Geochemistry of Miocene "blue tuff" samples

Distinctive, massive to stratified, pale blue volcaniclastics, initially referred to as the "blue tuff," were encountered at all four sites drilled during ODP Leg 127 in the Japan Sea. Detailed vertical sequence analysis, plagioclase chemistry, plagioclase 87Sr/86Sr isotopic composition, and 40Ar/39Ar age dating indicate that thick sequences of the blue tuff are not genetically related. Blue tuffs at Hole 794B were apparently deposited by density flows at ambient temperature. Deposition was penecontemporaneous with a large submarine phreatomagmatic eruption at 14.9 Ma in bathyal or deeper water depths. The blue tuffs at this location comprise mostly reworked hydroclastic glass shards and lesser amounts of plagioclase crystals. Pyrogenic plagioclase has an average An mole% of 18±3. Comparison of blue tuff plagioclase compositions with the composition of plagioclase from acoustic basement at Site 794 suggests that these rocks are not genetically related. As such, the extrapolation of sediment accumulation rate data in conjunction with this more precise age for the blue tuff corroborates previous minimum age estimates of 16.2 Ma for acoustic basement at Site 794. Blue tuffs at Hole 796B were probably deposited at ambient temperatures by downslope slumping and density flow of reworked pyrogenic debris. This debris includes abundant bubble wall glass shards and plagioclase crystals, with variable admixture of volcanic lithic and intrabasinal fragments. Pyrogenic fragments were produced by subaerial or shallow submarine, magmatic eruptions dated at 7.6 Ma. Blue tuffs contain a heterogeneous mixture of unrelated fragments including a mixed population of plagioclase crystals. The average An mole% of the predominant, probable comagmatic, plagioclase population is 30±4. The two sequences of blue tuff studied are distinct in age, mineral composition, and the eruptive origin of pyroclastic fragments. Preliminary 87Sr/86Sr isotopic compositions of plagioclase, however, indicates that blue tuffs at both locations are the product of typical, subduction-related island arc magmatism. Based on the results of this study, there is no justification for stratigraphic correlation of widespread, Miocene, blue to blue-gray bentonitic tuff and tuffaceous sandstones nor the interpretation that these strata are indicative of regional, explosive submarine volcanism genetically related to rifting and formation of the Japan Sea. Rather, these reworked pyroclastic strata of intermediate composition were deposited over a protracted 6-8 m.y. period in association with widespread, subduction-related submarine to subaerial volcanism in the Japan Sea backarc basin.

Os and Re concentrations and Os isotope ratios for DSDP and ODP metalliferous sediments from the Pacific Ocean (Table 1)

We report new 187Os/186Os data and Re and Os concentrations in metalliferous sediments from the Pacific to construct a composite Os isotope seawater evolution curve over the past 80 m.y. Analyses of four samples of upper Cretaceous age yield 187Os/186Os values of between 3 and 6.5 and 187Re/186Os values below 55. Mass balance calculations indicate that the pronounced minimum of about 2 in the Os isotope ratio of seawater at the K-T boundary probably reflects the enormous input of cosmogenic material into the oceans by the K-T impactor(s). Following a rapid recovery to 187Os/186Os of 3.5 at 63 Ma, data for the early and middle part of the Cenozoic show an increase in 187Os/186Os to about 6 at 15 Ma. Variations in the isotopic composition of leachable Os from slowly accumulating metalliferous sediments show large fluctuations over short time spans. In contrast, analyses of rapidly accumulating metalliferous carbonates do not exhibit the large oscillations observed in the pelagic clay leach data. These results together with sediment leaching experiments indicate that dissolution of non-hydrogenous Os can occur during the hydrogen peroxide leach and demonstrate that Os data from pelagic clay leachates do not always reflect the Os isotopic composition of seawater. New data for the late Cenozoic further substantiate the rapid increase in the 187Os/186Os of seawater during the past 15 Ma. We interpret the correlation between the marine Sr and Os isotope records during this time period as evidence that weathering within the drainage basin of the Ganges-Brahmaputra river system is responsible for driving seawater Sr and Os toward more radiogenic isotopic compositions. The positive correlation between 87Sr/86Sr and U concentration, the covariation of U and Re concentrations, and the high dissolved Re, U and Sr concentrations found in the Ganges-Brahmaputra river waters supports this interpretation. Accelerating uplift of many orogens worldwide over the past 15 Ma, especially during the last 5 Ma, could have contributed to the rapid increase in 187Os/186Os from 6 to 8.5 over the past 15 Ma. Prior to 15 Ma the marine Sr and Os record are not tightly coupled. The heterogeneous distribution of different lithologies within eroding terrains may play an important role in decoupling the supplies of radiogenic Os and Sr to the oceans and account for the periods of decoupling of the marine Sr and Os isotope records.

(Table 1) Osmium concentrations and isotopic ratios for ODP Leg 125 peridotites

Mantle peridotites drilled from the Izu-Bonin-Mariana forearc have unradiogenic 187Os/188Os ratios (0.1193 to 0.1273), which give Proterozoic model ages of 820 to 1230 million years ago. If these peridotites are residues from magmatism during the initiation of subduction 40 to 48 million years ago, then the mantle that melted was much more depleted in incompatible elements than the source of mid-ocean ridge basalts (MORB). This result indicates that osmium isotopes record information about ancient melting events in the convecting upper mantle not recorded by incompatible lithophile isotope tracers. Subduction zones may be a graveyard for ancient depleted mantle material, and portions of the convecting upper mantle may be less radiogenic in osmium isotopes than previously recognized.

Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.