Tephrostratigraphy and radiometric dating of authigenic carbonates

At convergent margins, fluids rise through the forearc in response to consolidation of the upper plate and dewatering of the subducting plate, and produce various cold-seep-related features on the seafloor (mud diapirs, mud mounds). At the Central American forearc, authigenic carbonates precipitated from rising fluids within such structures during active venting while typical mixed-mud sediments were ejected onto the surrounding seafloor where they became intercalated with normal pelagic background sediments, indicating that mud mounds evolved unsteadily through alternating active and inactive phases. Intercalated regional ash layers from Plinian eruptions at the Central American volcanic arc provide time marks that constrain the ages of mud ejection activity. U/Th dating of drill core samples of authigenic carbonate caps of mud mounds yields ages agreeing well with those constrained by ash layers and showing that carbonate caps grow inward rather than outward during active venting. Both dating approaches show that offshore Nicaragua and Costa Rica (1) active and inactive phases can occur simultaneously at neighboring mounds, (2) mounds along the forearc have individual histories of activity, but there are distinct time intervals when nearly all mounds have been active or inactive, (3) lifetimes of mounds reach several hundred thousand years, and (4) highly active periods last 10-50 k.y. with intervening periods of >10 k.y. of relative quiescence.

Geochemistry of secondary carbonates in ODP Leg 115 basalts

This report presents the results of a study of the stable isotopic and chemical composition of secondary carbonate minerals precipitated within basalts at Ocean Drilling Program Sites 707 and 715. At Site 715, the secondary carbonates are all composed of calcite and display a narrow range of carbon and oxygen stable isotope ratios, with values ranging from -2.75 per mil to 1.95 per mil PDB and -0.27 per mil to 2.86 per mil PDB, respectively. Strontium, iron, and manganese values of the samples are generally low. The geochemistry of Site 715 samples indicates that they precipitated from seawater-domi- nated fluids, at low temperatures, as is typical of secondary carbonates from most Deep Sea Drilling Project sites. In contrast, at Site 707, aragonite, siderite, and manganese-rich calcite occur as secondary carbonates in addition to calcite. The carbon isotopes of the Site 707 carbonates of all rock types are depleted in 13C. Values range from -2.79 per mil to -16.43 per mil PDB. Oxygen isotope values do not show a wide variation, ranging from -1.78 per mil to 1.17 per mil. The strontium contents of the samples range from 5200 to 8100 ppm for aragonites, and from 145 to 862 ppm for calcites. Iron and manganese contents are high in calcites and siderites and low in aragonites. Site 707 carbonates precipitated at low temperatures in a fairly closed system, in which basalt-seawater interaction has greatly influenced the chemistry of the pore fluids. The reactions occurring within the system before and in conjunction with secondary carbonate precipita- tion include oxidation of isotopically light methane, derived from fluids circulating within the basalts, and reduction of substantial amounts of iron and manganese oxides from the basalts.

Mineralogy and stable isotopic composition of carbonates and sulfide minerals from ODP Leg 164 sites

During Ocean Drilling Program Leg 164, gas hydrates were recovered in the Blake Ridge where the top of the gas hydrate zone lies at about 200 meters below seafloor (mbsf) and the bottom-simulating reflector (BSR) is located at about 450 mbsf. There is no sedimentological discontinuity crossing the BSR. The BSR is disrupted by the salt piercement of the Cape Fear Diapir. The authigenic carbonates (dolomite and siderite) are always present in small amounts (a few weight percent) in the sediments; they are also concentrated in millimeter- to centimeter-sized nodules and layers composed of dolomite above the top of the gas hydrate reservoir, and of siderite below the BSR. In the Blake Ridge, the dolomite/siderite boundary is located near 140 mbsf. The distribution with depth of the d18O values of dolomite and siderite shows a sharp decrease from high values (maximum 7.5 per mil) in the topmost 50 m, to very low values (minimum -2.7 per mil) at 140 mbsf, and at greater depth increase to positive values within the range of 1.8 per mil to 5.0 per mil. The d13C distribution is marked by the rapid increase with greater depth from low values (-31.3 per mil to -11.4 per mil) near 50 mbsf to positive values at 110 mbsf, which remain in the range of 1.7 to 5.4 down to 700 mbsf. Diagenetic carbonates were precipitated in pore waters in which d18O and d13C values were highly modified by strong fractionation effects, both in the water and in the CO2-CH4 systems associated with the formation and dissociation of gas hydrates.

Stable isotope analysis and biomarkers of carbonates from the Columbia River in southwestern Washington, USA

Exotic limestone masses with silicified fossils, enclosed within deep-water marine siliciclastic sediments of the Early to Middle Miocene Astoria Formation, are exposed along the north shore of the Columbia River in southwestern Washington, USA. Samples from four localities were studied to clarify the origin and diagenesis of these limestone deposits. The bioturbated and reworked limestones contain a faunal assemblage resembling that of modern and Cenozoic deep-water methane-seeps. Five phases make up the paragenetic sequence: (1) micrite and microspar; (2) fibrous, banded and botryoidal aragonite cement, partially replaced by silica or recrystallized to calcite; (3) yellow calcite; (4) quartz replacing carbonate phases and quartz cement; and (5) equant calcite spar and pseudospar. Layers of pyrite frequently separate different carbonate phases and generations, indicating periods of corrosion. Negative d13Ccarbonate values as low as -37.6 per mill V-PDB reveal an uptake of methane-derived carbon. In other cases, d13Ccarbonate values as high as 7.1 per mill point to a residual, 13C-enriched carbon pool affected by methanogenesis. Lipid biomarkers include 13C-depleted, archaeal 2,6,10,15,19-pentamethylicosane (PMI; d13C: -128 per mill), crocetane and phytane, as well as various iso- and anteiso-carbon chains, most likely derived from sulphate-reducing bacteria. The biomarker inventory proves that the majority of the carbonates formed as a consequence of sulphate-dependent anaerobic oxidation of methane. Silicification of fossils and early diagenetic carbonate cements as well as the precipitation of quartz cement - also observed in other methane-seep limestones enclosed in sediments with abundant diatoms or radiolarians - is a consequence of a preceding increase of alkalinity due to anaerobic oxidation of methane, inducing the dissolution of silica skeletons. Once anaerobic oxidation of methane has ceased, the pH drops again and silica phases can precipitate.

Chemical and isotopic compositions of authigenic carbonates from bottom sediments of Northwest Pacific marginal seas

The paper presents data on authigenic carbonate distribution in Holocene - Upper Pleistocene deposits of the Okhotsk, Japan, East China, Philippine and South China Seas. Description of carbonate samples, their chemical and isotope compositions are given. Chemical analysis of the samples indicates that almost all authigenic carbonates are composed of calcite or magnesian calcite; and only in one case, of siderite. Oxygen isotopic composition (d18O) ranges from +37.7 to +26.1 per mil (SMOW); it is, probably, connected with different temperatures of carbonate formation. A distinct geographic regularity is traced. Decrease in d18O values is observed from the cold Okhotsk Sea to the warm South China Sea. A very wide range of carbon isotopic composition (d13C from -42 to +3.8 per mil) indicates different sources of carbonic acid required for formation of these carbonates. As a basis for carbon isotopic composition we can distinguish three sources of carbonic acid in the studied sediments: microbiological methane oxidation, organic matter destruction during sediment diagenesis, and dissolved organogenic limestone. Thus, formation of authigenic carbonates in sediments from the marginal seas of the Northwest Pacific results from: 1) sediment diagenesis, 2) methane oxidation in zones of gas anomalies, 3) their precipitation from the supersaturated by carbonates sea shoal waters of tropical sea lagoons.