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.

Calcium isotopic composition of planktonic foraminifera from ODP Site 154-925

An 18 million year record of the Ca isotopic composition (d44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. ?44/42Ca in this record averages +0.37+/-0.05 (1 sigma SD) and ranges from +0.21? to +0.52?. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25? lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their d44/42Ca (i.e., by 0.06+/-0.06? (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in d44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (d44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (D_sed) results in unrealistically large variations in the total mass of Ca2+ in the oceans over the Neogene. Alternatively, variations of +/-0.05? in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in d44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in D_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in d44/42Ca_w and D_sed have been established, modeling the Ca2+ content of seawater from Ca isotope curves should be approached cautiously.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and Uisotopic compositions of the unleached rocks is: 87Sr/86Sr=0.70280-0.70299, average 0.70287+/-0.00005 (1 S.D., N=30 samples) (except one felsic vein with 87Sr/86Sr=0.7045), 143Nd/144Nd=0.51304-0.51314, average 0.51310+/-0.00002 (1 S.D., N=28), 206Pb/204Pb=17.43-18.55, 207Pb/204Pb=15.40-15.61 and 208Pb/204Pb=37.19-38.28. The range of Sr and the almost constant Nd isotopic composition resemble that found in the upper 500 m of Hole 735B, while Pb ranges to more radiogenic compositions. In general, there is a decrease in isotopic variation of Sr and Pb as well as ? (238U/204Pb), U and Pb with depth, with a trend towards relatively unradiogenic compositions. This correlates with a decrease in alteration and frequency of evolved rock-types in the core. Leached samples generally have less radiogenic Pb with values trending towards 206Pb/204Pb=17.35, 207Pb/204Pb=15.35 and 208Pb/204Pb=37.0, while their 87Sr/86Sr ratios deviate less systematically from unleached rocks and reach both higher, 0.70307, and lower values, 0.70276. Separated clinopyroxene has elevated 87Sr/86Sr up to 0.7035, while plagioclase generally has close to whole rock Sr. Leaching reduced 87Sr/86Sr in clinopyroxene and in two (out of nine) cases leached separates and whole rock display isotopic equilibrium. Relatively minor hydrothermal seawater alteration is thought to have increased 87Sr/86Sr in the rocks, while a secondary high temperature percolation of a mantle-derived agent is thought to be the cause for the trend towards radiogenic Pb. This material had intermediate 87Sr/86Sr and may have originated from non-MORB off axis mantle. The main primary igneous isotopic variation of the gabbros is suggested to have been derived from the MORB-mantle and is defined mainly by leached samples from both ODP Leg 176 and Leg 118 and can be explained by two-component mixing of an end-member with composition like Central Indian Ridge basalts and an end-member with composition unlike any MORB. The latter is characterized by very unradiogenic Pb, in particular 207Pb/204Pb, and may have an origin with affinity to old depleted mantle (DM). The isotopic composition of the magmas parental to the FeTi-oxide rich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Hydrogen isotopic composition of sediment cores from a transect off western Africa

The hydrogen isotopic composition of plant leaf-wax n-alkanes (dDwax) is a novel proxy for estimating dD of past precipitation (dDp). However, vegetation life-form and relative humidity exert secondary effects on dDwax, preventing quantitative estimates of past dDp. Here, we present an approach for removing the effect of vegetation-type and relative humidity from dDwax and thus for directly estimating past dDp. We test this approach on modern day (late Holocene; 0-3 ka) sediments from a transect of 9 marine cores spanning 21°N-23°S off the western coast of Africa. We estimate vegetation type (C3 tree versus C4 grass) using d13C of leaf-wax n-alkanes and correct dDwax for vegetation-type with previously-derived apparent fractionation factors for each vegetation type. Late Holocene vegetation-corrected dDwax (dDvc) displays a good fit with modern-day dDp, suggesting that the effects of vegetation type and relative humidity have both been removed and thus that dDvc is a good estimate of dDp. We find that the magnitude of the effect of C3 tree - C4 grass changes on dDwax is small compared to dDp changes. We go on to estimate dDvc for the mid-Holocene (6-8 ka), the Last Glacial Maximum (LGM; 19-23 ka) and Heinrich Stadial 1 (HS1; 16-18.5 ka). In terms of past hydrological changes, our leaf-wax based estimates of dDp mostly reflect changes in wet season intensity, which is complementary to estimates of wet season length based on leaf-wax d13C.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Isotopic composition of ground ice, ebullition gases and thermokarst lake water, North America

Thermokarst lakes are thought to have been an important source of methane (CH4) during the last deglaciation when atmospheric CH4 concentrations increased rapidly. Here we demonstrate that meltwater from permafrost ice serves as an H source to CH4 production in thermokarst lakes, allowing for region-specific reconstructions of dD-CH4 emissions from Siberian and North American lakes. dD CH4 reflects regionally varying dD values of precipitation incorporated into ground ice at the time of its formation. Late Pleistocene-aged permafrost ground ice was the dominant H source to CH4 production in primary thermokarst lakes, whereas Holocene-aged permafrost ground ice contributed H to CH4 production in later generation lakes. We found that Alaskan thermokarst lake dD-CH4 was higher (-334 ± 17 per mil) than Siberian lake dD-CH4 (-381 ± 18 per mil). Weighted mean dD CH4 values for Beringian lakes ranged from -385 per mil to -382 per mil over the deglacial period. Bottom-up estimates suggest that Beringian thermokarst lakes contributed 15 ± 4 Tg CH4 /yr to the atmosphere during the Younger Dryas and 25 ± 5 Tg CH4 /yr during the Preboreal period. These estimates are supported by independent, top-down isotope mass balance calculations based on ice core dD-CH4 and d13C-CH4 records. Both approaches suggest that thermokarst lakes and boreal wetlands together were important sources of deglacial CH4.