Carbonate mineralogical and isotopic analyses of TV-guided grab samples and TV-guided box corer samples from the Shumagin area

Methane seepage leads to Mg-calcite and aragonite precipitation at a depth of 4,850 m on the Aleutian accretionary margin. Stromatolitic and oncoid growth structures imply encrustation of microorganisms (microbial mats) in the host sediment with a unique growth direction downward into the sediment, forming crust-shaped lithologies. Biomarker investigations of the residue after carbonate dissolution show strong enrichments in crocetane and archaeol, which contain extremely low d13C values. This indicates the presence of methane-consuming archaea, and d13C values of -42 to -51 per mill PDB indicate that methane is the carbon source for the carbonate crusts. Thus, it appears that stromatolitic encrustations of methanotrophic anaerobic archaea probably occurs in a consortium with sulphate-reducing bacteria and that carbonate precipitation proceeds downward into the sediment, where ascending cold fluids provide a methane source. Strontium and oxygen isotope analyses as well as 14C ages of the carbonates suggest that the fluids come from deep within the sediment and that carbonate precipitation began about 3,000 years ago.

Geochemical and isotopic composition of sediments and pore waters from ODP Leg 164 sites

Authigenic carbonates were recovered from several horizons between 0 and 52 mbsf in sediments that overlay the Blake Ridge Diapir on the Carolina Rise (Ocean Drilling Program [ODP] Site 996). Active chemosynthetic communities at this site are apparently fed by fluid conduits extending beneath a bottom-simulating reflector (BSR). Gas hydrates occur at several depth intervals in these near-surface sediments. The carbonate nodules are composed of rounded to subangular intraclasts and carbonate cemented mussel shell fragments. Electron microprobe and X-ray diffraction (XRD) investigations show that aragonite is the dominant authigenic carbonate. Authigenic aragonite occurs both as microcrystalline, interstitial cement, and as cavity-filling radial fibrous crystals. The d13C values of the authigenic aragonite vary between -48.4 per mil and -30.5 per mil (Peedee belemnite [PDB]), indicating that carbon derived from 13C-depleted methane is incorporated into these carbonates. The d13C of pore water sum CO2 values are most negative in the upper 10 mbsf, near the sediment/water interface (-38 per mil ± 5 per mil), but noticeably more positive below 25 mbsf (+5 per mil ± 6 per mil). Because carbonates derive their carbon from HCO3-, dissimilarities between the d13C values of carbonate precipitates recovered from greater than 10 mbsf and d13C values of the associated pore fluids suggests that these carbonates formed near the seafloor. Differences of about 1 per mil in the oxygen isotopic composition of carbonate precipitates from different depths are possibly related to changes in bottom-water conditions during glacial and interglacial time periods. Measurements of the strontium isotopic composition on 13 carbonate samples show 87Sr/86Sr values between 0.709125 and 0.709206 with a mean of 0.709165, consistent with the approximate age of their host sediment. Furthermore, the 87Sr/86Sr values of six pore-water samples from Site 996 vary between 0.709130 and 0.709204. The similarity of these values to seawater (87Sr/86Sr = 0.709175), and to 87Sr/86Sr values of pore water from similar sample depths elsewhere on the Blake Ridge (Sites 994, 995, and 997), indicates a shallow Sr source. The 87Sr/86Sr values of the authigenic carbonates at Site 996 are not consistent with the Sr isotopic values predicted for carbonates precipitated from fluids transported upward along fault conduits extending through the base of the gas hydrate-stability zone. Based on our data, we see no evidence of continuing carbonate diagenesis with depth. Therefore, with the exception of their seafloor expression as carbonate crusts, fossil vent sites will not be preserved. Because these authigenic features apparently form only at the seafloor, their vertical distribution and sediment age imply that seepage has been going on in this area for at least 600,000 yr.

Chemical and isotopic compositions of authigenic carbonates from the area of the Sakhalin-Deryugin gas anomaly, Sea of Okhotsk

Features of sedimentation of carbonate mineral associations in the northeastern shelf of Sakhalin and other regions of the Sea of Okhotsk are considered. Special attention is paid to correlation between carbonate neoformations and abnormal fluxes of methane. In bottom sediments with high contents of methane carbonate-sulfide associations occur, their generation has been influenced by gas (mostly methane) fields. Joint consideration of distribution of gas and geochemical fields and mineral associations in the Sea of Okhotsk allows to understand better a mechanism of mineral generation in bottom sediments, possible formation of ore accumulations, and to use them as indicators for prognosis of mineral resources.

Sulfur contents and S, C and O isotopic compositions in serpentinized peridotites at ODP Site 153-920

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated d34S_sulfide (3.7 to 12.7?). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high d34S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (~400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ~300°C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5?) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 mln ton seawater S per year. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Composition of organic matter from samples of massive sulfides, bottom sediments, and seawater collected within the Logachev and Broken Spur hydrothermal fields, Mid-Atlantic Ridge

Lipid components of hydrothermal deposits from the unusual field at 14°45'N MAR and from the typical field at 29°N MAR were studied. For the first time mixed nature of organic matter (OM) from hydrothermal sulfide deposits was established with use of biochemical, gas chromatographic, and molecular methods of studies. In composition of OM lipids of phytoplankton, those of chemosynthesis bacteria and non-biogenic synthesis lipids were determined. Specific conditions of localization of sulfide deposits originated from ''black smokers'' (reducing conditions, absence of free oxygen, presence of reduced sulfur preventing OM from decomposition) let biogenic material, including bacterial one, be preserved in sulfide deposits. The hydrothermal system at 14°45'N MAR is characterized by geological, geochemical and thermodynamic conditions allowing abiogenic synthesis of methane and petroleum hydrocarbons. For sulfide deposits at 29°N and other active hydrothermal fields known at MAR, abiogenic synthesis of hydrocarbons occurs in lower scales.

Carbon and nitrogen isotopic composition of Early Toarcian sediments

Bulk sedimentary nitrogen isotope (d15Ntot) data have been generated from Lower Jurassic black, carbon-rich shales in the British Isles and northern Italy deposited during the early Toarcian oceanic anoxic event. A pronounced positive d15Ntot excursion through the exaratum Subzone of the falciferum Zone (defined by characteristic ammonites in the British Isles) broadly correlates with a relative maximum in weight percent total organic carbon and, in some sections, with a negative d13Corg excursion. Upwelling of a deoxygenated water mass that had undergone partial denitrification is the likely explanation for relative enrichment of d15Ntot, and parallels may be drawn with Quaternary sediments of the Arabian Sea, Gulf of California, and northwest Mexican margin. The development of Early Toarcian suboxic water masses and consequent partial denitrification is attributed to increases in organic productivity. Approximately coincident phenomena include the following: a relative climatic optimum, realignment of major oceanic current systems, and a possible release of methane gas hydrates from continental margin sediments early in the history of the oceanic anoxic event.

Petrography, minerals and isotopic composition at DSDP Leg 66 Holes

We collected 20 carbonate nodules from the inner trench slope deposits of the Middle America Trench area off Mexico. Carbonate nodules are found only within the methane-rich layer beneath the mixed layer of methane and hydrogen sulfide. They have been investigated by microscopic, scanning electron microscopic (SEM), X-ray diffraction, and stable isotopic analytical methods. Calcite, magnesian calcite, dolomite, and rhodochrosite were recognized as carbonate minerals. Each carbonate nodule is usually represented by single species of carbonate minerals. Carbonate nodules are subdivided into micrite nodules and recrystallized nodules according to textural features. The carbonate crystallites in each micrite nodule are equidimensional. Their sizes range from several to 30 µm, as revealed by SEM micrographs. The chemical composition of calcite is changed from pure calcite to high magnesian calcite, as shown by the shift of the (104) reflection in X-ray diffraction patterns. Fe substitution for Ca in dolomite was also observed. Carbon isotopic composition shows an unusually wide range - from -42.9 to +13.5 per mil - in PDB scale, whereas oxygen isotopic compositions of almost all the carbonate nodules are constantly enriched in 18O from +3.4 to +7.60 per mil in PDB scale. These wide variations in carbon isotopic composition indicate several sources for the carbon in carbonate nodules. Carbon with a negative d13C value was derived from biochemical oxidation of methane with a negative d13C value. On the other hand, carbon with positive d13C value was probably formed during methane production in an anoxic condition.

Organic-geochemical and petrographical composition of sediments from ODP Leg 164 sites

Sediments from Holes 994C, 995A, 997A, and 997B have been investigated for "combined" gases (adsorbed gas and that portion of free gas that has not escaped from the pore volume during core recovery and sample collection and storage), solvent-extractable organic compounds, and microscopically identifiable organic matter. The soluble materials mainly consist of polar compounds. The saturated hydrocarbons are dominated by n-alkanes with a pronounced odd-even predominance pattern that is derived from higher plant remains. Unsaturated triterpenoids and 17ß, 21ß-pentacyclic triterpenoids are characteristic for a low maturity stage of the organic matter. The low maturity is confirmed by vitrinite reflectance values of 0.3%. The proportion of terrestrial remains (vitrinite) increases with sub-bottom depth. Within the liptinite fraction, marine algae plays a major role in the sections below 180 mbsf, whereas above this depth sporinites and pollen from conifers are dominant. These facies changes are confirmed by the downhole variations of isoprenoid and triterpenoid ratios in the soluble organic matter. The combined gases contain methane, ethane, and propane, which is a mixture of microbial methane and thermal hydrocarbon gases. The variations in the gas ratios C1/(C2+C3) reflect the depth range of the hydrate stability zone. The carbon isotopic contents of ethane and propane indicate an origin from marine organic matter that is in the maturity stage of the oil window.

Organic matter, isotopic composition of calcite veins in basement basalt and pore water at DSDP Leg 78A Holes

Sediments of the Barbados Ridge complex, cored on DSDP Leg 78A, contain low concentrations of acid-insoluble carbon (0.05-0.25%) and nitrogen (C/N 1.5-5) and dispersed C1-C6 hydrocarbons (100-800 ppb). The concentrations of organic carbon and 13C in organic carbon decrease with depth, whereas the concentration of dispersed hydrocarbons increases slightly with depth. These trends may reflect the slow oxidation of organic matter, with selective removal of 13C and slow conversion of the residual organic matter to hydrocarbons. Very minor indications of nitrogen gas were observed at about 250 meters sub-bottom at two of the drilling sites. Basement basalts have calcite veins with d13C values in the range of 2.0 to 3.2 per mil and d18O-SMOW values ranging from 28.5 to +30.6 per mil. Interstitial waters have d18O-SMOW of 0.2 to -3.5 per mil and dD-SMOW of -2 to -15 per mil. The oxygen isotopic composition of the calcite veins in the basement basalts gives estimated equilibrium fractionation temperatures in the range of 11 to 24°C, assuming precipitation from water with d18O-SMOW in the range of +0.1 to -1.0 per mil. This suggests that basalt alteration and precipitation of vein calcite occurred in contact either with warmer Campanian seawater or, later, with pore water, after burial to depths of 200- 300 meters. Pore waters from all three sites are depleted in deuterium and 18O, and dissolved sulfate is enriched in 34S at Sites 541 and 542, but not at Site 543.

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.

Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Geochemical and biogeochemical parameters of bottom sediments from the area of the Spitsbergen (Svalbard) Archipelago

Quantitative characteristics for rates of diagenetic processes in the upper (0-30 cm) layer of sedimentary deposits in the area of the Spitsbergen (Svalbard) Archipelago (78°-80°N) were obtained by lithologo-geochemical, radioisotope (35S, 14C), and stable isotope (d34S, d13C) studies. It was proved that rates of diagenetic processes in polar deposits at 123-395 m depth affected by the East Spitsbergen ''warm'' current are mostly determined by bioproductivity and are commensurate with rates of processes in shelf deposits of temperate latitudes. High contents of migratory methane (up to 263 ml/dm**3) and isotopically-light organic carbon (Corg, d13C = -30 per mil PDB) were found in the 1 m layer of shelf deposits (at 123 m sea depth) with low bacterial in situ production of methane. It was shown that methane is not utilized in the deposits by the methanotrophic bacterial community and it may be supplied to the water mass and, probably, to the atmosphere.

Authigenic carbonate of ODP SIte 104-643

Different generations of complex authigenic carbonates formed in siliceous muds (lithologic Unit IV) and hemipelagic clays (lithologic Unit V) of ODP Site 643, Leg 104 Norwegian Sea. The dominant phase in Unit IV is an early diagenetic Mn, Fe-calcite with a strong negative d13C ( -14 to -16 per mil) signature, and slightly negative d180 values. The strong negative d13C results from extensive incorporation of 12C-enriched CO2 derived from bacterial degradation of marine organic matter into early Mn, Fe - calcite cements. Concomitant framboidal pyrite precipitation and abundant SEM microtextures showing excellent preservation of delicate structures of fragile diatom valves by outpourings with early Mn-calcites strongly support their shallow burial formation before the onset of compaction. Later generations of authigenic mineralizations in lithologic Unit IV include minor amounts of a second generation of calcite with platy crystals, possibly precipitated along with opal-A dissolution, and finally opal-CT crystallization in deeper seated environments overgrowing earlier precipitates with films and lepispheres. The last mineralization is collophane (fluor apatite) forming amorphous aggregates and tiny hexagonal crystals. Authigenic mineral assemblages in lithologic Unit V consist of rhodochrosites, transitional rhodochrosite/manganosiderites, and apatite. A negative d13C ( -7.1 to -15.6 per mil) and a fluctuating d18O signal indicates that the micritic to sparitic rhodochrosites, transitional rhodochrosites/manganosiderites were formed at various burial depths. CO2 resulted from organic matter degradation in the lowermost sulfate reduction zone and from biogenic methane generation in the lowermost sediments, resulting in variable and negative d13C signals. The change in carbonate mineralogy reflects major compositional differences compared to sediments in Unit IV. Most prominent is an increase in altered ash as a primary sediment component and a sudden decrease of siliceous microfossils. Upward diffusion of cations, lowered salinities in pore waters, and elevated temperatures provide diagenetic environments favoring increased remobilization processes.