Uranium contents and isotope ratios of uranium and strontium in sediments, leachates and pore fluids from ODP Hole 162-984A

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by a-recoil injection of 234Th. The fraction of 238U decays that result in a-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 0.0000004 to 0.000002 1/yr. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 1000 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ~ 0.1 1/age for ages spanning 1000 to 500,000,000 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.

Chemistry of serpentinized peridotites from ODP Hole 109-670A

In this paper we describe textural relationships in hydrated upper mantle peridotites emplaced at a nonconstructive ridge segment. Development of serpentinites and partially serpentinized peridotites takes place in four main stages: (1) pervasive serpentinization forming mainly lizardite, (2) a tensional stage forming chrysotile + talc + chlorite, (3) a deformational stage forming antigorite + tremolite, and (4) a late local tensional stage forming another generation of chrysotile veinlets. Mineral chemistry of serpentine pseudomorphs reflects in part primary mineral compositions. Olivine pseudomorphs are typically nickeliferous and depleted in aluminum and chromium. Orthopyroxene pseudomorphs have lower nickel contents and relatively high iron, aluminum, and chromium contents. Clinopyroxene pseudomorphs have very low nickel contents and relatively high aluminum and chromium contents. These chemical patterns in the serpentinites can be used to help discriminate between harzburgitic and lherzolitic protoliths. Oxygen isotopes and mineral parageneses suggest serpentine is derived from circulation of hydrothermal (200?C) fluids through the peridotite body. Crystallization of tremolite, talc, and chlorite may have occurred at temperatures up to 525?C if C02/H20 ratios were less than 0.25. Open fissures developing in aging upper mantle provide paths for important seawater circulation through a thin basaltic carapace down to shallow mantle rocks.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Boron isotope ratios of samples from ODP Leg 125 sites at a serpentine seamount, Mariana forearc

Serpentinite clasts and muds erupted from Conical Seamount, Mariana forearc, show substantial enrichment in boron (B) and 11B (delta11B up to +15?) relative to mantle values. These elevated B isotope signatures result from chemical exchange with B-rich pore fluids that are upwelling through the seamount. If the trends of decreasing delta11B with slab depth shown by cross-arc magmatic suites in the Izu and Kurile arcs of the western Pacific are extended to shallow depths (~25 km), they intersect the inferred delta11B of the slab-derived fluids (+13x) at Conical Seamount. Simple mixtures of a B-rich fluid with a high delta11B and B-poor mantle with a low delta11B are insufficient to explain the combined forearc and arc data sets. The B isotope systematics of subduction-related rocks thus indicate that the fluids evolved from downgoing slabs are more enriched in 11B than the slab materials from which they originate. Progressively lower delta11B in arc lavas erupted above deep slabs reflects both the progressive depletion of 11B from the slab and progressively greater inputs of mantle-derived B. This suggests that the slab releases 11B-enriched fluids from the shallowest levels to depths greater than 200 km.

Major element chemistr yof fallout tephra from ODP Hole 125-782A

New and published analyses of major element oxides (SiO2, TiO2, Al2O3, FeO*, MnO, MgO, CaO, K2O, Na2O and P2O5) from the central Izu Bonin and Mariana arcs (IBM) were compiled in order to investigate the evolution of the IBM in terms of major elements since arc inception at ~49 million years ago. The database comprises ?3500 volcanic glasses of distal tephra fallout and ?500 lava samples, ranging from the Quaternary to mid-Eocene in age. The data were corrected to 4 wt% MgO in order to display the highly resolved temporal trends. These trends show that the IBM major elements have always been "arc-like" and clearly distinct from N-MORB. Significant temporal variations of some major element oxides are apparent. The largest variations are displayed by K4.0. The data support a model wherein the K2O variability is caused by the addition of slab component with strongly differing K2O contents to a fairly depleted subarc mantle; variable extents of melting, or mantle heterogeneity, appear to play a negligible role. The other major element oxides are controlled by the composition and processes of the subarc mantle wedge. The transition from the boninitic and tholeiitic magmatism of the Eocene and Oligocene to the exclusively tholeiitic magmatism of the Neogene IBM is proposed to reflect a change in the composition of the subarc mantle wedge. The early boninitic magmas originate from an ultra-depleted subarc mantle, that is residual to either the melting of E-MORB mantle, or of subcontinental lithospheric mantle. During the Eocene and Oligocene, this residual mantle is gradually replaced by Indian MORB mantle advected from the backarc regions. The Indian MORB mantle is more radiogenic in Nd isotope ratios but also more fertile with respect to major and trace elements. Therefore the Neogene tholeiites have higher Al2O3 and TiO2 contents and lower mg# numbers at given SiO2 content. After the subarc mantle replacement was complete in the late Oligocene or early Miocene, the Neogene IBM entered a "steady state" that is characterized by the continuous advection of Indian MORB mantle from the reararc, which is fluxed by fluids and melt components from slab. The thickness of the IBM crust must have grown with time, but any effects of crustal thickening on the major element chemistry of the IBM magmas appear to be minor relative to the compositional changes that are related to source composition. Therefore next to the processes of melting, the composition of the mantle sources must play a major role in creating substantiative heterogeneities in the major element chemistry of the arc crust.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.

Chemical and isotopic compositions of rocks and minerals from the Ashadze and Logachev hydrothermal fields, Mid-Atlantic Ridge

This study was aimed at reconstructing a sequence of events in the magmatic and metamorphic evolution of peridotites, gabbroids, and trondhjemites from internal oceanic complexes of the Ashadze and Logachev hydrothermal vent fields. Collections of plutonic rocks from Cruises 22 and 26 of R/V "Professor Logachev", Cruise 41 of R/V "Akademik Mstislav Keldysh", and from the Serpentine Russian-French expedition aboard R/V "Pourquoi pas?" were objects of this study. Data reported here suggest that the internal oceanic complexes of the Ashadze and Logachev fields formed via the same scenario in these two regions of the Mid-Atlantic Ridge. On the other hand, an analysis of petrological and geochemical characteristics of the rocks indicated that the internal oceanic complexes of the MAR axial zone between 12°58'N and 14°45'N show pronounced petrological and geochemical heterogeneity manifested in variations in degree of depletion of mantle residues and in Nd isotopic compositions of rocks from the gabbro-peridotite association. Trondhjemites from the Ashadze hydrothermal field can be considered as partial melting products of gabbroids under influence of hydrothermal fluids. It was supposed that presence of trondhjemites in internal oceanic complexes of MAR can be used as a marker for the highest temperature deep-rooted hydrothermal systems. Perhaps, the region of the MAR axial zone, in which petrologically and geochemically contrasting internal oceanic complexes are spatially superimposed, serves as an area for development of large hydrothermal clusters with considerable ore-forming potential.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.