Hydrocarbon gases in Tertiary and Quaternary sediments offshore Peru

Hydrocarbon gases (methane, ethane, propane, isobutane, n-butane, ethene, and propene) are present in Tertiary and Quaternary shelf, upper-slope, and lower-slope deposits of the Peruvian continental margin. Methane dominates the composition of the hydrocarbon gas at all 10 sites examined during Ocean Drilling Program (ODP) Leg 112. Generation of methane is regulated by the amount of sulfate in pore water. Wherever sulfate concentrations approach or equal zero, methane concentrations increase rapidly, reaching values near 100,000 µL/L of wet sediment at eight of the 10 sites. Methane at all 10 sites results from methanogenesis, which is inhibited where sulfate is present and microbial reduction of sulfate occurs. Hydrocarbon gases heavier than methane also are present, but at much lower concentrations than methane. These hydrocarbons are thought to result from early thermal and microbial diagenesis, based on relative gas compositions and trends of concentrations with depth. With few exceptions, the results obtained in the shipboard and shore-based laboratories are comparable for methane and ethane in sediments of Leg 112. Reanalyses of canned sediments from ODP Leg 104 and from Deep Sea Drilling Project (DSDP) Legs 76 and 84 show that gas samples can be stored for as long as 8 yr, but the amounts of individual hydrocarbon gases retained vary. Nevertheless, the trends of the data sets with depth are similar for fresh and stored samples.

Characterization of sorbed volatile hydrocarbons from the Peru margin

Bacterial and thermogenic hydrocarbons are present in the sorbed-gas fraction of Peru margin sediments. At Ocean Drilling Program (ODP) Sites 681, 682, 684, and 686, bacterial gases are restricted to the early diagenetic zones, where dissolved sulfate has been exhausted and methanogenesis occurs. Methane migrating into the sulfate zone at Sites 681, 684, 686, and possibly 682, has been consumed anaerobically by methanotrophs, maintaining the low concentrations and causing an isotope shift in d13C(CH4) to more positive values. Significant amounts of C2+ hydrocarbons occur at the shelf Sites 680/681, 684, and 686/687, where these hydrocarbons may be associated with hypersaline fluids. There is evidence at Site 679 that sorbed C2+ hydrocarbons may also have been transported by hypersaline fluids. This characteristic C2+ hydrocarbon signature in the sorbed-gas fractions of sediments at Site 679 is not reflected in data obtained using the conventional "free-," "canned-," or "headspace-gas" procedures. The molecular and isotope compositions of the sorbed-gas fraction indicate that this gas may have a thermogenic source and may have spilled over with the hypersaline fluids from the Salaverry Basin into the Lima Basin. These traces of thermogenic hydrocarbon gases are over-mature (about 1.5% Ro) and are discordant with the less-mature sediments in which they are found. This observation supports the migration of these hydrocarbons, possibly from continental sources. Sorbed-gas analyses may provide important geochemical information, in addition to that of the free-gases. Sorbed-gases are less sensitive to activities in the interstitial fluids, such as methanogenesis and methanotrophy, and may faithfully record the migration of hydrocarbons associated with hypersaline fluids.

Geochemistry of Peru margin sediments

This data report tabulates results of chemical analyses of sediments from four sites (680, 682, 685, and 688) drilled during Leg 112 offshore Peru. These sediments were recovered from the forearc basins underlying the Peru upwelling area. They are equivalent in facies and age to the Pisco and Monterey formations, both of which are of considerable economic and geological interest as hydrocarbon source rocks deposited under conditions of coastal upwelling. Sediments recovered from the shelf (Site 680) and slope (Sites 682, 685, and 688) during Leg 112 are unconsolidated and are thermally immature. A lack of consolidation and thermal catagenesis makes these deposits ideal targets for chemical investigation into effects of early diagenesis in organic-carbon-rich siliceous muds.

Geochemistry and degree of organic carbon preservation in non-bioturbated, shaly sediments

Based on 13 published porewater H2S and sulphate profiles the amount of H2S escaping from non-bioturbated shales varies between some few % to 45% of the amount of bacterially generated H2S. This finding permits calculation of the original organic carbon (TOCor) content of immature nonbioturbated shales using TOC and sulphur content data. In two immature non-bioturbated sequences from Hungary (Toarcian and Oligocene) the first-order correlation between HI and TOC/TOCor was found to be stronger than that between HI and TOC, indicating that sulphate reduction was the leading process both in decrease in TOC content and degradation of kerogen source potential.

Quaternary through early Eocene benthic foraminifera off Peru

Stratigraphic assemblages of Quaternary through early Eocene benthic foraminifers were recovered among 10 Peru margin drill sites. Various hiatuses and intervals barren in foraminifers characterize the sections, but numerous samples contain abundant, well-preserved benthic foraminifers. Bathymetry of the extant species and California-based estimates of the paleobathymetry of the extinct species permit recognition of Quaternary sea-level fluctuations between shelf and upper bathyal depths that produced vertical migrations of oxygenated and low-oxygen habitats at the six shallow sites. Assemblages from lower-slope sites at about 9° and 11°S indicate a general subsidence of the continental margin from shelf or upper bathyal depths in Eocene time to the present lower bathyal depths. Data from 11°S suggest a major part of this subsidence occurred in late Oligocene to early Miocene time. Downslope-transported shelf specimens, particularly the small biserial species, Bolivina costata and B. vaughani, are major contributors to these lower bathyal assemblages from the middle Miocene through Quaternary time.

Eocene through Pleistocene planktonic foraminifera off Peru

Planktonic foraminifers were studied from 213 samples collected during Leg 112 at 10 sites located on the continental shelf and slope off Peru. Because planktonic foraminifers occur discontinuously downcore, detailed biostratigraphic zonation was not defined. However, it was possible to distinguish early and middle Eocene, early and late Miocene, Pliocene, and Pleistocene sediments on the basis of the planktonic foraminifers. The oldest sediments of Zone P6 of early Eocene age were obtained from the basal part of Hole 688E, which was penetrated to 779.0 m below seafloor (bsf). A biosiliceous facies of the area predominates above the N6-N7 zonal interval of early Miocene age. All sites are within the present coastal upwelling area off Peru, and many of the late Pliocene and Pleistocene assemblages are similar to those that are characteristic of modern upwelling areas. The core samples differ, however, by having a predominance of cold-water elements, such as Neogloboquadrina incompta and N. pachyderma. Warm-water species are prevalent at some horizons in the cores, suggesting shifts of the coastal upwelling centers or warmer climatic events.

Lithium sources in pore fluids of Peru slope

High Li concentrations, up to a maximum of 1155 µM are observed in the pore fluids of the Peru convergent margin slope sediments. At Ocean Drilling Program Sites 683 and 685 (ca. 9°S), the Li concentration depth gradients are twice as steep as at Site 682 and 688 (ca. 11°S). Within the sediments, the most important Li sources are from aluminosilicate minerals. Biogenic opal-A contains little Li and thus dilutes the Li concentration of the bulk sediments. The sediment compositions and the thermal regimes are similar at 9° and 11°S, suggesting there is an additional, non-sedimentary source for the observed high Li concentrations in the northern pore fluids. At 9°S, the 87Sr/86Sr ratios reach a maximum value of 0.709958. The observed radiogenic 87Sr/86Sr values in the pore fluids support the suggestion that the additional Li may derive from exchange reactions with underlying continental crust. The high concentrations of Li at 11°S may derive from basalt alteration at moderate to high temperatures, as suggested by the non-radiogenic 87Sr/86Sr ratios in these pore fluids, which reach a minimum value of 0.707218. Based on (1) Li concentrations in the pore fluids in slope sediments from Peru and several other margins, and (2) an approximate estimate of fluid flux from continental margins into the ocean, continental margins provide an estimated 1 to 3 * 10**10 moles Li/yr to the ocean. This source of oceanic Li, which has not been considered previously, is of the same order of magnitude as some estimates of hydrothermal and river Li fluxes and may have important consequences for the oceanic Li isotope budget. The sink is unknown for this newly discovered and possibly large Li source, but it may be more pervasive low-temperature alteration of oceanic basement than previously estimated, or burial of mineral phases, such as authigenic clay minerals, or metal oxyhydroxides which may be Li-rich.

Silicoflagellates, actiniscidians, and ebridians of ODP Leg 105 sites

Neogene and Quaternary silicoflagellates, actiniscidians, and ebridians are described from Sites 679 through 688 in the eastern Pacific off Peru. Five silicoflagellate zones and one horizon can be distinguished in the Neogene and Quaternary sequences. The encountered Eocene and Oligocene sequences are barren in silicoflagellates. Several hiatuses were noted in the Neogene and early Pleistocene sequences. Displaced silicoflagellates and ebridians from older strata were found occasionally, with a distinct increase in the Quaternary at Site 688. Distribution lists for species found are presented for Sites 682, 683, 685 and 688. Systematic discussion centers on the Distephanus bioctonarius group, with special reference to Hole 681A. Two new forms (Distephanus bioctonarius f. decimarius and Distephanus speculum subsp. speculum f. pseudoseptenarius) are described from the eastern Pacific Quaternary sequence.