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  • Articles  (4)
  • Open Access-Papers  (4)
  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2011. 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 Geochimica et Cosmochimica Acta 75 (2011): 6690-6704, doi:10.1016/j.gca.2011.07.047.
    Description: This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183Ma) are compared with data from Late Neogene (〈10Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment–water interface due the sulphidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment–water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.
    Description: SGN is funded by a NERC fellowship.
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of International Association of Geoanalysts for personal use, not for redistribution. The definitive version was published in Geostandards and Geoanalytical Research 37 (2013): 337–343, doi:10.1111/j.1751-908x.2012.00203.x.
    Description: Here we present the first determination of thallium (Tl) concentrations in the USGS reference materials BIR-1G, BHVO-2G and BCR-2G measured by solution ICP-MS. The Tl abundances in these three glasses span a range of about 2-230 ng g-1, which is similar to the values published for the respective powder materials. The determined range of Tl concentrations in these three glass reference materials makes them ideal as external references for investigating Tl concentrations in basaltic and andesitic volcanic glasses. We also performed a series of laser ablation ICP-MS measurements on the three samples, which show that this technique is able to determine Tl concentrations in glass samples with concentrations as low as 2 ng g-1.
    Description: This study was supported by funding from NSF grant EAR 1119373, a DOEI award from WHOI and an NERC fellowship to SGN.
    Keywords: Thallium ; USGS glass reference materials ; Laser ablation ICP-MS
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 172 (2017): 51, doi:10.1007/s00410-017-1368-7.
    Description: The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth's upper mantle, and their distribution in peridotite minerals, remains to be constrained. Here we developed a method to measure low concentrations of halogens (≥ 0.4 μg/g F and ≥ 0.3 μg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole 〉 clinopyroxene 〉 olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole 〉 clinopyroxene 〉 orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (〈 1 μg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 μg/g F and 0.14–0.38 μg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 μg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.
    Description: This research was supported by grant NSF EAR-P&G 1524311 and DOEI award 18563 to VLR. Urann was supported by the Stanley W. Watson Student Fellowship Fund based at WHOI.
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 15 (2014): 4905–4919, doi:10.1002/2014GC005536.
    Description: We present new laser ablation ICP-MS trace element concentration data for 28 elements in 97 mid-ocean ridge basalt (MORB) glasses that cover all major spreading centers as well as Tl concentration data for all mineral phases in five lherzolites from the Lherz massif, France. The ratio between the elements thallium (Tl) and cerium (Ce) is nearly constant in MORB, providing evidence that the depleted MORB mantle (DMM) has uniform Ce/Tl. Lherzolite mineral data reveal that sulfides are heterogeneous and contain between 23 and 430 ng/g of Tl while all other minerals contain Tl below the analytical detection limit of ∼1 ng/g. We argue that Tl in MORB is controlled by residual sulfide during mantle melting. To investigate the observed relationship between Tl and Ce, we conduct models of fractional mantle melting, which show that the constant Ce/Tl in MORB is only reproduced if the ratio between clinopyroxene and sulfide in the upper mantle varies by less than 10%. In addition, the rate of melting for these two phases must be nearly identical as otherwise melt depletion and refertilization processes would lead to Ce/Tl fractionation. These model results allow us to establish a relationship for the sulfur content of DMM: [S]DMM = SCSS × Mcpx /Rcpx, where SCSS is the sulfur concentration of a silicate melt at sulfide saturation, Rcpx is the melt reaction coefficient, and Mcpx is the modal abundance of clinopyroxene in the DMM. Using this equation, we calculate that the average upper mantle sulfur concentration is 195 ± 45 μg/g.
    Description: We acknowledge funding from NSF grant EAR 1119373 to SGN and an award from the WHOI Deep Ocean Exploration Institute to SGN and NS and funding from the Deep Carbon Observatory to MDB.
    Description: 2015-06-18
    Keywords: Thallium ; Sulfide ; Mantle ; Trace elements
    Repository Name: Woods Hole Open Access Server
    Type: Article
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