Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Organic carbon, reduced sulfur, and iron in Miocene to Holocene sediments from the Oman and Beguela upwelling systems

We examined sediments from Neogene and Quaternary sections of the Benguela and Oman upwelling systems (DSDP Site 532, ODP Sites 723 and 722) to determine environmental and geochemical factors which control and limit pyrite formation in organic-carbon-rich marine sediments. Those samples from the upwelling sites, which contained low to moderate concentrations of total organic carbon (0.7%-3%), had C/S ratios typical of normal marine sediments, i.e., around 2.8. In these sediments, TOC availability probably limited pyrite formation. Results that do not conform with accepted models were found for the sediments high in TOC (3^0-12.4%). The organic matter was of marine origin and contained considerable pyrolytic hydrocarbons, a fact that we take as a sign of low degradation, yet significant concentrations of dissolved sulfate coexisted with it (> 5 mmol/L in the case of Sites 532 and 723). Detrital iron was probably not limiting in either case, because the degree of pyritization was always less than 0.65. Therefore, controls on sulfate reduction and pyrite formation in the organic matter-rich sediments do not appear to conform simply to generally accepted diagenetic models. The data from these thermally immature, old, and organic-rich marine sediments imply that (1) the total reduced sulfur content of organic-rich marine upwelling sediments rarely exceeds an approximate boundary of 1.5% by weight, (2) the C/S ratio of these sediments is not constant and usually much higher than the empirical values proposed for marine sediments. We conclude that sedimentary pyrite formation in upwelling sediments is limited by an as yet unknown factor, and that caution is advised in using C/S ratios and C vs. S diagrams in paleoenvironmental reconstructions for organic-rich sediments.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

Sedimentary mineralogy of argillaceous sediments at DSDP Legs 56-57 Holes

Mineral assemblages of DSDP Holes 436 and 438A and the upper section of Hole 439 (871.5-911.0 m sub-bottom) resemble each other and are composed of montmorillonite (probably a small portion of montmorillonite/illite mixed-layer clays), illite, chlorite, kaolinite, quartz, plagioclase, hornblende, calcite, dolomite, siderite, gypsum, pyrite, and halite. In the middle section of Hole 439 (933.5-1041.0 m), clinoptilolite is also found. In the lower section of Hole 439 (1077.5-1150.0 m), montmorillonite is not confirmed, and clinoptilolite and mixed-layer illite are found. These assemblages, which also contain detrital kaolinite, are generally found in sediments from brackish-water environments. At Site 439, more than 1000 meters of sediment might have been removed by erosion at the base.

Mineral and chemical compositions of sedimentary and volcano-sedimentary rocks drilled in DSDP Legs 43 and 44

Sedimentary cover on the bottom of the Northwest Atlantic Ocean is underlain by Late Jurassic - Cretaceous tholeiite-basalt formation. It consists of come sedimentary formations with different lithologic features and age. Their composition, stratigraphic position and, distribution are described on materials of deep-sea drilling. Mineralogical and geochemical studies of DSDP Leg 43 and Leg 44 holes lead to new ideas about composition and genesis of some sediment types of and their associations. High metal contents in the chalk formation of black clays on the Bermuda Rise probably result from exhalations. Connection of red-colored and speckled deposits with hiatuses in sedimentation is shown. Main stages of geological history of the North American Basin are reflected in accumulation of the followed formations: ancient carbonate formation (Late Jurassic - Early Cretaceous), formation of black clays rich in organic matter (Cretaceous), formation of speckled clays (Late Cretaceous), siliceous-clayey turbidite formation (Eocene), hemipelagic and pelagic clayey formation (Neogene), and terrigenous turbidite formation (Pleistocene).

Chemical and mineral compositions of sedimentary deposits and magmatic rocks from DSDP Legs 41, 45, 48, and 49

This collective monography by a group of lithologists from the Geological Institute of the USSR Academy of Sciences summarizes materials of the Deep-Sea Drilling Project from the Atlantic Ocean. It gives results of processing materials on the sequences drilled during DSDP Legs 41, 45, 48 and 49. These studies were based on lithological-facial analysis combined with detailed mineralogical-petrographic description. Its chapters give a number of ideas on formation of the Earth sedimentary cover, which can be used for compilation of regional and global schemes of ocean paleogeography, reconstruction of history of some structures in the World Ocean, correlation between sedimentary processes on continents and in oceans, estimation of perspectives for oil and gas fields and ore formation.

Sulfur isotopic variations in nodular and disseminated pyrite at DSDP Hole 93-603B

Analyses of modern marine sediments have suggested that availability and type of organic matter, sedimentation rate, and openness of the sulfate system influence the degree of isotopic fractionation between seawater sulfate and sedimentary iron sulfides. Isotopic studies of ancient sulfides should, therefore, provide insights into conditions of deposition and early diagenesis. Analysis of d34S of disseminated pyrite from Cretaceous sediments of Hole 603B yielded fractionations relative to coeval seawater sulfate ranging from 40 to 55 per mil, which are within the range for modern oxic marine sediments reported by others. Sulfur/carbon ratios are similar to those found from modern marine sediments and suggest that disseminated pyrite formation was dependent upon available organic carbon. These results imply that depositional and early diagenetic conditions during the Cretaceous in Hole 603B were similar to those occurring in initially oxic marine environments today. Macroscopic (nodular) pyrite from Hole 603B is isotopically variable (d34S values = - 48 to + 33 per mil), but generally more positive than disseminated pyrite. The isotopic evidence suggests that macroscopic pyrite formed during late stages of sulfate reduction in a system closed with respect to sulfate. However, detailed analyses of large pyrite nodules did not yield a consistent pattern of isotopic variation from center to rim.