Methane hydrate at DSDP Site 84-570

Deep Sea Drilling Project (DSDP) studies at Site 570 on the landward slope of the Middle America Trench off Guatemala allow for the first time a quantitative estimate of the methane hydrate content in the massive mudstones deposited there. Drilling across the Guatemalan transect on DSDP Legs 67 and 84 has resulted in the greatest number of visual observations of gas hydrate in any marine area. At Site 570, a 1.5-m-long section of massive methane hydrate was unexpectedly cored in an area where none of the usual signs of gas hydrate in seismic records were present. The sediment section is similar to that recovered at the other eight sites off Guatemala, but drilling at Site 570 may have penetrated through a fault zone that provided the space for accumulation of massive gas hydrate. The methane hydrate was analyzed using the following well logs: density, sonic, resistivity, gamma-ray, caliper, neutron porosity, and temperature. The density, sonic, and resistivity logs define a 15-m-thick hydrated zone within which a 4-m-thick nearly pure hydrate section is contained. The methane gas content ranges from 240 m**3 to 1400 m**3 per m**2 of lateral extent; and if the body extends a square kilometer, its total volume of stored gas could be from 240*10**6m**3 to 1400*10**6m**3. Because the acoustic impedance of hydrate calculated from the sonic and density logs shows no anomalous values, the shape and extent of the hydrate body cannot be defined in seismic records. Thus the body is theoretically nonreflective in contrast to the base of the hydrate reflection. The base of the gas hydrate reflection is presumed to be the result of the velocity contrast between sediment containing gas hydrate and sediment containing free gas.

Geochemistry of interstitial waters of DSDP Leg 96 sites

Interstitial water studies were done at 9 of the 11 sites visited in the Mississippi Fan and Orca and Pigmy Basins during DSDP Leg 96. High concentrations of sulfate were observed at Mississippi Fan Sites 616, 617, 620, and 623. The maximum sulfate value of 38.8 mM, recorded at Site 617, is the highest ever found in DSDP sediments. Hypersaline interstitial water was observed at Site 618 in Orca Basin. Concentration ratios of salinity to chlorinity and to sodium in interstitial waters are similar to those of Orca Basin bottom water, suggesting that the chemistry of interstitial water is affected by the dissolution of buried salt.

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.

Geotechnical properties of sediments at DSDP Leg 84 Holes

The geotechnical characteristics of 22 sediment samples from Leg 84 sites were studied in an effort to associate these with processes active along the Middle America slope and with sedimentation mechanisms. Geotechnical properties measured include water content, porosity, bulk density, Atterberg limits, consolidation characteristics, permeability, and vane shear strength. A majority of samples obtained from Sites 565, 568, and 570 show significant disturbance resulting from degassing. This disturbance apparently results in underconsolidation, although other mechanisms such as excess pore pressures generated from the subduction process can also contribute to this state. Overconsolidated sediments were found at Sites 565, 566, and 569. The overconsolidated sediments at Sites 565 and 569 may result from downslope transport mechanisms rearranging and stressing the sediment mass under consideration. The sediment condition at Site 566 is probably a result of eroded overburden: an estimated 87 m of overlying sediments may have been removed. Geotechnical and permeability relationships with depth are consistent with those found for other hemipelagic sediments of silty clay to clayey silt textures.

(Figure 2) Range and distribution chart of dinoflagellate cysts recovered from Campanian to Maestrichtian sediments at DSDP Hole 95-612

Fifty-nine samples from the basal 110 m of DSDP Hole 612 (United States Atlantic Margin) were analyzed for palynomorph content. In total, 84 species and subspecies of dinoflagellate cysts were recorded which, on comparison with published data and shipboard analyses, indicate a Campanian to Maestrichtian age for this part of the succession. The Campanian/Maestrichtian contact is taken to occur in the upper part of Core 612-69.

Calcium carbonate, sedimentation and mass accumulation rates at DSDP Site 85-572

At Site 572, located at 1°N, 114° W (3903 m water depth), we recovered a continuous hydraulic piston cored section of upper Miocene to upper Pleistocene pelagic sediments. The sediment is composed of biogenic carbonate and silica with nonbiogenic material as a minor component. Detailed analysis of the calcium carbonate content shows that the degree of variability in carbonate deposition apparently changed markedly between the late Miocene and Pliocene at this equatorial Pacific site. During this interval carbonate mass accumulation rates decreased from 2.6 to 0.8 g/cm**2 per 10**3 yr. If we assume that variations in CaCO3 content reflect changes in the degree of dissolution, then the detailed carbonate analysis would suggest that the degree of variability in carbonate deposition decreases by a factor of 5 as the dominant wavelength of variations increases significantly. However, if the variability in carbonate concentration is described in terms of changes in mean mass accumulation, calculations then suggest that relatively small changes in noncarbonate rates may be important in controlling the observed carbonate records. In addition, the analysis suggests that the degree of variability observed in pelagic carbonate data may in part reflect total accumulation rates. Intervals with high sedimentation rates show lower amplitude variations in concentration than intervals with lower sedimentation rates for the same degree of change in the carbonate accumulation rate.

Paleomagnetism and bedding orientations at DSDP Sites 87-582, 87-583 and 87-584

Paleomagnetic measurements of sediment samples provide the magnetostratigraphy at Deep Sea Drilling Sites 582, 583, and 584 in the Nankai Trough and the Japan Trench. Drastic changes in the rate of sediment accumulation are documented by the magnetostratigraphic and biostratigraphic correlations. The changes in the accumulation rate correspond to the supply of sediments and variations in the accretionary process, which are directly related to the tectonic cycles in the geologic evolution of the Japanese island arc. Faults and folds within the drilled sedimentary sequences are oriented by paleomagnetic declination. Their directions and stress patterns are related to the relative plate motion along the trough and trench. The original remanent magnetization of the sediment was modified and remagnetized in the tectonic process of accretion by physical deformation, faulting, and intrusion of dewatering veinlets.

Magnetic properties, grain sizes and minerals at DSDP Site 83-504B

Twenty-seven samples from the Leg 83 section of Hole 504B have been investigated using magnetic, optical, and electron optical methods. The primary magnetic mineral to crystallize was titanomagnetite of approximate composition Fe2.4Ti0.6O4 (TM60), but none survives, nor is there evidence of titanomaghemite produced by oxidation of TM60. The average measured magnetic properties can be interpreted in terms of magnetite, Fe3O4, having average grain size of <1 µm and present in average volume concentration of - 0.5%. The intensity of the natural remanent magnetization (NRM) of the rocks could also be accounted for as being a thermoremanence carried by this mineral. Although the heterogeneity of the titanomagnetite grains could be detected optically, the texture of the intergrown phases is poorly developed. In some samples from the massive units of the lower part of the section, trellis patterns were visible. The Fe3O4 present in the intergrowths is too intimately mixed with the other intergrown phases to be revealed by electron microprobe analysis that simply returns the bulk composition of the intergrowth (oxidized TM60). The path by which the mineral assemblage evolved from TM60 to an Fe304-containing intergrowth, under the temperature and pressure conditions obtaining in the Leg 83 section, makes interesting speculation. Deuteric oxidation, maghemitization/inversion, or some hypothetical low-temperature/high-pressure oxidation by a leaching-of-iron process may all play roles.

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.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Benthic foraminiferal composition at the inner wall of the Middle America Trench, Costa Rica

The sediments of Deep Sea Drilling Project Site 565 and University of Texas Marine Science Institute Cores IG-24-7-38 to -42 taken on the landward slope of the Middle America Trench exhibit characteristics of material subject to reworking during downslope mass flow. These characteristics include a generally homogeneous texture, lack of sedimentary structures, pervasive presence of a penetrative scaly fabric, and presence of transported benthic foraminifers. Although these features occur throughout the sediments examined, trends in bulk density, porosity, and water content, and abrupt shifts in these index physical properties and in sediment magnetic properties at Site 565 indicate that downslope sediment creep is presently most active in the upper 45 to 50 m of sediment. It cannot be determined whether progressive dewatering of sediment has brought the material at this depth to a plastic limit at which sediment can no longer flow (thus resulting in its accretion to the underlying sediments) or whether this depth represents a surface along which slumping has occurred. We suspect both are true in part, that is, that mass movements and downslope reworking accumulate sediments in a mobile layer of material that is self-limiting in thickness.

Stable isotope record of DSDP Hole 81-552A in the northeastern Atlantic Ocean

Oxygen and carbon isotope ratios in benthic foraminifers have been determined at 10 cm intervals through the top 59 m of DSDP Hole 552A. This provides a glacial record of remarkable resolution for the late Pliocene and Pleistocene. The major glacial event which marked the onset of Pleistocene-like glacial-interglacial alternations was at about 2.4 m.y. ago. These very high-resolution data do not support the notion of significant Northern Hemisphere glaciation between 3.2 and 2.4 m.y. ago.

Interstitial water chemistry at DSDP Leg 82 Holes

Interstitial waters were collected at only two sites during Leg 82, Sites 558 and 563. Only very small changes in dissolved calcium and magnesium occur, presumably resulting from reactions in the underlying basement basalts. Dissolved strontium profiles indicate maxima, which can be understood in terms of carbonate recrystallization processes. Data on Sr/Ca in carbonates cannot be used to estimate the extent of recrystallization that has occurred in these sediments.

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.