ALBERT

Description: Methane carbon-isotopic compositions (d13C values relative to the PDB standard) at Sites 565, 566, 567, and 569 were lighter (enriched in 12C) than -60 per mil, indicating a biogenic origin. In the deeper sections at Sites 568 and 570, d13C values were heavier, approaching -40 per mil, and therefore suggest a thermogenic source. A significant thermogenic source was discounted, however, because the carbon dioxide d13C values in these sections were also anomalously heavy, suggesting that the methane may have formed biogenically by reduction of the heavy carbon dioxide. d13C values of ethane and higher hydrocarbons were measured in several sections from Sites 566 and 570 that contained sufficient C2-C4 hydrocarbon concentrations. Ethane values in six sections (245-395 m sub-bottom) from Site 570 were fairly uniform, ranging from -24 to -26 per mil. These values are among the heaviest ethane values reported for natural gases. The isobutane/ n-butane and isopentane/n-pentane ratios of the core gases suggested that the C2-C5 hydrocarbons are thermally produced by low-temperature chemical diagenesis of indigenous organic matter. This process apparently generates isotopically heavy C2-C5 hydrocarbons. High gas concentrations in the serpentinite basement rocks at Sites 566 and 570 appear to have resulted from migrated biogenic methane gas containing small amounts of immature C2-C5 hydrocarbons.

Description: 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.

Description: 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.

Description: In this chapter, we will report on the amino acids in the total acid hydrolysate of eight sediment samples from Leg 68 Site 502. This site was located on a topographic high at a depth of 3051 meters in the Colombian Basin of the western Caribbean Sea. Four holes were cored at the site by means of the hydraulic piston corer to a maximum sediment depth of 218 meters. The composite section is a virtually continuous, undisturbed sediment record covering almost 8 million years from the Holocene to late Miocene. Age estimates for the section are based on excellent magnetostratigraphic and biostratigraphic records. Four lithostratigraphic units (A, B, C, and D) were recognized, based on differences in color and content of clay, ash, foraminifers, and siliceous microfossils (Prell, Gardner, et al., 1980): A, yellowish brown to light brownish gray foraminifer-bearing (〉 10%) nannofossil marl; B, gray to olive gray foraminifer-bearing nannofossil marl with occasional ash beds; C, light gray to dark greenish gray calcareous clay and foraminifer-bearing (〈 10%) nannofossil marl; D, pale green to grayish green calcareous, ash-bearing clay with siliceous microfossils. The calcium carbonate content of these sediments increases from about 27 to about 49% from late Miocene to middle Pliocene (about 3.6 Ma) and remains uniform at about 48 to 50% from that time throughout the Quaternary. The eight sediment samples for amino acid analyses came from the third (502B) and fourth (502C) holes at Site 502. Samples ranged in sub-bottom depth from 4.3 to 225 meters spanning time from 0.3 to 7.7 Ma.

Description: Two sites of the Deep Sea Drilling Project in contrasting geologic settings provide a basis for comparison of the geochemical conditions associated with marine gas hydrates in continental margin sediments. Site 533 is located at 3191 m water depth on a spit-like extension of the continental rise on a passive margin in the Atlantic Ocean. Site 568, at 2031 m water depth, is in upper slope sediment of an active accretionary margin in the Pacific Ocean. Both sites are characterized by high rates of sedimentation, and the organic carbon contents of these sediments generally exceed 0.5%. Anomalous seismic reflections that transgress sedimentary structures and parallel the seafloor, suggested the presence of gas hydrates at both sites, and, during coring, small samples of gas hydrate were recovered at subbottom depths of 238m (Site 533) and 404 m (Site 568). The principal gaseous components of the gas hydrates wer methane, ethane, and CO2. Residual methane in sediments at both sites usually exceeded 10 ml/l of wet sediment. Carbon isotopic compositions of methane, CO2, and SumCO2 followed parallel trends with depth, suggesting that methane formed mainly as a result of biological reduction of oxidized carbon. Salinity of pore waters decreased with depth, a likely result of gas hydrate formation. These geochemical characteristics define some of the conditions associated with the occurrence of gas hydrates formed by in situ processes in continental margin sediments.