Isotopic composition of interstitial fluids in sediment at DSDP Sites 87-582 and 87-583

The isotopic compositions of dissolved CO2 and CH4 in sediments of the Nankai Trough indicate that CH4 is formed during early diagenesis by microbial reduction of CO2. At the shallowest sampled depths, the CO2 dissolved in the pore water is unusually enriched in 12C (d13C = -35.2 per mil), indicating contribution of CO2 from oxidation of CH4. The most intense microbiological activity appears to be confined to the uppermost 50 m of sediment, based on relative lack of change in the isotopic compositions below this depth. Gas hydrate probably is not present at these localities (Sites 582, 583) because of CH4 concentrations that are insufficient to saturate the pore water with respect to gas hydrate stability.

Consolidation properties and strength characteristics of ODP Site 204-1244 sediments

Eight whole-core samples from Ocean Drilling Program Site 1244, Hydrate Ridge, Cascadia continental margin, were provided to Massachusetts Institute of Technology (Cambridge, Massachusetts, USA) for geotechnical characterization. The samples were collected from depths ranging from 5 to 136 meters below seafloor (mbsf). Seven of the eight whole-core samples were located within the gas hydrate stability zone, whereas the eighth sample was located in the free gas zone. Atterberg limits testing showed that the average liquid limit of the soil is 81% and the average plastic limit is 38%, giving an average plasticity index of 43%. The liquid limit is sensitive to oven drying, shown by a drop in liquid limit to 64% when tests were performed on an oven-dried sample. Loss on ignition averages 5.45 wt%. Constant rate of strain consolidation (CRSC) tests were performed to obtain the compression characteristics of the soil, as well as to determine the stress history of the site. CRSC tests also provided hydraulic conductivity and coefficient of consolidation characteristics for these sediments. The compression ratio (Cc) ranges from 0.340 to 0.704 (average = 0.568). Cc is fairly constant to a depth of 79 mbsf, after which Cc decreases downhole. The recompression ratio (Cr) ranges from 0.035 to 0.064 (average = 0.052). Cr is constant throughout the depth range. In situ hydraulic conductivity varies between 1.5 x 10**-7 and 3 x 10**-8 cm/s and shows no trend with depth. Ko-consolidated undrained compression/extension (CKoUC/E) tests were also performed to determine the peak undrained shear strength, stress-strain curve, and friction angle. The normalized undrained strength ranges from 0.29 to 0.35. The friction angle ranges from 27 to 37. Because of the limited amount of soil, CRSC and CKoUC/E tests were also conducted on resedimented specimens.

The SUGAR Toolbox

The SUGAR Toolbox contains scripts coded in MATLAB for calculating various thermodynamic, kinetic, and geologic properties of substances occurring in the marine environment, particularly gas hydrate and seep systems. Brief descriptions of the toolbox scripts and some notes on the underlying basic theory as well as tables of additional property values can be found in the accompanying documentation.

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.

Summary of physical properties on cores used for petrofabric analyses triaxial experiments at DSDP Leg 67 Holes

Deformation features within the cores are studied with a view towards elucidating the structure of the Middle America Trench along the transect drilled during Leg 67. Where possible, inferences are made as to the physical environment of deformation. Extensional tectonics prevails in the area of the seaward slope and trench. Fracturing and one well-preserved normal fault are found mostly within the lower Miocene chalks, at the base of the sedimentary section. These chalks have high porosities (40%-60%) and water content (30%-190%, based on % dry wt.). Experimental triaxial compression tests conducted on both dry and water-saturated samples of chalk from Holes 495 and 499B show that only in the saturated samples is more brittle behavior observed. Brittle failure of the chalks is greatly facilitated by pore fluid pressures that lead to low effective pressures. Additional embrittlement (weakening) can take place as a result of the imposed extensional stress resulting from bending of a subducting elastic oceanic plate. The chalks exhibit, in a landward direction, an increase in density and mechanical strength and a decrease in water content. These changes are attributed to mechanical compaction that may have resulted from tectonic horizontal compression. The structure of the landward slope is not well understood because the slope sites had to be abandoned due to the presence of gas hydrate. The relationship of the chaotic, brittle deformation (observed in the cores from Hole 494A) at the base of the landward slope to tectonic processes remains unclear. The deformation observed on the slope sites (Holes 496 and 497) is mostly fracturing and near-vertical sigmoidal veinlets. These are interpreted as being the result of gas/fluid overpressurization due to the decomposition of the gas hydrate, and not due to tectonic loading of accreted sediments. Aside from four small displacement (less than 1cm) reverse faults observed in the lower Miocene chalks (which may be the product of soft-sediment deformation), there is a noticeable absence of structures reflecting a dominance of horizontal (tectonic) compression along the transect drilled. The absence of such features, the lack of continuity of sediment types across the trench-landward slope, and the normal stratigraphic sequence in Hole 494A do not support any known accretionary model.

Isotopic composition of interstitial fluids and origin of methane at DSDP Leg 84 Holes

CH4 and CO2 species in pore fluids from slope sediments off Guatemala show extreme 13C-enrichment (d13C of -41 and +38 per mil, respectively) compared with the typical degree of 13C-enrichment in pore fluids of DSDP sediments (d13C of - 60 and + 10 per mil). These unusual isotopic compositions are believed to result from microbial decomposition of organic matter, and possibly from additional isotopic fractionation associated with the formation of gas hydrates. In addition to the isotopic fractionation displayed by CH4 and CO2, the pore water exhibits a systematic increase in d18O with decrease in chlorinity. As against seawater d18O values of 0 and chlorinity of 19 per mil, the water collected from decomposed gas hydrate from Hole 570 had a d18O of + 3.0 per mil and chlorinity of 9.5 per mil. The isotopic compositions of pore-fluid constituents change gradually with depth in Hole 568 and discontinuously with depth in Hole 570.

Gas hydrates at DSDP Leg 84

On DSDP Leg 84, gas hydrates were found at three sites (565, 568, and 570) and were inferred, on the basis of inorganic and organic geochemical evidence, to be present at two sites (566 and 569); no evidence for gas hydrates was observed at Site 567. Recovered gas hydrates appeared as solid pieces of white, icelike material occupying fractures in mudstone or as coarse-grained sediment in which the pore space exhibited rapid outgassing. Also a 1.05-m-long core of massive gas hydrate was obtained at Site 570. Downhole logging indicated that this hydrate was actually 3 to 4 m thick. Measurements of the amount of methane released during the decomposition of these recovered samples clearly showed that gas hydrates had been found. The distribution of evolved hydrocarbon gases indicated that Structure I gas hydrates were present because of the apparent inclusion of methane and ethane and exclusion of propane and higher molecular weight gases. The water composing the gas hydrates was fresh, having chlorinities ranging from 0.5 to 3.2 per mil. At Sites 565, 568, and 570, where gas hydrates were observed, the chlorinity of pore water squeezed from the sediment decreased with sediment depth. The chlorinity profiles may indicate that gas hydrates can often occur finely dispersed in sediments but that these gas hydrates are not recovered because they do not survive the drilling and recovery process. Methane in the gas hydrates found on Leg 84 was mainly derived in situ by biogenic processes, whereas the accompanying small amounts of ethane likely resulted from low-temperature diagenetic processes. Finding gas hydrates on Leg 84 expands observations made earlier on Leg 66 and particularly Leg 67. The results of all of these legs show that gas hydrates are common in landward slope sediments of the Middle American Trench from Mexico to Costa Rica.

Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.

Sediment properties, contents and accumulation rates of Hg in cores of Upper Quaternary sediments from the Deryugin Basin, Okhotsk Sea

The Hg distribution and some mineralogical-geochemical features of bottom sediments up to a depth of 10 m in the Deryugin Basin showed that the high and anomalous Hg contents in the Holocene deposits are confined to a spreading riftogenic structure and separate fluid vents within it. The accumulations of Hg in the the sediments were caused by its fluxes from gas and low-temperature hydrothermal vents under favorable oceanological conditions in the Holocene. The two mainly responsible for the high and anomalous Hg contents are infiltration (fluxes of hydrothermal or gas fluids from the sedimentary cover) and plume (Hg precipitation from water plumes with certain hydrochemical conditions forming above endogenous sources). The infiltration anomalies of Hg were revealed in the following environments: (1) near gas vents on the northeastern Sakhalin slope, where high Hg contents are associated only with Se and were caused by the accumulation of gases ascending from beneath the gas hydrate layer; (2) in the area of inferred occasionally operating low-temperature hydrothermal seeps in the central part of the Deryugin Basin, in which massive barite chimneys, hydrothermal Fe-Mn crusts, and anomalous contents of Mn, Ba, Zn, and Ni in sediments develop.

Isotopic composition of bottom and interstitial waters in the area of gas plumes, Sea of Okhotsk

Data on isotopic composition of interstitial and bottom waters collected in an area of gas hydrate occurrence in the Sea of Okhotsk are presented. Investigations indicate that heavy isotopes of oxygen and hydrogen are used in generation of gas hydrate, so that isotopic composition of its water of constitution is: d18O = +1.9 per mil, d2H = +23 per mil (relative to SMOW). Production of authigenic carbonates results in isotopic exchange with interstitial water, which in turn alters its isotopic composition by an increase in d18O. Bottom waters are isotopically light relative to the SMOW standard and to the average isotopic composition of interstitial waters in the area of gas hydrate occurrence in study.

Mineralogy and geochemistry of Miocene tuff from ODP Hole 129-802A

Drilling at Ocean Drilling Program Site 802 in the central Mariana Basin, northwest Pacific Ocean, revealed an unexpected 222-m-thick sequence of well-cemented tuff of Miocene age. The deposits are unusual in that their source is presumably an unmapped seamount and they exhibit several peculiar petrological and mineralogical features. The well-developed secondary mineral sequence which includes analcime is rare in such relatively young, unburied deposits, in an area where there is little other evidence of hydrothermal activity. The massive tuff section also contains abundant fissure veins made of a rare silicate carbonate sulfate hydroxide hydrate of calcium, called thaumasite, which has not before been described in deep submarine deposits. The smectite-zeolite-thaumasite paragenesis coincides with the presence of chloride and calcium-enriched interstitial waters. The diagenetic evolution of the deposit appears to have been largely controlled by the depositional mode. The discharges of disaggregated and rejuvenated volcaniclasts seem to have been abrupt and repeated. The Miocene tuff at Site 802 thus provides new insights on the interactions between basaltic glass, biogenic phases, and seawater, in a specific deep-sea environment.