Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC-ICP-MS

International audienceAlthough initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass-dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two-stage chromatography procedure, Ni isotope ratios were measured by MC-ICP-MS and were corrected for instrumental mass bias using a double-spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous- and mantle-derived rocks displayed a restricted range of δ60/58Ni values between −0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO-1), coal (CLB-1) and a metal-contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite-hosted Ni-rich sulfides varied from −0.10 to −1.03‰

Multiple sulphur and iron isotope composition of detrital pyrite in Archaean sedimentary rocks : a new tool for provenance analysis

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 286 (2009): 436-445, doi:10.1016/j.epsl.2009.07.008.Multiple S (δ34S and δ33S) and Fe (δ56Fe) isotope analyses of rounded pyrite grains from 3.1 to 2.6 Ga conglomerates of southern Africa indicate their detrital origin, which supports anoxic surface conditions in the Archaean. Rounded pyrites from Meso- to Neoarchaean gold and uranium-bearing strata of South Africa are derived from both crustal and sedimentary sources, the latter being characterised by non-mass dependent fractionation of S isotopes (Δ33S as negative as -1.35‰) and large range of Fe isotope values (δ56Fe between -1.1 and 1.2‰). Most sediment-sourced pyrite grains are likely derived from sulphide nodules in marine organic matter-rich shales, sedimentary exhalites and volcanogenic massive sulphide deposits. Some sedimentary pyrite grains may have been derived from in situ sulphidised Fe-oxides, prior to their incorporation into the conglomerates, as indicated by unusually high positive δ56Fe values. Sedimentary sulphides without significant non-mass dependent fractionation of S isotopes were also present in the source of some conglomerates. The abundance in these rocks of detrital pyrite unstable in the oxygenated atmosphere may suggest factors other than high pO2 as the cause for the absence of significant non-mass dependent fractionation processes in the 3.2 – 2.7 Ga atmosphere. Rounded pyrites from the ca. 2.6 Ga conglomerates of the Belingwe greenstone belt in Zimbabwe have strongly fractionated δ34S, Δ33S and δ56Fe values, the source of which can be traced back to black shale-hosted massive sulphides in the underlying strata. The study demonstrates the utility of combined multiple S and Fe isotope analysis for provenance reconstruction of Archaean sedimentary successions.AH acknowledges support by NAI International Collaboration Grant and NRF grant FA2005040400027. AB participation was supported by NSF grant EAR-937 05-45484, NAI award No. NNA04CC09A, and NSERC 938 Discovery grant. Rouxel's contribution was supported by NSF OCE-0622982

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9–10°N

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Chemical Geology 252 (2008): 214-227, doi:10.1016/j.chemgeo.2008.03.009.In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9-10°N to better constrain processes affecting Fe- isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) is there significant Fe isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S- isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between –0.11 to –0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (-0.6±0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42- followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower temperature, Fe-depleted vents.Support for W. Bach and K. Edwards was provided by NSF grant OCE-0241791 and support for O. Rouxel was provided by funding from the WHOI Deep Ocean Exploration Institute and NSF grant OCE-0622982 and OCE-0647948

Épuiser sa présence : rapports amoureux et téléphonie mobile

Cet article examine les spécificités des rapports amoureux actuels en tant que ceux-ci sont équipés par toute une série de technologies à même d’organiser concrètement le contenu des relations. Il en est ainsi du téléphone portable, qui s’est immiscé dans le cœur de la vie amoureuse. Aussi, au moyen d’une phénoménologie de la relation amoureuse, il s’agira d’examiner les recompositions des régimes présentiels et relationnels engendrés par le téléphone portable. À partir d’un corpus de 4 974 messages instantanés échangés par neuf couples distincts, le but est d’appréhender la fragilisation du mouvement vers autrui que pourrait entraîner l’utilisation de ces technologies, dont l’effet essentiel est probablement d’organiser une coprésence particulière des êtres.This article analyzes the recomposition of presential and relational regimes caused by the mobile phone in love relationships. We will discuss phenomenological specificities of in-love copresence before examining results that introduce the effects of “availability” raised by these devices. This analysis will be based on a corpus of 4,974 SMS exchanged by nine different couples. We will especially highlight the specificities of the “technical principle” inherent to these devices. The analysis of this "short time technology" helps to discern a radicalization of the feeling of remotness to the other.in this “technologically equipped copresence.”Este artículo pretende analizar las especificidades de las relaciones amorosas en la actualidad, en la medida en que estas utilizan una serie de tecnologías, que incluso llegan a organizar el contenido de las relaciones. El mejor ejemplo es el teléfono móvil, que se ha situado en el centro de la vida amorosa. Mediante una fenomenología de la relación amorosa, se busca analizar las recomposiciones de los regímenes presenciales y relacionales generados por el teléfono móvil. Este análisis se apoya en un corpus de 4974 mensajes de texto (SMS) intercambiados por 9 parejas distintas. De manera más específica se busca analizar la fragilización del movimiento hacia la otra persona que pudiera resultar de la utilización de estas tecnologías con probabilidad, el efecto esencial es el de organizar una co-presencia particular de las personas

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

This paper is not subject to U.S. copyright. The definitive version was published in Geophysical Research Letters 38 (2011): L16605, doi:10.1029/2011GL048367.Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.We appreciate support from the USGS CMGP, NCCWSC, and the Mendenhall Postdoctoral Program

Time-series analysis of two hydrothermal plumes at 9°50′N East Pacific Rise reveals distinct, heterogeneous bacterial populations

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Geobiology 10 (2012): 178-192, doi:10.1111/j.1472-4669.2011.00315.xWe deployed sediment traps adjacent to two active hydrothermal vents at 9°50’N on the East Pacific Rise (EPR) to assess variability in bacterial community structure associated with plume particles on the time scale of weeks to months, to determine if an endemic population of plume microbes exists, and to establish ecological relationships between bacterial populations and vent chemistry. Automated rRNA intergenic spacer analysis (ARISA) indicated there are separate communities at the two different vents and temporal community variations between each vent. Correlation analysis between chemistry and microbiology indicated that shifts in the coarse particulate (>1 mm) Fe/(Fe+Mn+Al), Cu, V, Ca, Al, 232Th, and Ti as well as fine-grained particulate (<1 mm) Fe/(Fe+Mn+Al), Fe, Ca and Co are reflected in shifts in microbial populations. 16S rRNA clone libraries from each trap at three time points revealed a high percentage of Epsilonproteobacteria clones and hyperthermophilic Aquificae. There is a shift towards the end of the experiment to more Gammaproteobacteria and Alphaproteobacteria, many of whom likely participate in Fe and S cycling. The particle attached plume environment is genetically distinct from the surrounding seawater. While work to date in hydrothermal environments has focused on determining the microbial communities on hydrothermal chimneys and the basaltic lavas that form the surrounding seafloor, little comparable data exists on the plume environment that physically and chemically connects them. By employing sediment traps for a time series approach to sampling, we show that bacterial community composition on plume particles changes on time scales much shorter than previously known.This work was supported by the NSF Marine Geology and Geophysics program, the Science and Technology program, and the Gordon and Betty Moore Foundation

Optical electron transfer through 2,7-diethynylfluorene spacers in mixed-valent complexes containing electron-rich "(η2-dppe)(η5-C5Me5)Fe" endgroups.

International audienceWe report in this communication the study of the intramolecular electron transfer through a 2,7-diethynylfluorenyl spacer in the Fe(II)/Fe(III) mixed-valent (MV) complex [(η(2)-dppe)(η(5)-C(5)Me(5))FeC≡C(2,7-C(21)H(24))C≡CFe(η(5)-C(5)Me(5))(η(2)-dppe)][PF(6)] (1[PF(6)]). The complex is generated in situ by comproportionation from its homovalent dinuclear Fe(II) and Fe(III) parents (1 and 1[PF(6)](2)). It is shown that electronic delocalization is much more effective through a 2,7-fluorenyl than through a 4,4'-biphenyl bridging unit

Nickel and Chromium Stable Isotopic Composition of Ureilites: Implications for the Earth's Core Formation and Differentiation of the Ureilite Parent Body

We report the first Ni and Cr stable isotope data for ureilite meteorites that are the mantle residue of a carbon-rich differentiated planet. Ureilites have similar Ni stable isotope compositions as chondrites, suggesting that the core-mantle differentiation of ureilite parent body (UPB) did not fractionate Ni isotopes. Since the size of Earth is potentially larger than that of UPB; with diameter >690 km), resulting in higher temperatures at the core-mantle boundary of Earth, it can be predicted that the terrestrial core formation may not directly cause Ni stable isotope fractionation. On the other hand, we also report high-precision Cr stable isotope composition of ureilites, including one ureilitic trachyandesite (ALM-A) that is enriched in lighter Cr stable isotopes relative to the main-group ureilites, which suggests that the partial melting occurred on UPB. The globally heavy Cr in the UPB compared to chondrites can be caused by sulfur-rich core formation processes

The isotope composition of inorganic Germanium in seawater and deep sea sponges

Although dissolved concentrations of germanium (Ge) and silicon (Si) in modern seawater are tightly correlated, uncertainties still exist in the modern marine Ge cycle. Germanium stable isotope systematics in marine systems should provide additional constraints on marine Ge sources and sinks, however the low concentration of Ge in seawater presents an analytical challenge for isotopic measurement. Here, we present a new method of pre-concentration of inorganic Ge from seawater which was applied to measure three Ge isotope profiles in the Southern Ocean and deep seawater from the Atlantic and Pacific Oceans. Germanium isotopic measurements were performed on Ge amounts as low as 2.6 ng using a double-spike approach and a hydride generation system coupled to a MC-ICP-MS. Germanium was co-precipitated with iron hydroxide and then purified through anion-exchange chromatography. Results for the deep (i.e. > 1000 m depth) Pacific Ocean off Hawaii (nearby Loihi Seamount) and the deep Atlantic off Bermuda (BATS station) showed nearly identical δ74/70Ge values at 3.19 ± 0.31 ‰ (2SD, n = 9) and 2.93 ± 0.10 ‰ (2SD, n = 2), respectively. Vertical distributions of Ge concentration and isotope composition in the deep Southern Ocean for water depth > 1300 m yielded an average δ74/70Ge = 3.13 ± 0.25 ‰ (2SD, n = 14) and Ge/Si = 0.80 ± 0.09 μmol/mol (2SD, n = 12). Significant variations in δ74/70Ge, from 2.62 to 3.71 ‰, were measured in the first 1000 m in one station of the Southern Ocean near Sars Seamount in the Drake Passage, with the heaviest values measured in surface waters. Isotope fractionation by diatoms during opal biomineralization may explain the enrichment in heavy isotopes for both Ge and Si in surface seawater. However, examination of both oceanographic parameters and δ74/70Ge values suggest also that water mass mixing and potential contribution of shelf-derived Ge also could contribute to the variations. Combining these results with new Ge isotope data for deep-sea sponges sampled nearby allowed us to determine a Ge isotope fractionation factor of -0.87 ± 0.37 ‰ (2SD, n = 12) during Ge uptake by sponges. Although Ge has long been considered as a geochemical twin of Si, this work underpins fundamental differences in their isotopic behaviors both during biomineralization processes and in their oceanic distributions. This suggests that combined with Si isotopes, Ge isotopes hold significant promise as a complementary proxy for delineating biological versus source effects in the evolution of the marine silicon cycle through time