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Now showing items 1 - 11 of 11

  • Noble gases recycled into the mantle through cold subduction zones

    Andrew J. Smye   Colin R.M. Jackson   Matthias Konrad-Schmolke   Marc A. Hesse   Steve W. Parman   David L. Shuster   Chris J. Ballentine  

    Abstract Subduction of hydrous and carbonated oceanic lithosphere replenishes the mantle volatile inventory. Substantial uncertainties exist on the magnitudes of the recycled volatile fluxes and it is unclear whether Earth surface reservoirs are undergoing net-loss or net-gain of H 2 O and CO 2 . Here, we use noble gases as tracers for deep volatile cycling. Specifically, we construct and apply a kinetic model to estimate the effect of subduction zone metamorphism on the elemental composition of noble gases in amphibole – a common constituent of altered oceanic crust. We show that progressive dehydration of the slab leads to the extraction of noble gases, linking noble gas recycling to H 2 O. Noble gases are strongly fractionated within hot subduction zones, whereas minimal fractionation occurs along colder subduction geotherms. In the context of our modelling, this implies that the mantle heavy noble gas inventory is dominated by the injection of noble gases through cold subduction zones. For cold subduction zones, we estimate a present-day bulk recycling efficiency, past the depth of amphibole breakdown, of 5–35% and 60–80% for 36 Ar and H 2 O bound within oceanic crust, respectively. Given that hotter subduction dominates over geologic history, this result highlights the importance of cooler subduction zones in regassing the mantle and in affecting the modern volatile budget of Earth's interior. Highlights • We model the transport of noble gases during subduction of oceanic crust. • Fractionation of noble gases is controlled by the availability of free fluid. • Hot subduction zones fractionate slab-bound noble gases. • Mantle heavy noble gas signature is consistent with recent increase in recycling efficiency of noble gases and water.
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  • Thermodynamic modelling of diffusion-controlled garnet growth

    Matthias Konrad-Schmolke   Mark R. Handy   Jochen Babist and Patrick J. O’Brien  

    Numerical thermodynamic modelling of mineral composition and modes for specified pressure-temperature paths reveals the strong influence of fractional garnet crystallisation, as well as water fractionation, on garnet growth histories in high pressure rocks. Disequilibrium element incorporation in garnet due to the development of chemical inhomogeneities around porphyroblasts leads to pronounced episodic growth and may even cause growth interruptions. Discontinuous growth, together with pressure- and temperature-dependent changes in garnet chemistry, cause zonation patterns that are indicative of different degrees of disequilibrium element incorporation. Chemical inhomogeneities in the matrix surrounding garnet porphyroblasts strongly affect garnet growth and lead to compositional discontinuities and steep compositional gradients in the garnet zonation pattern. Further, intergranular diffusion-controlled calcium incorporation can lead to a characteristic rise in grossular and spessartine contents at lower metamorphic conditions. The observation that garnet zonation patterns diagnostic of large and small fractionation effects coexist within the same sample suggests that garnet growth is often controlled by small-scale variations in the bulk rock chemistry. Therefore, the spatial distribution of garnet grains and their zonation patterns, together with numerical growth models of garnet zonation patterns, yield information about the processes limiting garnet growth. These processes include intercrystalline element transport and dissolution of pre-existing grains. Discontinuities in garnet growth induced by limited element supply can mask traces of the thermobarometric history of the rock. Therefore, thermodynamic modelling that considers fractional disequilibrium crystallisation is required to interpret compositional garnet zonation in terms of a quantitative pressure and temperature path of the host rock.
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  • Thermodynamic modelling of diffusion-controlled garnet growth

    Matthias Konrad-Schmolke   Mark R. Handy   Jochen Babist   Patrick J. O’Brien  

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  • Combined thermodynamic–geochemical modeling in metamorphic geology: Boron as tracer of fluid–rock interaction

    Matthias Konrad-Schmolke   Ralf Halama  

    Abstract Quantitative geochemical modeling is today applied in a variety of geological environments from the petrogenesis of igneous rocks to radioactive waste disposal. In addition, the development of thermodynamic databases and computer programs to calculate equilibrium phase diagrams has greatly advanced our ability to model geodynamic processes. Combined with experimental data on elemental partitioning and isotopic fractionation, thermodynamic forward modeling unfolds enormous capacities that are far from exhausted. In metamorphic petrology the combination of thermodynamic and trace element forward modeling can be used to study and to quantify processes at spatial scales from μm to km. The thermodynamic forward models utilize Gibbs energy minimization to quantify mineralogical changes along a reaction path of a chemically open fluid/rock system. These results are combined with mass balanced trace element calculations to determine the trace element distribution between rock and melt/fluid during the metamorphic evolution. Thus, effects of mineral reactions, fluid–rock interaction and element transport in metamorphic rocks on the trace element and isotopic composition of minerals, rocks and percolating fluids or melts can be predicted. Here we illustrate the capacities of combined thermodynamic–geochemical modeling based on two examples relevant to mass transfer during metamorphism. The first example focuses on fluid–rock interaction in and around a blueschist-facies shear zone in felsic gneisses, where fluid-induced mineral reactions and their effects on boron (B) concentrations and isotopic compositions in white mica are modeled. In the second example, fluid release from a subducted slab, the associated transport of B as well as variations in B concentrations and isotopic compositions in liberated fluids and residual rocks are modeled. We compare the modeled results of both examples to geochemical data of natural minerals and rocks and demonstrate that the combination of thermodynamic and geochemical models enables quantification of metamorphic processes and insights into element cycling that would have been unattainable if only one model approach was chosen. Graphical abstract Highlights • Combined thermodynamic–geochemical models of subduction zone processes • Modeling of dehydration patterns and boron release during subduction • Combined [B]–δ 11 B trends as tracers of fluid–rock interaction
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  • Retrograde metasomatic effects on phase assemblages in an interlayered blueschist–greenschist sequence (Coastal Cordillera, Chile)

    Ralf Halama   Matthias Konrad-Schmolke  

    Abstract Interlayered blueschists and greenschists of the Coastal Cordillera (Chile) are part of a Late Palaeozoic accretionary complex. They represent metavolcanic rocks with oceanic affinities based on predominantly OIB-type REE patterns and immobile trace element ratios. Both rock types have similar mineralogies, albeit with different mineral modal abundances. Amphibole is the major mafic mineral and varies compositionally from glaucophane to actinolite. The presence of glaucophane relicts as cores in zoned amphiboles in both blueschists and greenschists is evidence for a pervasive high-pressure metamorphic stage, indicating that tectonic juxtaposition is an unlikely explanation for the cm–dm scale interlayering. During exhumation, a retrograde greenschist-facies overprint stabilized chlorite + albite + winchitic/actinolitic amphibole + phengitic white mica ± epidote ± K-feldspar at 0.4 ± 0.1 GPa. Geochemical variability can be partly ascribed to primary magmatic and partly to secondary metasomatic processes that occurred under greenschist-facies conditions. Isocon diagrams of several adjacent blueschist–greenschist pairs with similar protolith geochemistry were used to evaluate metasomatic changes due to retrograde fluid–rock interaction. The most important geochemical changes are depletion of Si and Na and addition of water in the greenschists compared to the blueschists. Transition metals and LILE are mobilized to varying degrees. The unsystematic deviations from magmatic fractionation trends suggest open system conditions and influx of an external fluid. Pseudosection and water isopleth calculations show that the rocks were dehydrating during most of their exhumation history and remained at water-saturated conditions. The mineralogical changes, in particular breakdown of blue amphibole and replacement by chlorite, albite and calcic/sodic–calcic amphibole, are the prime cause for the distinct coloring. Pseudo-binary phase diagrams were used as a means to link bulk rock geochemical variability to modal and chemical changes in the mineralogy. The geochemical changes induced by fluid–rock interaction are important in two ways: First, the bulk rock chemistry is altered, leading to the stabilization of higher modal proportions of chlorite in the greenschists. Second, the retrograde overprint is a selective, layer-parallel fluid infiltration process, causing more intense greenschist-facies recrystallization in greenschist layers and therefore preferential preservation of blue amphibole in blueschist layers. Hence, the distinct colors were acquired by a combination of compositional variability, both primary magmatic and secondary metasomatic, and the different intensity of retrograde fluid infiltration. Highlights • Interlayering of blueschists and greenschists in the Coastal Cordillera (Chile) • Distinction between primary magmatic and secondary metasomatic geochemical effects • Evidence for retrograde greenschist-facies overprint during exhumation • Rocks experienced selective infiltration overprinting during retrogression. • Modeling of metasomatic processes using pseudo-binary phase diagrams
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  • Garnet growth at high- and ultra-high pressure conditions and the effect of element fractionation on mineral modes and composition

    Matthias Konrad-Schmolke   Patrick J. O\"Brien   Christian de Capitani   Dennis A. Carswell  

    In this paper we show that thermodynamic forward modelling, using Gibbs energy minimisation with consideration of element fractionation into refractory phases and/or liberated fluids, is able to extract information about the complex physical and chemical evolution of a deeply subducted rock volume. By comparing complex compositional growth zonations in garnets from high-and ultra-high pressure samples with those derived from thermodynamic forward modelling, we yield an insight into the effects of element fractionation on composition and modes of the co-genetic metamorphic phase assemblage. Our results demonstrate that fractionation effects cause discontinuous growth and re-crystallisation of metamorphic minerals in high pressure rocks. Reduced or hindered mineral growth at UHP conditions can control the inclusion and preservation of minerals indicative for UHP metamorphism, such as coesite, thus masking peak pressure conditions reached in subducted rocks.
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  • Garnet growth at high- and ultra-high pressure conditions and the effect of element fractionation on mineral modes and composition

    Matthias Konrad-Schmolke   Patrick J. O'Brien   Christian de Capitani   Dennis A. Carswell  

    In this paper we show that thermodynamic forward modelling, using Gibbs energy minimisation with consideration of element fractionation into refractory phases and/or liberated fluids, is able to extract information about the complex physical and chemical evolution of a deeply subducted rock volume. By comparing complex compositional growth zonations in garnets from high-and ultra-high pressure samples with those derived from thermodynamic forward modelling, we yield an insight into the effects of element fractionation on composition and modes of the co-genetic metamorphic phase assemblage. Our results demonstrate that fractionation effects cause discontinuous growth and re-crystallisation of metamorphic minerals in high pressure rocks. Reduced or hindered mineral growth at UHP conditions can control the inclusion and preservation of minerals indicative for UHP metamorphism, such as coesite, thus masking peak pressure conditions reached in subducted rocks.
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  • Combined thermodynamic and rare earth element modelling of garnet growth during subduction: Examples from ultrahigh-pressure eclogite of the Western Gneiss Region, Norway

    Matthias Konrad-Schmolke   Thomas Zack   Patrick J. O'Brien   Dorrit E. Jacob  

    Major and trace element zonation patterns were determined in ultrahigh-pressure eclogite garnets from the Western Gneiss Region (Norway). All investigated garnets show multiple growth zones and preserve complex growth zonation patterns with respect to both major and rare earth elements (REE). Due to chemical differences of the host rocks two types of major element compositional zonation patterns occur: (1) abrupt, step-like compositional changes corresponding with the growth zones and (2) compositionally homogeneous interiors, independent of growth zones, followed by abrupt chemical changes towards the rims. Despite differences in major element zonation, the REE patterns are almost identical in all garnets and can be divided into four distinct zones with characteristic patterns.In order to interpret the major and trace element distribution and zoning patterns in terms of the subduction history of the rocks, we combined thermodynamic forward models for appropriate bulk rock compositions to yield molar proportions and major element compositions of stable phases along the inferred pressure-temperature path with a mass balance distribution of REEs among the calculated stable phases during high pressure metamorphism. Our thermodynamic forward models reproduce the complex major element zonation patterns and growth zones in the natural garnets, with garnet growth predicted during four different reaction stages: (1) chlorite breakdown, (2) epidote breakdown, (3) amphibole breakdown and (4) reduction in molar clinopyroxene at ultrahigh-pressure conditions.Mass-balance of the rare earth element distribution among the modelled stable phases yielded characteristic zonation patterns in garnet that closely resemble those in the natural samples. Garnet growth and trace element incorporation occurred in near thermodynamic equilibrium with matrix phases during subduction. The rare earth element patterns in garnet exhibit distinct enrichment zones that fingerprint the minerals involved in the garnet-forming reactions as well as local peaks that can be explained by fractionation effects and changes in the mineral assemblage.
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  • Combined thermodynamic and rare earth element modelling of garnet growth during subduction: Examples from ultrahigh-pressure eclogite of the Western Gneiss Region, Norway

    Matthias Konrad-Schmolke   Thomas Zack   Patrick J. O\"Brien   Dorrit E. Jacob  

    Major and trace element zonation patterns were determined in ultrahigh-pressure eclogite garnets from the Western Gneiss Region (Norway). All investigated garnets show multiple growth zones and preserve complex growth zonation patterns with respect to both major and rare earth elements (REE). Due to chemical differences of the host rocks two types of major element compositional zonation patterns occur: (1) abrupt, step-like compositional changes corresponding with the growth zones and (2) compositionally homogeneous interiors, independent of growth zones, followed by abrupt chemical changes towards the rims. Despite differences in major element zonation, the REE patterns are almost identical in all garnets and can be divided into four distinct zones with characteristic patterns.In order to interpret the major and trace element distribution and zoning patterns in terms of the subduction history of the rocks, we combined thermodynamic forward models for appropriate bulk rock compositions to yield molar proportions and major element compositions of stable phases along the inferred pressure-temperature path with a mass balance distribution of REEs among the calculated stable phases during high pressure metamorphism. Our thermodynamic forward models reproduce the complex major element zonation patterns and growth zones in the natural garnets, with garnet growth predicted during four different reaction stages: (1) chlorite breakdown, (2) epidote breakdown, (3) amphibole breakdown and (4) reduction in molar clinopyroxene at ultrahigh-pressure conditions.Mass-balance of the rare earth element distribution among the modelled stable phases yielded characteristic zonation patterns in garnet that closely resemble those in the natural samples. Garnet growth and trace element incorporation occurred in near thermodynamic equilibrium with matrix phases during subduction. The rare earth element patterns in garnet exhibit distinct enrichment zones that fingerprint the minerals involved in the garnet-forming reactions as well as local peaks that can be explained by fractionation effects and changes in the mineral assemblage.
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  • Effects of fluid–rock interaction on <sup>40</sup>Ar/<sup>39</sup>Ar geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

    Ralf Halama   Matthias Konrad-Schmolke   Masafumi Sudo   Horst R. Marschall   Michael Wiedenbeck  

    Abstract In situ UV laser spot 40 Ar/ 39 Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid–rock interaction. In weakly deformed samples, apparent 40 Ar/ 39 Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88–82 and 77–74 Ma, respectively. The younger cores have on average lower B contents (∼36 μg/g) than the older ones (∼43–48 μg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable δ 11 B values (−18‰ to −10‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40 Ar/ 39 Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40 Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ± 1.1 Ma for rims surrounding older cores (82.6 ± 0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar δ 11 B values (−15‰ to −9‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40 Ar/ 39 Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40 Ar/ 39 Ar ages (64.7–68.8 Ma), yielding an inverse isochron age of 65.0 ± 3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-δ 11 B fluid (δ 11 B = +7 ± 4‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40 Ar/ 39 Ar data in partially metasomatized rocks.
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  • Fluid migration above a subducted slab — Thermodynamic and trace element modelling of fluid–rock interaction in partially overprinted eclogite-facies rocks (Sesia Zone, Western Alps)

    Matthias Konrad-Schmolke   Thomas Zack   Patrick J. O\"Brien   Matthias Barth  

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