Rhenium and osmium concentrations and isotopic compositions in altered ocean crust rocks at ODP Site 185-801

Re and Os concentrations and Os isotopic ratios were determined for composite samples prepared from volcanoclastics (VCL) and basaltic flows (FLO) from Jurassic oceanic crust (Ocean Drilling Program Leg 185, Site 801 in the western Pacific), with the aim of determining the effect of seafloor weathering on the Re-Os budget. A supercomposite sample, prepared from a proportionate mixture of the various composite powders, served to represent the average composition of the altered oceanic crust [Kelley, K.A., Plank, T., Ludden, J. and Staudigel, H., (2003). Composition of altered oceanic crust at ODP Sites 801 and 1149, Geochem. Geophys. Geosyst. 4(6) 8910, doi:10.1029/2002GC000435.]. Re contents vary from 0.2 to 1.3 ng/g, and from 2.2 to 3.1 ng/g in the VCL and FLO composites respectively. Os contents vary from 0.005 to 0.047 ng/g in the VCL, and from 0.008 to 0.027 ng/g in the FLO composites. The FLO composites have much higher Re/Os ratios and thus have more radiogenic Os compositions (187Os/188Os = 1.38 to 8.48) than the VCL composites (187Os/188Os = 0.32 to 4.40). The VCL composite from the upper section of the crust shows evidence for substantial Re loss and Os uptake, consistent with oxidative weathering processes. However, Re uptake during weathering processes under more reducing conditions, evident in the FLO samples from throughout the section and to a lesser extent in the lower VCL samples, more than compensates for this Re loss in the upper VCL. Os concentrations were essentially unchanged by these reductive processes. Model age calculations suggest that Re uptake continued for tens of millions of years after crust formation. Abundant secondary pyrite is found throughout the altered Hole 801C crust in zones of restricted seawater flow, and this may have accommodated an important part of the input Re. The Re content of the supercomposite (~2.2 ng/g) is about 1 ng/g higher than would be expected on the basis of its Yb content. If the results from Hole 801C are typical, they suggest that the Re concentration of at least the upper part of the oceanic crust may be nearly doubled during seafloor alteration. Such large extents of Re uptake would have a significant effect on the oceanic Re budget. Furthermore, assuming that they survive passage through the subduction zone, these elevated Re contents would greatly decrease the proportion of subducted oceanic crust required in the source region to explain the radiogenic Os compositions of many ocean island basalts.

Rb-Sr systematics of volcanic rocks and alteration minerals of ODP Hole 104-642E

Subaerially erupted tholeiites at Hole 642E were never exposed to the high-temperature seawater circulation and alteration conditions that are found at subaqueous ridges. Alteration of Site 642 rocks is therefore the product of the interaction of rocks and fluids at low temperatures. The alteration mineralogy can thus be used to provide information on the geochemical effects of low temperature circulation of seawater. Rubidium-strontium systematics of leached and unleached tholeiites and underlying, continentally-derived dacites reflect interactions with seawater in fractures and vesicular flow tops. The secondary mineral assemblage in the tholeiites consists mainly of smectite, accompanied in a few flows by the assemblage celadonite + calcite (+/- native Cu). Textural relationships suggest that smectites formed early and that celadonite + calcite, which are at least in part cogenetic, formed later than and partially at the expense of smectite. Smectite precipitation occurred under variable, but generally low, water/rock conditions. The smectites contain much lower concentrations of alkali elements than has been reported in seafloor basalts, and sequentially leached fractions of smectite contain Sr that has not achieved isotopic equilibrium. 87Sr/86Sr results of the leaching experiments suggest that Sr was mostly derived from seawater during early periods of smectite precipitation. The basalt-like 87Sr/86Sr of the most readily exchangeable fraction seems to suggest a late period of exposure to very low water /rock. Smectite formation may have primarily occurred in the interval between the nearly 58-Ma age given by the lower series dacites and the 54.5 +/- 0.2 Ma model age given by a celadonite from the top of the tholeiitic section. The 54.5 +/- 0.2 Ma Rb-Sr model age may be recording the timing of foundering of the Voring Plateau. Celadonites precipitated in flows below the top of the tholeiitic section define a Rb-Sr isochron with a slope corresponding to an age of 24.3 +/- 0.4 Ma. This isochron may be reflecting mixing effects due to long-term chemical interaction between seawater and basalts, in which case the age provides only a minimum for the timing of late alteration. Alternatively, inferrential arguments can be made that the 24.3 +/- 0.4 isochron age reflects the timing of the late Oligocene-early Miocene erosional event that affected the Norwegian-Greenland Sea. Correlation of 87Sr/86Sr and 1/Sr in calcites results in a two-component mixing model for late alteration products. One end-member of the mixing trend is Eocene or younger seawater. Strontium from the nonradiogenic endmember can not, however, have been derived directly from the basalts. Rather, the data suggest that Sr in the calcites is a mixture of Sr derived from seawater and from pre-existing smectites. For Site 642, the reaction involved can be generalized as smectite + seawater ++ celadonite + calcite. The geochemical effects of this reaction include net gains of K and CO2 by the secondary mineral assemblage. The gross similarity of the reactions involved in late, low-temperature alteration at Site 642 to those observed in other sea floor basalts suggests that the transfer of K and C02 to the crust during low-temperature seawater-ocean crust interactions may be significant in calculations of global fluxes.

Osmium-isotope geochemistry of ODP Site 159-959

Analyses of Re, Os, and Ir concentrations, as well as Os-isotopic compositions, are reported for a suite of sediments from Ocean Drilling Program Site 959. These samples vary in age from late Neogene to Late Cretaceous, and represent a range in depositional oxidation-reduction conditions from suboxic in the Neogene to anoxic in the Late Cretaceous. Age assignments based on shipboard biostratigraphic data are used to calculate initial 187Os/186Os ratios of Neogene nannofossil/foraminifer oozes and Eocene to upper Oligocene laminated diatomites. These calculated initial ratios are in general agreement with published data constraining the Os-isotopic evolution of seawater through time, indicating that the Os-isotopic composition of these sediments is controlled largely by the Os isotopic composition of contemporaneous seawater. Results from analyses of Upper Cretaceous to lower Paleocene claystones do not exhibit elevated Ir concentrations and exhibit Re-Os systematics that are highly consistent with closed-system production of 187Os by in situ 187Re decay. Scatter in both the Cretaceous and Cenozoic data sets is likely the result of the influence of nonhydrogenous Os, carried by clastics, on the bulk sediment Os-isotopic composition, or post-depositional mobility of Re and/or Os.

(Table 1) Concentrations and carbon isotopic compositions of CH4 and CO2 at DSDP Site 76-533

The principal gaseous carbon-containing components identified in the first 400 m of sediment at Deep Sea Drilling Project Site 533, Leg 76, are methane (CH4) and carbon dioxide (CO2). Below a sub-bottom depth of about 25 m, sediment cores commonly contained pockets caused by the expansion of gas upon core recovery. The carbon isotopic composition (d13C per mil relative to PDB standard) of CH4 and CO2 in these gas pockets has been measured, resulting in the following observations: (1) d13C-CH4 values increase with depth from approximately -94 per mil in the uppermost sediment to about -66 per mil in the deepest sediment, reflecting a systematic but nonlinear depletion of 12C with depth. (2) d13C-CO2 values also increase with depth of sediment from about -25 per mil to about -4 per mil, snowing a depletion of 12C that closely parallels the trend of the isotopic composition of CH4. The magnitude and parallel distribution of d13C values for both CH4 and CO2 are consistent with the concept that the formation of the CH4 resulted from the microbiological reduction of CO2 from organic substances. These results imply that CH4 and CO2 incorporated in gas hydrates at this site are biogenic.

Chemical and isotopic compositions of pore fluids from ODP Sites 169-1034 and 169-1037

We have analysed the concentrations of Li, K, Rb, Cs, and B, and the isotopic ratios of Li and B of a suite of pore fluids recovered from ODP Sites 1037 (Leg 169; Escanaba Trough) and 1034 (Leg 169S; Saanich Inlet). In addition, we have analysed dissolved K, Rb, and Cs concentrations for estuarine mixing of the Ganges-Brahmaputra river system. Together, these data sets have been used to assess the role of sediments in the marine geochemical cycles of the alkali elements and boron. Uptake onto clay minerals during estuarine mixing removes 20-30% of the riverine input of dissolved Cs and Rb to the oceans. Prior to this study, the only other recognised sink of Rb and Cs was uptake during low-temperature alteration of the oceanic crust. Even with this additional sink there is an excess of inputs over outputs in their modern oceanic mass balance. Pore fluid data show that Li and Rb are transferred into marine sediments during early diagenesis. However, modeling of the Li isotope systematics of the pore fluids from Site 1037 shows that seawater Li taken up during marine sedimentation can be readily returned to solution in the presence of less hydrated cations, such as NH4+. This process also appears to result in high concentrations of pore fluid Cs (relative to local seawater) due to expulsion of adsorbed Cs from cation exchange sites. Flux calculations based on pore fluid data for a series of ODP sites indicate that early diagenesis of clay sediments removes around 8% of the modern riverine input of dissolved Li. Although NH4+-rich fluids do result in a flux of Cs to the oceans, on the global scale this input only augments the modern riverine Cs flux by ~3%. Nevertheless, this may have implications for the fate of radioactive Cs in the natural environment and waste repositories.

Stable isotopic composition and carbonate concentrations of sediments of the Cretaceous/Paleogene boundary in the Antarctic

Stable isotopic records across the Cretaceous/Paleogene (K/P) boundary in Maud Rise Holes 689B and 690C indicate that significant climatic changes occurred during the latest Cretaceous, beginning approximately 500 k.y. prior to the mass extinction event and the enrichment of iridium at the K/P boundary (66.4 Ma). An oxygen isotopic decrease of ~0.7 per mil - ~1.0 per mil is recorded in the Late Cretaceous planktonic and benthic foraminifers between 66.9 and 66.6 Ma. The negative isotope excursion was followed by a positive excursion of similar magnitude between 66.6 Ma (latest Cretaceous) and ~66.3 Ma (earliest Paleocene). No other isotopic excursions of this magnitude are recorded in the planktonic and benthic microfossil records 1.0 m.y prior to, and for 2.0 m.y following the mass extinction event at the K/P boundary. The magnitude and duration of these isotopic excursions were similar to those at the Paleocene/Eocene and Eocene/Oligocene boundaries. A major d13C excursion occurred 200 k.y. prior to the boundary, involving a positive shift in planktonic and benthic d13C of ~0.5 per mil - 0.75 per mil. Similar changes observed in other deep-sea sequences indicate that this reflected a global change in d13C of the oceanic total dissolved carbon (TDC) reservoir. The magnitude of this inferred carbon reservoir change and its association with high latitude surface-water temperature changes recorded in the d18O records implies that it was linked to global climate change through feedback loops in the carbon cycle. At the K/P boundary, the surface-to-deep water d13C gradient is reduced by approximately 0.6 per mil - ~0.2 per mil. However, unlike sequences elsewhere, the planktonic-benthic d13C gradient (Delta d13C) was not eliminated in the Antarctic. The surface-to-deep water gradient was re-established gradually during the 400 k.y. following the mass extinction. Full recovery of the Delta d13C occurred by ~60.0 Ma. In addition to the reduced vertical d13C gradient across the K/P boundary, there was a negative excursion in both planktonic and benthic d13C beginning approximately 100 k.y. after the boundary (66.3 Ma). This excursion resulted in benthic d13C values in the early Paleogene that were similar to those in the pre-K/P boundary intervals. This negative shift appears to reflect a change in the d13C of the oceanic TDC reservoir shift that may have resulted from reduced carbon burial and/or increased carbon flux to the oceans. Any model that attempts to explain the demise of the oceanic plankton at the end of the Cretaceous should consider the oceanic environmental changes that were occurring prior to the massive extinction event.

The source of the Great Dyke, Zimbabwe, and its tectonic significance: Evidence from Re-Os isotopes

Re-Os data for chromite separates from 10 massive chromitite seams sampled along the 550-km length of the 2.58-Ga Great Dyke layered igneous complex, Zimbabwe, record initial 187Os/188Os ratios in the relatively narrow range between 0.1106 and 0.1126. This range of initial 187Os/188Os values is only slightly higher than the value for the coeval primitive upper mantle (0.1107) as modeled from the Re-Os evolution of chondrites and data of modern mantle melts and mantle derived xenoliths. Analyses of Archean granitoid and gneiss samples from the Zimbabwe Craton show extremely low Os concentrations (3-9 ppt) with surprisingly unradiogenic present-day 187Os/188Os signatures between 0.167 and 0.297. Only one sample yields an elevated 187Os/188Os ratio of 1.008. Using these data, the range of crustal contamination of the Great Dyke magma would be minimally 0%-33% if the magma source was the primitive upper mantle, whereas the range estimated from Nd and Pb isotope systematics is 5%-25%. If it is assumed that the primary Great Dyke magma derived from an enriched deep mantle reservoir (via a plume), a better agreement can be obtained. A significant contribution from a long-lived subcontinental lithospheric mantle (SCLM) reservoir with subchondritic Re/Os to the Great Dyke melts cannot be reconciled with the Os isotope results at all. However, Os isotope data on pre-Great Dyke ultramafic complexes of the Zimbabwe Craton and thermal modeling show that such an SCLM existed below the Zimbabwe Craton at the time of the Great Dyke intrusion. It is therefore concluded that large melt volumes such as that giving rise to the Great Dyke were able to pass lithospheric mantle keels without significant contamination in the late Archean. Because the ultramafic-mafic melts forming the Great Dyke must have originated below the SCLM (which extends to at least a 200-km depth ), the absence of an SCLM signature precludes a subduction-related magma-generation process.

Petrology and geochemistry of early cretaceous bimodal continental flood volcanism of the NW Etendeka, Namibia. Part 1: Introduction, mafic lavas and re-evaluation of mantle source components

The bimodal NW Etendeka province is located at the continental end of the Tristan plume trace in coastal Namibia. It comprises a high-Ti (Khumib type) and three low-Ti basalt (Tafelberg, Kuidas and Esmeralda types) suites, with, at stratigraphically higher level, interstratified high-Ti latites (three units) and quartz latites (five units), and one low-Ti quartz latite. Khumib basalts are enriched in high field strength elements and light rare earth elements relative to low-Ti types and exhibit trace element affinities with Tristan da Cunha lavas. The unradiogenic Pb-206/Pb-204 ratios of Khumib basalts are distinctive, most plotting to the left of the 132 Ma Geochron, together with elevated Pb-207/Pb-204 ratios, and Sr-Nd isotopic compositions plotting in the lower Nd-143/Nd-144 part of mantle array (EM1-like). The low-Ti basalts have less coherent trace element patterns and variable, radiogenic initial Sr (similar to0.707-0.717) and Pb isotope compositions, implying crustal contamination. Four samples, however, have less radiogenic Pb and Sr that we suggest approximate their uncontaminated source. All basalt types, but particularly the low-Ti types, contain samples with trace element characteristics (e.g. Nb/Nb-*) suggesting metasediment input, considered source-related. Radiogenic isotope compositions of these samples require long-term isolation of the source in the mantle and depletions (relative to unmodified sediment) in certain elements (e.g. Cs, Pb, U), which are possibly subduction-related. A geodynamic model is proposed in which the emerging Tristan plume entrained subducted material in the Transition Zone region, and further entrained asthenosphere during plume head expansion. Mixing calculations suggest that the main features of the Etendeka basalt types can be explained without sub-continental lithospheric mantle input. Crustal contamination is evident in most low-Ti basalts, but is distinct from the incorporation of a metasedimentary source component at mantle depths.

Arc crust-magma interaction in the Andean Southern Volcanic Zone from thermobarometry, mineral composition, radiogenic isotope and rare earth element systematics of the Azufre-Planchon-Peteroa volcanic complex, Chile

The Andean Southern Volcanic Zone (SVZ) is a vast and complex continental arc that has been studied extensively to provide an understanding of arc-magma genesis, the origin and chemical evolution of the continental crust, and geochemical compositions of volcanic products. The present study focuses on distinguishing the magma/sub-arc crustal interaction of eruptive products from the Azufre-Planchon-Peteroa (APP 35°15'S) volcanic center and other major centers in the Central SVZ (CSVZ 37°S–42°S), Transitional SVZ (TSVZ 34.3–37.0°S), and Northern SVZ (NSVZ 33°S–34°30'S). New Hf and Nd isotopic and trace element data for SVZ centers are consistent with former studies that these magmas experienced variable depths of crystal fractionation, and that crustal assimilation is restricted to the lower crustal depths with an apparent role of garnet. Thermobarometric calculations applied to magma compositions constrain the depth of magma separation from mantle sources in all segments of the SVZ to(70-90 km). Magmatic separation at the APP complex occurs at an average depth of ~50 km which is confined to the mantle lithosphere and the base of the crust suggesting localized thermal abrasion both reservoirs. Thermobarometric calculations indicate that CSVZ primary magmas arise from a similar average depth of (~54 km) which confines magma separation to the asthenospheric mantle. The northwards along-arc Sr-Nd-Hf isotopic data and LREE enrichment accompanied with HREE depletion of SVZ mafic magmas correlates well with northward increasing crustal thickness and decreasing primary melt separation from mantle source regions indicating an increased involvement of lower crustal components in SVZ magma petrogenesis. ^ The study concludes that the development of mature subduction zones over millions of years of continuous magmatism requires that mafic arc derived melts stagnate at lower crustal levels due to density similarities and emplace at lower crustal depths. Basaltic underplating creates localized hot zone environments below major magmatic centers. These regions of high temperature/partial melting, and equilibration with underplated mafic rocks provides the mechanism that controls trace element and isotopic variability of primary magmas of the TSVZ and NSVZ from their baseline CSVZ-like precursors.^

(Table 1) Sr, Nd and Os isotopic composition from marine sediments of the Bengal Fan

Sr, Nd, and Os isotopic data are presented for sediments from diverse locations in the Bay of Bengal. These data allow the samples to be divided into three groups, related to their sedimentary contexts. The first group, mainly composed of sediments from the shelf off Bangladesh and the currently active fan, has Sr and Nd characteristics consistent with a dominantly Himalayan source. Their 187Os/188Os ratios (~1.2-1.5) show that the average detrital material delivered by the Ganga-Brahmaputra (G-B) river system is not unusually radiogenic. A large difference in 187Os/188Os ratio exists between these Bengal Fan sediments and Ganga bedloads (187Os/188Os ~2.5, Pierson-Wickmann et al. (2000, doi:10.1016/S0012-821X(00)00003-0)). This difference mainly reflects addition of a less radiogenic Brahmaputra component, though mineralogical sorting and loss of radiogenic Os during transport may also play some role. The second sample group contains sediments from elsewhere in the Bay, particularly those located on the continental slope. They display Os isotopic compositions (0.99-1.11) similar to that of present seawater and higher Os and Re concentrations. These characteristics suggest the presence of a large hydrogenous contribution, consistent with the lower sedimentation rate of these samples. Sr and Nd ratios indicate that a significant fraction of these sediments is derived from erosion of non-Himalayan sources, such as the Indo-Burman range. These observations could be explained by the deflection of sediments from the G-B river system by westward currents in the head of the Bay. The third group contains only one sample, but shows that in addition to a Himalayan source, sediment discharge from Sri Lanka may influence the detrital component in the distal part of the fan. The similarity between the isotopic compositions of the group I R/V Sonne samples and those of Ocean Drilling Program Leg 116 (France-Lanord et al., 1993; Reisberg et al., 1997, doi:10.1016/S0012-821X(00)00003-0) suggests that the material eroding in the Himalayas has been roughly constant since the Miocene. The high Os isotopic ratios of leachates of both Sonne group I and Miocene Leg 116 sediments imply that much of the leachable highly radiogenic Os component was conserved during transport through the estuary or interaction with seawater. In constrast, samples with lower, but still relatively high, sedimentation rates (Sonne groups II and III and Pliocene Leg 116) seem to have significantly adsorbed or exchanged Os and Re with seawater. This suggests that in some cases the Os isotopic ratios of leachates of detrital sediments can be used to constrain the ancient marine Os record, or conversely, to date unfossiliferous sediments.

Nd and Sm content and isotopic composition of the carbonate-free clay fraction of sediment core HU90-013-013

Sm-Nd concentrations and Nd isotopes were investigated in the fine fraction of two Labrador Sea cores to reconstruct the deep circulation patterns through changes in sedimentary supply since the last glacial stage. Three sources are involved: the North American Shield, Palaeozoic rocks from northeastern Greenland, and mid-Atlantic volcanism. The variable input of these sources provides constraints on the relative sedimentary supply, in conjunction with inception of deep currents. During the last glacial stage a persistent but sluggish current occurred inside the Labrador Basin. An increasing discharge of volcanic material driven by the North East Atlantic Deep Water is documented since 14.3 kyr, signaling the setup of a modern-like deep circulation pattern throughout the Labrador, Irminger, and Iceland basins. During the last deglacial stage the isotopic record was punctually influenced by erosion processes related mainly to ice-sheet instabilities, especially 11.4, 10.2, and 9.2 kyr ago.

Molecular and isotopic compositions of hydrocarbons at DSDP Site 76-533

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (d13C = -68 per mil; C1/C2 = 5000) was the dominant gas (>90%); (2) little fractionation in the C1/C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experiments; (3) the percent of C3, i-C4, and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) C1/C2 ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also contained trace amounts of saturated, acyclic, cyclic, and aromatic C5-C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (d13C of -68 per mil for methane and a C1/C2 ratio of about 6000). Regular trends in the d13C of methane (about -95 to -60 per mil) and C1/C2 ratios (about 25000 to 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

Iron isotope systematics in Arctic rivers

The input of iron to the Arctic Ocean plays a critical role in the productivity of aquatic ecosystems and is potentially impacted by climate change. We examine Fe isotope systematics of dissolved and colloidal Fe from several Arctic and sub-Arctic rivers in northern Eurasia and Alaska. We demonstrate that the Fe isotopic (δ56Fe) composition of large rivers, such as the Ob’ and Lena, has a restricted range of δ56Fe values ca.–0.11 ± 0.13‰, with minimal seasonal variability, in stark contrast to smaller organic-rich rivers with an overall δ56Fe range from–1.7 to + 1.6‰. The preferential enrichment with heavy Fe isotopes observed in low molecular weight colloidal fraction and during the high-flow period is consistent with the role of organic complexation of Fe. The light Fe isotope signatures of smaller rivers and meltwater reflect active redox cycling. Data synthesis reveals that small organic-rich rivers and meltwater in Arctic environments may contribute disproportionately to the input of labile Fe in the Arctic Ocean, while bearing contrasting Fe isotope compositions compared to larger rivers.