeted sampling and precise positioning of the in situ instruments were achieved with the manned research submersible Shinkai 6500 (JAMSTEC, Nankoku, Kochi, Japan). Sampling was first performed close to the rim of the JTC colony and then at the center. Immediately after sample recovery onboard, the sediment core was sub-sampled for ex situ rate measurements or preserved for later analyses. In sediment of the clam colony, low sulfate reduction (SR) rates (max. 128 nmol ml**-1 d**-1) were coupled to the anaerobic oxidation of methane (AOM). They were observed over a depth range of 15 cm, caused by active transport of sulfate due to bioturbation of the vesicomyid clams. A distinct separation between the seep and the surrounding seafloor was shown by steep horizontal geochemical gradients and pronounced microbial community shifts. The sediment below the clam colony was dominated by anaerobic methanotrophic archaea (ANME-2c) and sulfate-reducing Desulfobulbaceae (SEEP-SRB-3, SEEP-SRB-4). Aerobic methanotrophic bacteria were not detected in the sediment and the oxidation of sulfide seemed to be carried out chemolithoautotrophically by Sulfurovum species. Thus, major redox processes were mediated by distinct subgroups of seep-related microorganisms that might have been selected by this specific abyssal seep environment. Fluid flow and microbial activity was low but sufficient to support the clam community over decades and to build up high biomasses. Hence, the clams and their microbial communities adapted successfully to a low-energy regime and may represent widespread chemosynthetic communities in the Japan Trench.

Chemistry of interstitial waters of samples from DSDP Leg 25

Interstitial water analyses from sediments collected during Leg 25 of the Deep Sea Drilling Project have revealed that in the southwest Indian Ocean, great chemical activity exists in sediments in various depositional environments. Variable sedimentation rates allow us to set some interesting boundary conditions on chemical and transport processes in these interstitial waters, particularly with regard to the distribution of dissolved sulfate. In terrigenous rapidly deposited sediments, large depletions are observed in magnesium and potassium, whereas relatively small decreases in dissolved calcium occur. In slowly deposited detrital sediments, also, large decreases in potassium and magnesium coincide with very large calcium increases. In truly pelagic sediments, a one to one replacement of magnesium by calcium is observed in the interstitial waters, presumably due to reactions in the basal sediment layers. Biogenous deposits have great influence on dissolved silica (sponge spicules and radiolarians) and on dissolved strontium (carbonate recrystallization). Otherwise, dissolved silica reflects the clay mineralogy and shows variations which seem particularly dependent on the presence or absence of kaolinite. Variable dissolved manganese values reflect reducing conditions and/or availability of manganese in the solid phases for mobilization in reducing sediments.

Chemical and isotope compositions of thermal and surficial waters from the Chukotka Peninsula

Twenty three groups of thermomineral springs in the eastern Chukotka with discharge temperature from 2 to 97°C and mineralization from 1.47 to 37.14 g/l are studied and compared with surface freshwater from their localities. dD and d18O values in surface waters vary from -121.4 to -89.5 per mil and from -16.4 to -11.1 per mil, respectively, while respective values in thermomineral waters range from -134.2 to -92.5 per mil and from -17.6 to -10.5 per mil. dD value in surface waters decreases from the east to the west, i.e. toward interior areas of the peninsula. Hydrothermal springs most depleted in deuterium (dD < -120 per mil) are localized in the geodynamically active Kolyuchinskaya-Mechigmen Depression. According to the proposed formation model of Chukotka thermomineral waters their observed chemical and isotopic characteristics could result from mixing (in different proportions) of surface waters with the deep-sourced isotopically light mineralized component (dD = ca. -138 per mil, d18O = ca. -19 per mil, ? = from 9.5 to 14.7 g/l). The latter originates most likely from subpermafrost waters subjected to slight cryogenic metamorphism.

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.

Oxidation rate of thiosulfate and elemental sulfur in the Black Sea

Oxidation rate of 35S-thiosulfate under simulated natural conditions and abundance of thiosulfate-oxidizing bacteria in a redox zone of the Black Sea are lower during winter and spring than in summer, especially in halistatic regions. Oxidation of thiosulfate under natural conditions is performed chiefly by lithotropic thionic bacteria, whose activity is limited by low temperatures. Adding thiosulfate and readily available organic matter to water samples from the redox zone and raising temperature of water stimulated activity of heterotrophic thiosulfate-oxidizing bacteria. Oxidation of elemental sulfur tagged with 35S apparently invovled two stages: abiotic oxidation of thiosulfate and subsequent bacterial oxidation of thiosulfate to sulfate.

Mineralogy, chemistry and stable isotope composition of hydrothermal altered sheeted dikes of ODP Hole 111-504B

During ODP Leg 111 Hole 504B was extended 212 m deeper into the sheeted dikes of oceanic Layer 2, for a total penetration of 1288 m within basement. Study of the mineralogy, chemistry, and stable isotopic compositions of the rocks recovered on Leg 111 has confirmed and extended the previous model for hydrothermal alteration at the site: axial greenschist hydrothermal metamorphism was followed by seawater recharge and subsequent off-axis alteration. The dikes are depleted in 18O (mean delta18O = +5.1 ? +/- 0.6 ?) relative to fresh mid-ocean ridge basalt. Oxygen isotopic data on whole rocks and isolated secondary minerals indicate temperatures during axial metamorphism of 250°-350°C and water/rock ratios about one. Increasing amounts of actinolite with depth in the dike section, however, suggest that temperatures increased downward in the dikes. Pyrite + pyrrhotite + chalcopyrite + magnetite was the stable sulfide + oxide mineral assemblage during axial alteration, but these minerals partly re-equilibrated later at temperatures less than 200°C. The dikes sampled on Leg 111 contain an average of 500 ppm sulfur, slightly lower than igneous values. The delta34S values of sulfide average 0?, which indicates the presence of basaltic sulfide and incorporation of little or no seawater-derived sulfide into the rocks. These data are consistent with models for the presence of rock-dominated sulfur in deep hydrothermal fluids. The presence of anhydrite at 1176 m within basement indicates that unaltered seawater can penetrate to significant depths in the crust during recharge.

Chemical and isotope composition of carbonate nodules and host bottom sediments from Core DM9-666, Gulf of California

Results of mineralogical and isotopic analyzes of sulfur and carbon in carbonate nodules and host bottom sediments and results of 14C measurement in carbonate nodules are reported. It is proved that the carbonate nodules formed 11-22 thousand years ago in anaerobic diagenesis of bottom sediments rich in organic matter. Isotopic light metabolic carbon dioxide was a source of carbonate for nodules. It formed during microbial degradation of organic matter of bottom sediments.

Chemical composition of bottom sediments and interstitial waters from DSDP Sites 252, 285, 315, 317, 336, and 386

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H218O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H218O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.