Composition of surface layer bottom sediments from the Chukchi Sea

Abundance of noble metals and bulk chemical composition have been studied in bottom sediments of the Chukchi Sea. Distribution of noble metals and their correlation with major and trace elements in the sediments have been analyzed using multicomponent statistics. It was established that average contents of noble metals in the bottom sediments of the Chukchi Sea significantly exceed those both in shelf terrigenous sediments and stratisphere. Osmium and iridium enrich mixed and pelitic sediments relative to shallow-water sediments and their influx is presumably determined by erosion of coastal and bottom unconsolidated deposits. High Ag, Ru, Au, and Pt contents were identified in clayey sediments enriched in biogenic elements in the some areas of the Southern Chukchi plain (Chukchi Sea) confined to intersection zones of submeridional and sublatitudinal structures of the graben-rift system, which formed in Mesozoic and activated in Late Cenozoic.

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.

Os isotope ratios of sediments from the Eocene-Oligocene boundary

Osmium (Os) isotope analyses of bulk sediments from the South Atlantic, Equatorial Pacific, and the Italian Apennines yield a well-dated and coherent pattern of 187Os/188Os variation from the late Eocene to the early Oligocene. The resulting composite record demonstrates the global character of two prominent features of the low-resolution LL44-GPC3 Os isotope record (Pegram and Turekian, 1999, doi:10.1016/S0016-7037(99)00308-7). These are: (1) a pronounced minimum in 187Os/188Os (0.22-0.27) in the late Eocene, between 34 and 34.5 Ma, and (2) a subsequent rapid increase in 187Os/188Os, to approximately 0.6 by 32 Ma. An ultramafic weathering event and an increased influx of extraterrestrial particles to the Earth are discussed as alternative explanations for the late Eocene 187Os/188Os minimum. Comparison of the 187Os/188Os to benthic foraminiferal oxygen isotope records demonstrates that the nearly three-fold increase in 187Os/188Os from the late Eocene minimum coincides with the growth and decay of the first large ice sheet of the Oligocene (Oi1 (Miller et al., 1991, doi:10.1029/90JB02015)). The fine structure of the Os isotope record indicates that enhanced release of radiogenic Os, unrelated to the recovery from late Eocene minimum, lagged the initiation of the Oi1 event by roughly 0.5 Myr. This record, in conjunction with weathering studies in modern glacial soils (Blum, in: W.F. Ruddiman (Ed.), Tectonic Uplift and Climate Change, Plenum Press, New York, 1997, pp. 259-288; Peucker-Ehrenbrink and Blum, 1998, doi:10.1016/S0016-7037(98)00227-0), suggests that exposure of freshly eroded material during deglaciation following Oi1 enhanced chemical weathering rates, and may have contributed to ice sheet stabilization by drawing down atmospheric carbon dioxide. The improved temporal resolution and age control of the refined Eocene-Oligocene Os isotope record also makes it possible to illustrate the late Eocene Os isotope excursion as a tool for global correlation of marine sediments.

Rhenium and platinum-group element concentrations and Os isotope data for Philippine Sea Plate basalts from DSDP Legs 31, 58, and 59

Platinum-group elements (PGE), rhenium and osmium isotope data are reported for basalts from Deep Sea Drilling Project cores in the Philippine Sea Plate (PSP). Lithophile trace element and isotopic characteristics indicate a range of source components including DMM, EMII and subduction-enriched mantle. MORB-like basalts possess smooth, inclined chondrite-normalised PGE patterns with high palladium-PGE/iridium-PGE ratios, consistent with previously published data for MORB, and with the inferred compatibility of PGE. In contrast, while basalts with EMII-type lithophile element chemistry possess high Pt/Ir ratios, many have much lower Pd/Ir and unusually high Ru/Ir of >10. Similarly, back-arc samples from the Shikoku and Parece-Vela basins have very high Ru/Ir ratios (>30) and Pd/Ir as low as 1.1. Such extreme Pd/Ir and Ru/Ir ratios have not been previously reported in mafic volcanic suites and cannot be easily explained by variable degrees of melting, fractional crystallisation or by a shallow-level process such as alteration or degassing. The data appear most consistent with sampling of at least two mantle components with distinct PGE compositions. Peridotites with the required PGE characteristics (i.e. low Pd, but relatively high Ru and Re) have not been documented in oceanic mantle, but have been found in sub-continental mantle lithosphere and are the result of considerable melt depletion and selective metasomatic enrichment (mainly Re). The long-term presence of subduction zones surrounding the Philippine Sea Plate makes this a prime location for metasomatic enrichment of mantle, either through fluid enrichment or infiltration by small melt fractions. The Re-Os isotope data are difficult to interpret with confidence due to low Os concentrations in most samples and the uncertainty in sample age. Data for Site 444A (Shikoku Basin) give an age of 17.7+/-1.3 Ma (MSWD = 14), consistent with the proposed age of basement at the site and thus provides the first robust radiometric age for these samples. The initial 187Os/188Os of 0.1298+/-0.0069 is consistent with global MORB, and precludes significant metasomatic enrichment of Os by radiogenic slab fluids. Re-Os data for Sites 446A (two suites, Daito Basin) and 450 (Parece-Vela Basin) indicate ages of 73, 68 and 43 Ma, which are respectively, 30, 17 and >12 Ma older than previously proposed ages. The alkalic and tholeiitic suites from Site 446A define regression lines with different 187Os/188Osinitial (0.170+/-0.033 and 0.112+/-0.024, respectively) which could perhaps be explained by preferential sampling of interstitial, metasomatic sulphides (with higher time-integrated Re/Os ratios) by smaller percentage alkalic melts. One sample, with lithophile elements indistinguishable from MORB, is Os-rich (146 pg/g) and has an initial 187Os/188Os of 0.1594, which is at the upper limit of the accepted OIB range. Given the Os-rich nature of this sample and the lack of evidence for subduction or recycled crust inputs, this osmium isotope ratio likely reflects heterogeneity in the DMM. The dataset as a whole is a striking indication of the possible PGE and Os isotope variability within a region of mantle that has experienced a complex tectonic history.

Geochemistry of sediments from the Cretaceous-Tertiary boundary

Siderophilic element concentrations are high in sediments from the Cretaceous-Tertiary boundary. An extraterrestrial source is indicated. Concentrations are too high to be understood in terms of the impact of a chondritic asteroid. Either the projectile was a metal-sulphide core or the infalling material (probably weak cometary matter) was slowed down during atmospheric passage.

Os isotope ratios of Late Eocene sediments from the tropical Pacific

High resolution records (ca. 100 kyr) of Os isotope composition (187Os/188Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene 187Os/188Os excursion and confirm that the Late Eocene 187Os/ 188Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink (2003, doi:10.1016/S0012-821X(03)00137-7), is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene 187Os/188Os minimum can be placed at 34.5 +/- 0.1 Ma in the marine records. In addition, two other distinct features of the 187Os/188Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. +/-0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO2. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the 187Os/188Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; 187Os/188Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of 187Os/188Os records with high resolution benthic foraminiferal delta18O records across the Eocene-Oligocene transition suggests that 187Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater 187Os/188Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine 187Os/188Os records are obscured by recovery from the Late Eocene 187Os/188Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.

Summary of phase compositions of experimental silicate melt, un-normalised analyses

The solubility of Re and Au in haplobasaltic melt has been investigated at 1673-2573 K, 0.1 MPa-2 GPa and IW-1 to +2.5, in both carbon-saturated and carbon-free systems. Results extend the existing, low pressure and temperature, dataset to more accurately predict the results of metal-silicate equilibrium at the base of a terrestrial magma ocean. Solubilities in run-product glasses were measured by laser ablation ICP-MS, which allows for the explicit assessment of contamination by metal inclusions. The Re and Au content of demonstrably contaminant-free glasses increases with temperature, and shows variation with oxygen fugacity (fO2) similar to previous results, although lower valence states for Re (1+, 2+) are suggested by the data. At 2 GPa, and Delta IW of +1.75 to +2, the metal-silicate partition coefficient for Re (DMet/Sil) is defined by the relation LogD[met/sil][Re] = 0.50(±0.022)*10**4/T(K)+3.73(±0.095) For metal-silicate equilibrium to endow Earth's mantle with the observed time-integrated chondritic Re/Os, (and hence 187Os/188Os), DMet/Sil for both elements must converge to a common value. Combined with previously measured DMet/Sil for Os, the estimated temperature at which this convergence occurs is 4500 (±900) K. At this temperature, however, the Re and Os content of the equilibrated silicate is ~100-fold too low to explain mantle abundances. In the same experiments, much lower Dmet/sil values have been determined for Au, and require the metal-silicate equilibration temperature to be <3200 K, as hotter conditions result in an excess of Au in the mantle. Thus, the large disparity in partitioning between Re or Os, and Au at core-forming temperatures argues against their mantle concentrations set solely by metal-silicate equilibrium at the base of a terrestrial magma ocean.

Geochemistry on Yangla copper deposit, China

The Yangla copper deposit, situated in the middle section of Jinshajiang tectonic belt between Zhongza-Zhongdian block and Changdu-Simao block, is a representative and giant copper deposit that has been discovered in Jinshajiang-Lancangjiang-Nujiang region in recent years. There are coupled relationship between Yangla granodiorite and copper mineralization in the Yangla copper deposit. Five molybdenite samples yielded a well-constrained 187Re-187Os isochron age of 233.3±3 Ma, the metallogenesis is therefore slightly younger than the crystallization age of the granodiorite. S, Pb isotopic compositions of the Yangla copper deposit indicate that the ore-forming materials were derived from the mixture of upper crust and mantle, also with the magmatic contributions. In the late Early Permian, the Jinshajiang Oceanic plate was subducted to the west, resulting in the formation of a series of gently dipping thrust faults in the Jinshajiang tectonic belt, meanwhile, accompanied magmatic activities. In the early Late Triassic, which was a time of transition from collision-related compression to extension in the Jinshajiang tectonic belt, the thrust faults were tensional; it would have been a favorable environment for forming ore fluids. The ascending magma provided a channel for the ore-forming fluid from the mantle wedge. After the magma arrived at the base of the early-stage Yangla granodiorite, the platy granodiorite at the base of the body would have shielded the late-stage magma from the fluid. The magma would have cooled slowly, and some of the ore-forming fluid in the magma would have entered the gently dipping thrust faults near the Yangla granodiorite, resulting in mineralization.

Os isotope record of ODP Site 159-959

The known temporal relationship between the benthic foraminiferal d18O record and the marine Os isotope record is used to reinterpret the absolute chronology and paleoceanographic context of an episode of organic carbon burial on the West African margin Ocean Drilling Program (ODP) Site 959. Although organic-rich sediments require significant corrections for in situ decay of 187Re to 187Os, these results demonstrate the utility of the marine Os isotope record for chemostratigraphic correlation of organic-rich sediments that are devoid of age diagnostic microfossils with pelagic carbonate sequences. Revision of the ODP Site 959 chronology shifts the age assignment of an interval of biosiliceous, organic-rich sediment deposition from the Oligocene to the late Eocene and earliest Oligocene, likely culminating with the first major glaciation of the Oligocene (Oi1). We speculate that enhanced organic carbon burial over much of the West African margin may have contributed to drawdown of atmospheric carbon dioxide before and during the Oi1 event and suggest that Os isotope chemostratigraphy provides a valuable tool for further exploring this possibility.

Concentrations and accumulation rates of platinum-group elements and rhenium in Pacific and Atlantic sediments, DSDP and ODP data

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ~1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ~95% relative to chondritic Ir proportions. A similar depletion in Os (~90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ~1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ~65 Ma, the effective diffusivities are ~10**?13 cm**2/s, much smaller than that of soluble cations in pore waters (~10**?6 cm**2/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios >/=1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ~25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.