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  • 11
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    PANGAEA
    In:  Supplement to: Amini, Marghaleray; Eisenhauer, Anton; Böhm, Florian; Fietzke, Jan; Bach, Wolfgang; Garbe-Schönberg, Dieter; Rosner, Martin; Bock, Barbara; Lackschewitz, Klas Sven; Hauff, V (2008): Calcium Isotope (d44/40Ca) Fractionation along Hydrothermal Pathways, Logatchev Field (Mid-Atlantic Ridge, 14°45'N). Geochimica et Cosmochimica Acta, 72(16), 4107-4122, https://doi.org/10.1016/j.gca.2008.05.055
    Publication Date: 2024-01-09
    Description: We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45' N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a d44/40Ca_HydEnd of -0.95+/-0.07 per mil relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that d44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a d44/40Ca of -1.17+/-0.04 per mil (SW) for the host-rocks in the reaction zone and -1.45+/-0.05 per mil (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed d44/40Ca for Bulk Earth of -0.92+/-0.18 per mil (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta 61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta 62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about D44/40Ca = -0.5 per mil relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average d44/40Ca of -1.54+/-0.08 per mil (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.
    Keywords: 209-1271A; 209-1271B; 209-1274A; DRILL; Drilling/drill rig; Joides Resolution; Leg209; Ocean Drilling Program; ODP; South Atlantic Ocean
    Type: Dataset
    Format: application/zip, 3 datasets
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  • 12
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    PANGAEA
    In:  Supplement to: Bach, Wolfgang; Rosner, Martin; Jöns, Niels; Rausch, Svenja; Robinson, Laura F; Paulick, Holger; Erzinger, Jörg (2011): Carbonate veins trace seawater circulation during exhumation and uplift of mantle rocks: Results from ODP Leg 209. Earth and Planetary Science Letters, 311(3-4), 242-252, https://doi.org/10.1016/j.epsl.2011.09.021
    Publication Date: 2024-01-09
    Description: Carbonate veins hosted in ultramafic basement drilled at two sites in the Mid Atlantic Ridge 15°N area record two different stages of fluid-basement interaction. A first generation of carbonate veins consists of calcite and dolomite that formed syn- to postkinematically in tremolite-chlorite schists and serpentine schists that represent gently dipping large-offset faults. These veins formed at temperatures between 90 and 170 °C (oxygen isotope thermometry) and from fluids that show intense exchange of Sr and Li with the basement (87Sr/86Sr = 0.70387 to 0.70641, d7Li L-SVEC = + 3.3 to + 8.6 per mil). Carbon isotopic compositions range to high d13C PDB values (+ 8.7 per mil), indicating that methanogenesis took place at depth. The Sr-Li-C isotopic composition suggests temperatures of fluid-rock interaction that are much higher (T 〉 350-400 °C) than the temperatures of vein mineral precipitation inferred from oxygen isotopes. A possible explanation for this discrepancy is that fluids cooled conductively during upflow within the presumed detachment fault. Aragonite veins were formed during the last 130 kyrs at low-temperatures within the uplifted serpentinized peridotites. Chemical and isotopic data suggest that the aragonites precipitated from cold seawater, which underwent overall little exchange with the basement. Oxygen isotope compositions indicate an increase in formation temperature of the veins by 8-12 °C within the uppermost ~ 80 m of the subseafloor. This increase corresponds to a high regional geothermal gradient of 100-150 °C/km, characteristic of young lithosphere undergoing rapid uplift.
    Keywords: 209-1271A; 209-1271B; 209-1274A; DRILL; Drilling/drill rig; Joides Resolution; Leg209; Ocean Drilling Program; ODP; South Atlantic Ocean
    Type: Dataset
    Format: application/zip, 3 datasets
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  • 13
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    PANGAEA
    In:  Supplement to: Eickmann, Benjamin; Bach, Wolfgang; Rosner, Martin; Peckmann, Jörn (2009): Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge. Chemical Geology, 268(1-2), 97-106, https://doi.org/10.1016/j.chemgeo.2009.08.002
    Publication Date: 2024-06-26
    Description: The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (〈 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.
    Keywords: ARK-XVII/2; Center for Marine Environmental Sciences; DERIDGE; Dredge, pipe; DRG_P; From Mantle to Ocean: Energy-, Material- and Life-cycles at Spreading Axes; HYDROMAR1; M60/3; M60/3-49-GTV; M60/3-53-ROV-2; M60/3-54-GTV; M60/3-67-GTV; MARUM; Meteor (1986); Mid-Atlantic Ridge at 10-15°N; Polarstern; PS59/238; PS59/249; PS59 AMORE; Remote operated vehicle; ROV; Television-Grab; TVG
    Type: Dataset
    Format: application/zip, 2 datasets
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  • 14
    Publication Date: 2024-06-26
    Keywords: Center for Marine Environmental Sciences; Cerium; Cerium anomaly; DERIDGE; Dysprosium; Elevation of event; Erbium; Europium; Europium anomaly; Event label; From Mantle to Ocean: Energy-, Material- and Life-cycles at Spreading Axes; Gadolinium; HYDROMAR1; ICP-MS, Thermo Finnigan, Element 2; Lanthanum; Latitude of event; Longitude of event; M60/3; M60/3-49-GTV; M60/3-53-ROV-2; M60/3-54-GTV; M60/3-67-GTV; MARUM; Meteor (1986); Mid-Atlantic Ridge at 10-15°N; Neodymium; Rare-earth elements; Remote operated vehicle; ROV; Samarium; Sample ID; Television-Grab; TVG; Ytterbium; Yttrium
    Type: Dataset
    Format: text/tab-separated-values, 1414 data points
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  • 15
    Publication Date: 2024-06-26
    Keywords: ARK-XVII/2; Center for Marine Environmental Sciences; DERIDGE; Dredge, pipe; DRG_P; Elevation of event; Event label; Fraction; From Mantle to Ocean: Energy-, Material- and Life-cycles at Spreading Axes; HYDROMAR1; ICP-MS, Thermo Finnigan, Element 2; Latitude of event; Longitude of event; M60/3; M60/3-49-GTV; M60/3-53-ROV-2; M60/3-54-GTV; M60/3-67-GTV; Magnesium; Magnesium/Calcium ratio; Manganese; MARUM; Meteor (1986); Mid-Atlantic Ridge at 10-15°N; Minerals; Polarstern; Precision; PS59/238; PS59/249; PS59 AMORE; Remote operated vehicle; ROV; Sample ID; see reference(s); Strontium; Strontium/Calcium ratio; Strontium-87/Strontium-86 ratio; Television-Grab; Temperature, technical; TVG; δ18O
    Type: Dataset
    Format: text/tab-separated-values, 451 data points
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  • 16
    Publication Date: 2021-06-30
    Description: Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their 18O/16O and 7Li/6Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in 7Li/28Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ18O, Δ’17O and δ7Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ18O determinations, which was found to be 〈 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.
    Description: Key Points: Three widely available tourmaline reference materials are characterized for δ7Li, δ17O and δ18O, while new EPMA and SIMS measurements refine their major element compositions. SIMS data document homogeneity for these isotope ratios. SIMS matrix effect causes bias of 1.9‰ between elbaite and schorl, whereas silicate glass shows even more severe bias.
    Description: U.S. National Science Foundation
    Description: Natural Environment Research Council http://dx.doi.org/10.13039/501100000270
    Description: US Department of Energy http://dx.doi.org/10.13039/100000015
    Keywords: 551.9 ; tourmaline ; lithium isotopes ; oxygen isotopes ; reference materials ; SIMS ; matrix effect
    Type: article
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  • 17
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): B07103, doi:10.1029/2010JB007931.
    Description: Expeditions 304 and 305 of the Integrated Ocean Drilling Program cored and logged a 1.4 km section of the domal core of Atlantis Massif. Postdrilling research results summarized here constrain the structure and lithology of the Central Dome of this oceanic core complex. The dominantly gabbroic sequence recovered contrasts with predrilling predictions; application of the ground truth in subsequent geophysical processing has produced self-consistent models for the Central Dome. The presence of many thin interfingered petrologic units indicates that the intrusions forming the domal core were emplaced over a minimum of 100–220 kyr, and not as a single magma pulse. Isotopic and mineralogical alteration is intense in the upper 100 m but decreases in intensity with depth. Below 800 m, alteration is restricted to narrow zones surrounding faults, veins, igneous contacts, and to an interval of locally intense serpentinization in olivine-rich troctolite. Hydration of the lithosphere occurred over the complete range of temperature conditions from granulite to zeolite facies, but was predominantly in the amphibolite and greenschist range. Deformation of the sequence was remarkably localized, despite paleomagnetic indications that the dome has undergone at least 45° rotation, presumably during unroofing via detachment faulting. Both the deformation pattern and the lithology contrast with what is known from seafloor studies on the adjacent Southern Ridge of the massif. There, the detachment capping the domal core deformed a 100 m thick zone and serpentinized peridotite comprises ∼70% of recovered samples. We develop a working model of the evolution of Atlantis Massif over the past 2 Myr, outlining several stages that could explain the observed similarities and differences between the Central Dome and the Southern Ridge.
    Keywords: Atlantis Massif ; Integrated Ocean Drilling Program ; Oceanic Core Complex
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 18
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2004. 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 5 (2004): Q09F26, doi:10.1029/2004GC000744.
    Description: We present first results of a petrographic study of hydrothermally altered peridotites drilled during Ocean Drilling Program (ODP) Leg 209 in the 15°20′N fracture Zone area on the Mid-Atlantic Ridge (MAR). We find that serpentinization is extensive at all drill sites. Where serpentinization is incomplete, phase relations indicate two major reaction pathways. One is reaction of pyroxene to talc and tremolite, and the other is reaction of olivine to serpentine, magnetite, and brucite. We interpret these reactions in the light of recent peridotite-seawater reaction experiments and compositions of fluids venting from peridotite massifs at a range of temperatures. We suggest that the replacement of pyroxene by talc and tremolite takes place at temperatures 〉350°–400°C, where olivine is stable. The breakdown of olivine to serpentine, magnetite, and brucite is favored at temperatures below 250°C, where olivine reacts faster then pyroxene. High-temperature hydrothermal fluids venting at the Logatchev and Rainbow sites are consistent with rapid reaction of pyroxene and little or no reaction of olivine. Moderate-temperature fluids venting at the Lost City site are consistent with ongoing reaction of olivine to serpentine and brucite. Many completely serpentinized peridotites lack brucite and talc because once the more rapidly reacting phase is exhausted, interaction with the residual phase will change fluid pH and silica activity such that brucite or talc react to serpentine. At two sites we see strong evidence for continued fluid flow and fluid-rock interaction after serpentinization was complete. At Site 1268, serpentinites underwent massive replacement by talc under static conditions. This reaction requires either removal of Mg from or addition of Si to the system. We propose that the talc-altered rocks are Si-metasomatized and that the source of Si is likely gabbro-seawater reaction or breakdown of pyroxene deeper in the basement. The basement at Site 1268 is heavily veined, with talc and talc-oxide-sulfide veins being the most common vein types. It appears that the systems evolved from reducing (oxygen fugacity buffered by magnetite-pyrrhotite-pyrite and lower) to oxidizing (dominantly hematite). We propose that this transition is indicative of high fluid flux under retrograde conditions and that the abundance of hematite may relate to the Ca-depleted nature of the basement that prevents near-quantitative removal of seawater sulfate by anhydrite precipitation. At site 1272 we find abundant iowaite partly replacing brucite. While this is the first report of iowaite from a mid-ocean ridge setting, its presence indicates, again, fairly oxidizing conditions. Our preliminary results indicate that peridotite-seawater and serpentinite-seawater interactions can take place under a wider range of temperature and redox conditions than previously appreciated.
    Description: This research used data and/or samples supplied by the Ocean Drilling Program (ODP). ODP is sponsored by the U.S. National Science Foundation (NSF) and participating countries under management of Joint Oceanographic Institutions (JOI), Inc.
    Keywords: Hydrothermal system ; Ocean Drilling Program ; Oceanic crust ; Serpentinite ; Water-rock interaction
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 19
    Publication Date: 2021-07-21
    Description: The continuous improvement of analytical procedures using multi-collector technologies in ICP-mass spectrometry has led to an increased demand for isotope standards with improved homogeneity and reduced measurement uncertainty. For magnesium, this has led to a variety of available standards with different quality levels ranging from artefact standards to isotope reference materials certified for absolute isotope ratios. This required an intercalibration of all standards and reference materials, which we present in this interlaboratory comparison study. The materials Cambridge1, DSM3, ERM-AE143, ERM-AE144, ERM-AE145, IRMM-009 and NIST SRM 980 were cross-calibrated with expanded measurement uncertainties (95% confidence level) of less than 0.030‰ for the δ25/24Mg values and less than 0.037‰ for the δ26/24Mg values. Thus, comparability of all magnesium isotope delta (δ) measurements based on these standards and reference materials is established. Further, ERM-AE143 anchors all magnesium δ-scales to absolute isotope ratios and therefore establishes SI traceability, here traceability to the SI base unit mole. This applies especially to the DSM3 scale, which is proposed to be maintained. With ERM-AE144 and ERM-AE145, which are product and educt of a sublimation–condensation process, for the first time a set of isotope reference materials is available with a published value for the apparent triple isotope fractionation exponent θapp, the fractionation relationship ln α(25/24Mg)/ln α(26/24Mg).
    Keywords: 551.9 ; delta scale ; traceability ; scale anchor ; absolute isotope ratio ; comparability ; triple isotope fractionation
    Language: English
    Type: article
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  • 20
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2011. 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 12 (2011): Q03001, doi:10.1029/2010GC003322.
    Description: In situ secondary ion mass spectrometry (SIMS) analyses of δ7Li, Li/Ca, and Mg/Ca were performed on five synthetic aragonite samples precipitated from seawater at 25°C at different rates. The compositions of δ7Li in bulk aragonites and experimental fluids were measured by multicollector inductively coupled plasma–mass spectrometry (MC-ICP-MS). Both techniques yielded similar δ7Li in aragonite when SIMS analyses were corrected to calcium carbonate reference materials. Fractionation factors α7Li/6Li range from 0.9895 to 0.9923, which translates to a fractionation between aragonite and fluid from −10.5‰ to −7.7‰. The within-sample δ7Li range determined by SIMS is up to 27‰, exceeding the difference between bulk δ7Li analyses of different aragonite precipitates. Moreover, the centers of aragonite hemispherical bundles (spherulites) are enriched in Li/Ca and Mg/Ca relative to spherulite fibers by up to factors of 2 and 8, respectively. The Li/Ca and Mg/Ca ratios of spherulite fibers increase with aragonite precipitation rate. These results suggest that precipitation rate is a potentially important consideration when using Li isotopes and elemental ratios in natural carbonates as a proxy for seawater composition and temperature.
    Description: SIMS analyses were supported by U.S. NSF, EAR, Instrumentation and Facilities Program. The development of the method for bulk d7Li analysis and the MC‐ICP‐MS measurements were covered by NSF grant EAR/IF‐0318137. Precipitation experiments were supported by NSF through grants OCE‐0402728, OCE‐0527350, and OCE‐0823527 to Glenn Gaetani and Anne Cohen and through grant EAR‐0337481 to Bruce Watson.
    Keywords: Isotope ; Aragonite ; Rate ; SIMS ; Magnesium ; Lithium
    Repository Name: Woods Hole Open Access Server
    Type: Article
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