Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

(Table 2) Isotopic composition of pyrite sulfur in bottom sediments and carbonate nodules from the Gulf of California at Station DM9-666

New data on phosphorites collected by dredging and trawling at depths from 2700 to 520 m in the open Atlantic Ocean (i.e. outside of the shelf and the continental slope) are reported. Aphanitic, granular, brecciated, and conglomerate-like types are distinguished among the phosphorites. A comparison of the studied phosphorites with ones from the Atlantic shelf of Africa and from seamounts of other oceans is made.

(Table 1) Sulfur isotopes and description of anhydrite in DSDP Holes 70-504B and 83-504B

Anhydrite occurs in veins in hydrothermally altered basalts recovered from Hole 504B during Leg 83 of the Deep Sea Drilling Project. Sulfur isotopic data indicate that the anhydrites formed from fluids with sulfur isotopic compositions similar to seawater sulfate. Anhydrite probably formed as a pulse of relatively unreacted seawater was heated when it entered a relatively hot hydrothermal system containing evolved fluids. Reheating and continued evolution of the system followed anhydrite deposition. Preservation of anhydrite in Hole 504B was probably favored by the high temperatures and by the low permeability that resulted from the sealing of cracks with secondary minerals. Evidence also indicates that anhydrite was partly replaced by laumontite and prehnite at relatively high temperatures, and possibly by calcite at lower temperatures.

Elemental data for composites from DSDP Sites 417A, 417D, and 418A

While the input of river-alkalinity into seawater is relatively well known, the complementary acidity production is poorly understood. Using the major-element budget of seafloor alteration of the upper 500 m of 120-Ma-old oceanic crust at DSDP/ODP Sites 417A, 417D and 418A in the central western Atlantic, we estimate the acidity flux associated with the low-temperature weathering of the upper oceanic crust. The acidity flux is calculated based on major-element fluxes and charge-balance considerations. The relevant chemical fluxes from seawater to the upper crust are 4.1+-0.1; 1.4+-1.4; 2.2+-0.6 and -12+-2 10**11 mol/yr for K, Mg, Na and silicate-Ca, respectively. The associated acidity flux is (3.5+-3)10**11 eq/y. Relative to continental weathering, these fluxes are significant for K and silicate-Ca, but are minor for Na, Mg and acidity. Thus, riverine fluxes of alkalinity are not significantly balanced by acidity fluxes from low-temperature upper ocean crust alteration.

Elemental and stable isotopic composition of fine fraction samples of ODP Site 115-709 (Table 1)

Stable isotopic and minor element compositions were measured on the fine fraction of pelagic carbonate sediments from Ocean Drilling Program Site 709 in the central Indian Ocean. This section ranges in age from 47 Ma to the present. The observed compositional variations are the result of either paleoceanographic changes (past oceanic chemical or temperature variations) or diagenetic changes. The CaCO3 record is little affected by diagenesis. From previous work, carbonate content is known to be determined by the interplay of biological productivity, water column dissolution, and dilution. The carbon isotopic record is generally similar to previously published curves. A good correlation was observed between sea-level high stands and high 13C/12C ratios. This supports Shackleton's hypothesis that as the proportion of organic carbon buried in marine sediments becomes larger, oceanic-dissolved inorganic carbon becomes isotopically heavier. This proportion appears to be higher when sea level is higher and organic carbon is buried in more extensive shallow-shelf sediments. The strontium content and oxygen isotopic composition of carbonate sediments are much more affected by burial diagenesis. Low strontium concentrations are invariably associated with high values of d18O, probably indicating zones of greater carbonate recrystallization. Nevertheless, there is an inverse correlation between strontium concentration and sea level that is thought to be a result of high-strontium aragonitic sedimentation on shallow banks and shelves during high stands. Iron and manganese concentrations and, to a lesser extent, magnesium and strontium concentrations and carbon isotopic ratios are affected by early diagenetic reactions. These reactions are best observed in a slumped interval of sediments that occurs between 13.0 and 17.5 Ma. As a result of microbial reduction of manganese and iron oxides and dissolved sulfate, it is hypothesized that small amounts of mixed-metal carbonate cements are precipitated. These have low carbon isotopic ratios and high concentrations of metals.