Concentrations and isotopic ratios of thorium and uranium in pelagic sediments

The predictable in situ production of 230Th from the decay of uranium in seawater, and its subsequent removal by scavenging onto falling particles, provides a valuable tool for normalizing fluxes to the seafloor. We describe a new application, determination of the 232Th that dissolves in the water column and is removed to the seafloor. 232Th is supplied to the ocean in continental minerals, dissolution of which leads to a measurable standing stock in the water column. Sedimentary adsorbed 232Th/230Th ratios have the potential to provide a proxy for estimating the amount of dissolved material that enters the ocean, both today and in the past. Ten core top samples were treated with up to eight different leaching techniques in order to determine the best method for the separating adsorbed from lattice bound thorium. In addition, separate components of the sediments were analyzed to test whether clay dissolution was an important contribution to the final measurement. There was no systematic correlation between the strength of acid used in the leach and the measured 232Th/230Th ratios. In all cases clean foraminifera produced the same ratio as leaches on bulk sediment. In three out of five samples leaches performed on non-carbonate detritus in the <63 µm size fraction were also identical. Without additional water column data it is not yet clear whether there is a simple one to one correlation between the expected deep-water 232Th/230Th and that produced by leaching, especially in carbonate-rich sediments. However, higher ratios, and associated high 232Th adsorbed fluxes, were observed in areas with high expected detrital inputs. The adsorbed fraction was ~35-50% of the total 232Th in seven out of ten samples. Our 230Th normalized 232Th fluxes are reasonable by comparison to global estimates of detrital inputs to the ocean. In nine cases out of ten, the total 230Th-normalized 232Th flux is greater than predicted from the annual dust fall at each specific location, but lower than the average global detrital input from all sources.

Carbonate minerals, uranium and thorium concentration and U-Th ages of sediments from ODP Leg 166 sites

We have performed U-Th isotope analyses on pure aragonite samples from the upper sections of Leg 166 cores to assign each aragonite-rich sediment package to the correct sea-level highstand. The uppermost sediment package from each of the four sites investigated (Sites 1003, 1005, 1006, and 1007) yielded a Holocene U-Th age. Sediment packages from deeper in the cores have suffered diagenesis. This diagenesis consists of significant U loss (up to 40%) in the site nearest the platform (Site 1005), slight U gain in sites further from the platform, and continuous loss of pure 234U caused by alpha recoil at all sites. The difference in diagenesis between the sites can be explained by the different fluid-flow histories they have experienced. Site 1005 is sufficiently close to the platform to have probably experienced a change in flow direction whenever the banks have flooded or become exposed. Other sites have probably experienced continuous flow into the sediment. Although diagenesis prevents assignment of accurate ages, it is sufficiently systematic that it can be corrected for and each aragonite-rich package assigned to a unique highstand interval. Site 1005 has sediment packages from highstands associated with marine isotope Stages 1, 5, 7, 9, and 11. Site 1006 is similar, except that the Stage 7 highstand is missing, at least in Hole 1006A. Site 1003 has sediment only from Stage 1 and 11 highstands within the U-Th age range. And Site 1007 has sediment only from the stage 1 highstand. This information will allow the construction of better age models for these sites. No high-aragonite sediments are seen for Stage 3 or Substages 5a and 5c. Unless rather unusual erosion has occurred, this indicates that the banks did not flood during these periods. If true, this would require the sea level for Substages 5a and 5c to have remained at least ~10 m lower than today.

Uranium concentrations and isotope ratios Bahamas seawater and ODP holes pore-water

The geometry, timing, and rate of fluid-flow through carbonate margins and platforms is not well constrained. In this study, we use U concentrations and isotope ratios measured on small volumes of pore-water from Bahamas slope sediment, coupled with existing chlorinity data, to place constraints on the fluid-flow in this region and, by implication, other carbonate platforms. These data also allow an assessment of the behaviour of U isotopes in an unusually well constrained water-rock system. We report pore-water U concentrations which are controlled by dissolution of high-U organic material at shallow depths in the sediment and by reduction of U to its insoluble 4+ state at greater depths. The dominant process influencing pore-water (234U/238U) is alpha recoil. In Holocene sediments, the increase of pore-water (234U/238U) due to recoil provides an estimate of the horizontal flow rate of 11 cm/year, but with considerable uncertainty. At depths in the sediment where conditions are reducing, features in the U concentration and (234U/238U) profiles are offset from one another which constrains the effective diffusivity for U in these sediments to be c. 1-2 * 10**-8 cm**2/s. At depths between the Holocene and these reducing sediments, pore-water (234U/238U) values are unusually low due to a recent increase in the dissolution rate of grain surfaces. This suggests a strengthening of fluid flow, probably due to the flooding of the banks at the last deglaciation and the re-initiation of thermally-driven venting of fluid on the bank top and accompanying recharge on the slopes. Interpretation of existing chlorinity data, in the light of this change in flow rate, constrain the recent horizontal flow rate to be 10.6 ( 3.4) cm/year. Estimates of flow rate from (234U/238U) and Cl[-] are therefore in agreement and suggest flow rates close to those predicted by thermally-driven models of fluid flow. This agreement supports the idea that flow within the Bahamas Banks is mostly thermally driven and suggests that flow rates on the order of 10 cm/year are typical for carbonate platforms where such flow occurs.

Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.

Uranium and thorium isotopes and sedimentation rates in metalliferous sediments from the western flank of the East Pacific Rise at 21°-22°S

Isotopic compositions of uranium (234U and 238U) and thorium (230Th and 232Th) were measured in metalliferous sediments from the western flank of the East Pacific Rise at 21°-22°S, in the area of hydrothermal activity and massive sulfide accumulation at the axis of the EPR. Concentration of 232Th (on the carbonate-free base) is consistent with composition of mafic extrusive rocks; isotope ratios 232Th/238U and 234U/238U indicate that about 70% of uranium passes into sediments from sea water with hydrothermal iron hydroxide. Mean sedimentation rates are calculated for seven cores by the nonequilibrium 230Th method with use of the constant concentration model. Flux of 230Th to bottom sediments is calculated and its mean value is used to determine sedimentation rate in four other cores. The constant flux model is used to calculate change of sedimentation rate with depth for seven cores over time interval of 100-300 ky. Sedimentation rates varied not much (0.3-0.6 cm/ky). The greatest changes occurred in two cores: one located near massive sulfide structures, and another near the spreading axis. Determinations of mean rates by the radiocarbon method and the nonequilibrium thorium method are in good agreement.

Major elements oxides and mineralogy of primary minerals in ODP Hole 195-1201D basalts

The basement cored at Site 1201 (west Philippine Basin) during Ocean Drilling Program Leg 195 consists of a 91-m-thick sequence of basalts, mostly pillow lavas and perhaps one sheet lava flow, with a few intercalations of hyaloclastite and interpillow sedimentary material. Hydrothermal alteration pervasively affected the basalt sequence, giving rise to a variety of secondary minerals such as K-Fe-Mg-clay minerals, oxyhydroxides and clay minerals mixtures, natrolite group zeolites, analcite, alkali feldspar, and carbonate. The primary minerals of pillow and sheet basalts that survived the intense hydrothermal alteration were investigated by electron microprobe with the aim of characterizing their chemical composition and variability. The primary minerals are mostly plagioclase, ranging in composition from bytownite through labradorite to andesine, chromian-magnesian-diopside, and spinels, both Ti magnetite (partially maghemitized) and chromian spinel. Overall, the chemical features of the primary minerals of Site 1201 basalts correspond to the primitive character of the bulk rocks, suggesting that the parent magma of these basalts was a mafic tholeiitic magma that most likely only suffered limited fractional crystallization and crystallized at high temperatures (slightly below 1200°C) and under increasing fO2 conditions. The major element composition of clinopyroxene suggests a backarc affinity of the mantle source of Site 1201 basement.

Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).