@article{KonradSchmolkeZackO'Brienetal.2011, author = {Konrad-Schmolke, Matthias and Zack, Thomas and O'Brien, Patrick J. and Barth, Matthias}, title = {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)}, series = {Earth \& planetary science letters}, volume = {311}, journal = {Earth \& planetary science letters}, number = {3-4}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0012-821X}, doi = {10.1016/j.epsl.2011.09.025}, pages = {287 -- 298}, year = {2011}, abstract = {The amount and composition of subduction zone fluids and the effect of fluid-rock interaction at a slab-mantle interface have been constrained by thermodynamic and trace element modelling of partially overprinted blueschist-facies rocks from the Sesia Zone (Western Alps). Deformation-induced differences in fluid flux led to a partial preservation of pristine mineral cores in weakly deformed samples that were used to quantify Li, B, Stand Pb distribution during mineral growth, -breakdown and modification induced by fluid-rock interaction. Our results show that Li and 13 budgets are fluid-controlled, thus acting as tracers for fluid-rock interaction processes, whereas Stand Pb budgets are mainly controlled by the fluid-induced formation of epidote. Our calculations show that fluid-rock interaction caused significant Li and B depletion in the affected rocks due to leaching effects, which in turn can lead to a drastic enrichment of these elements in the percolating fluid. Depending on available fluid-mineral trace element distribution coefficients modelled fluid rock ratios were up to 0.06 in weakly deformed samples and at least 0.5 to 4 in shear zone mylonites. These amounts lead to time integrated fluid fluxes of up to 1.4-10(2) m(3) m(-2) in the weakly deformed rocks and 1-8-10(3) m(3) m(-2) in the mylonites. Combined thermodynamic and trace element models can be used to quantify metamorphic fluid fluxes and the associated element transfer in complex, reacting rock systems and help to better understand commonly observed fluid-induced trace element trends in rocks and minerals from different geodynamic environments.}, language = {en} } @article{KonradSchmolkeHandyBabistetal.2005, author = {Konrad-Schmolke, Matthias and Handy, Mark R. and Babist, Jochen and O'Brien, Patrick J.}, title = {Thermodynamic modelling of diffusion-controlled garnet growth}, issn = {0010-7999}, year = {2005}, abstract = {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}, language = {en} } @article{KonradSchmolkeZackO'Brien2009, author = {Konrad-Schmolke, Matthias and Zack, Thomas and O'Brien, Patrick J.}, title = {Combining thermodynamic and trace element modeling : a tool to quantify mineral reactions and trace element budgets during metamorphism}, issn = {0016-7037}, doi = {10.1016/j.gca.2009.05.009}, year = {2009}, language = {en} } @article{KonradSchmolkeO'BrienZack2011, author = {Konrad-Schmolke, Matthias and O'Brien, Patrick J. and Zack, Thomas}, title = {Fluid Migration above a Subducted Slab-Constraints on Amount, Pathways and Major Element Mobility from Partially Overprinted Eclogite-facies Rocks (Sesia Zone, Western Alps)}, series = {Journal of petrology}, volume = {52}, journal = {Journal of petrology}, number = {3}, publisher = {Oxford Univ. Press}, address = {Oxford}, issn = {0022-3530}, doi = {10.1093/petrology/egq087}, pages = {457 -- 486}, year = {2011}, abstract = {The Western Alpine Sesia-Lanzo Zone (SLZ) is a sliver of eclogite-facies continental crust exhumed from mantle depths in the hanging wall of a subducted oceanic slab. Eclogite-facies felsic and basic rocks sampled across the internal SLZ show different degrees of retrograde metamorphic overprint associated with fluid influx. The weakly deformed samples preserve relict eclogite-facies mineral assemblages that show partial fluid-induced compositional re-equilibration along grain boundaries, brittle fractures and other fluid pathways. Multiple fluid influx stages are indicated by replacement of primary omphacite by phengite, albitic plagioclase and epidote as well as partial re-equilibration and/or overgrowths in phengite and sodic amphibole, producing characteristic step-like compositional zoning patterns. The observed textures, together with the map-scale distribution of the samples, suggest open-system, pervasive and reactive fluid flux across large rock volumes above the subducted slab. Thermodynamic modelling indicates a minimum amount of fluid of 0 center dot 1-0 center dot 5 wt \% interacting with the wall-rocks. Phase relations and reaction textures indicate mobility of K, Ca, Fe and Mg, whereas Al is relatively immobile in these medium-temperature-high-pressure fluids. Furthermore, the thermodynamic models show that recycling of previously fractionated material, such as in the cores of garnet porphyroblasts, largely controls the compositional re-equilibration of the exhumed rock body.}, language = {en} } @article{KonradSchmolkeBabistHandyetal.2006, author = {Konrad-Schmolke, Matthias and Babist, Jochen and Handy, Mark R. and O'brien, Patrick J.}, title = {The physico-chemical properties of a subducted slab from garnet zonation patterns (Sesia Zone, Western Alps)}, series = {Journal of petrology}, volume = {47}, journal = {Journal of petrology}, number = {11}, publisher = {Oxford Univ. Press}, address = {Oxford}, issn = {0022-3530}, doi = {10.1093/petrology/egl039}, pages = {2123 -- 2148}, year = {2006}, abstract = {Garnets in continentally derived high-pressure (HP) rocks of the Sesia Zone (Western Alps) exhibit three different chemical zonation patterns, depending on sample locality. Comparison of observed garnet zonation patterns with thermodynamically modelled patterns shows that the different patterns are caused by differences in the water content of the subducted protoliths during prograde metamorphism. Zonation patterns of garnets in water-saturated host rocks show typical prograde chemical zonations with steadily increasing pyrope content and increasing XMg, together with bell-shaped spessartine patterns. In contrast, garnets in water-undersaturated rocks have more complex zonation patterns with a characteristic decrease in pyrope and XMg between core and inner rim. In some cases, garnets show an abrupt compositional change in core-to-rim profiles, possibly due to water-undersaturation prior to HP metamorphism. Garnets from both water-saturated and water-undersaturated rocks show signs of intervening growth interruptions and core resorption. This growth interruption results from bulk-rock depletion caused by fractional garnet crystallization. The water content during burial influences significantly the physical properties of the subducted rocks. Due to enhanced garnet crystallization, water-undersaturated rocks, i.e. those lacking a free fluid phase, become denser than their water-saturated equivalents, facilitating the subduction of continental material. Although water-bearing phases such as phengite and epidote are stable up to eclogite-facies conditions in these rocks, dehydration reactions during subduction are lacking in water-undersaturated rocks up to the transition to the eclogite facies, due to the thermodynamic stability of such hydrous phases at high P-T conditions. Our calculations show that garnet zonation patterns strongly depend on the mineral parageneses stable during garnet growth and that certain co-genetic mineral assemblages cause distinct garnet zonation patterns. This observation enables interpretation of complex garnet growth zonation patterns in terms of garnet-forming reactions and water content during HP metamorphism, as well determination of detailed P-T paths.}, language = {en} } @article{WilkeO'BrienAltenbergeretal.2010, author = {Wilke, Franziska Daniela Helena and O'Brien, Patrick J. and Altenberger, Uwe and Konrad-Schmolke, Matthias and Khan, M. Ahmed}, title = {Multi-stage reaction history in different eclogite types from the Pakistan Himalaya and implications for exhumation processes}, issn = {0024-4937}, doi = {10.1016/j.lithos.2009.07.015}, year = {2010}, abstract = {Metabasites were sampled from rock series of the subducted margin of the Indian Plate, the so-called Higher Himalayan Crystalline, in the Upper Kaghan Valley, Pakistan. These vary from corona dolerites, cropping out around Saif- ul-Muluk in the south, to coesite-eclogite close to the suture zone against rocks of the Kohistan arc in the north. Bulk rock major- and trace-element chemistry reveals essentially a single protolith as the source for five different eclogite types, which differ in fabric, modal mineralogy as well as in mineral chemistry. The study of newly-collected samples reveals coesite (confirmed by in situ Raman spectroscopy) in both garnet and omphacite. All eclogites show growth of amphiboles during exhumation. Within some coesite-bearing eclogites the presence of glaucophane cores to barroisite is noted whereas in most samples porphyroblastic sodic-calcic amphiboles are rimmed by more aluminous calcic amphibole (pargasite, tschermakite, and edenite). Eclogite facies rutile is replaced by ilmenite which itself is commonly surrounded by titanite. In addition, some eclogite bodies show leucocratic segregations containing phengite, quartz, zoisite and/or kyanite. The important implication is that the complex exhumation path shows stages of initial cooling during decompression (formation of glaucophane) followed by reheating: a very similar situation to that reported for the coesite-bearing eclogite series of the Tso Morari massif, India, 450 km to the south-east.}, language = {en} } @article{ZackKonradSchmolke2009, author = {Zack, Thomas and Konrad-Schmolke, Matthias}, title = {Distinguishing trace element redistribution during mineral reactions from fluid-induced trace element mobility in blueschists}, issn = {0016-7037}, doi = {10.1016/j.gca.2009.05.019}, year = {2009}, language = {en} } @misc{KonradSchmolkeHalama2014, author = {Konrad-Schmolke, Matthias and Halama, Ralf}, title = {Combined thermodynamic-geochemical modeling in metamorphic geology: Boron as tracer of fluid-rock interaction}, series = {Lithos : an international journal of mineralogy, petrology, and geochemistry}, volume = {208}, journal = {Lithos : an international journal of mineralogy, petrology, and geochemistry}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0024-4937}, doi = {10.1016/j.lithos.2014.09.021}, pages = {393 -- 414}, year = {2014}, 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 mu m 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. (C) 2014 Elsevier B.V. All rights reserved.}, language = {en} } @article{KonradSchmolkeHalamaManea2016, author = {Konrad-Schmolke, Matthias and Halama, Ralf and Manea, Vlad C.}, title = {Slab mantle dehydrates beneath KamchatkaYet recycles water into the deep mantle}, series = {Geochemistry, geophysics, geosystems}, volume = {17}, journal = {Geochemistry, geophysics, geosystems}, publisher = {American Geophysical Union}, address = {Washington}, issn = {1525-2027}, doi = {10.1002/2016GC006335}, pages = {2987 -- 3007}, year = {2016}, abstract = {The subduction of hydrated slab mantle is the most important and yet weakly constrained factor in the quantification of the Earth's deep geologic water cycle. The most critical unknowns are the initial hydration state and the dehydration behavior of the subducted oceanic mantle. Here we present a combined thermomechanical, thermodynamic, and geochemical model of the Kamchatka subduction zone that indicates significant dehydration of subducted slab mantle beneath Kamchatka. Evidence for the subduction of hydrated oceanic mantle comes from across-arc trends of boron concentrations and isotopic compositions in arc volcanic rocks. Our thermodynamic-geochemical models successfully predict the complex geochemical patterns and the spatial distribution of arc volcanoes in Kamchatka assuming the subduction of hydrated oceanic mantle. Our results show that water content and dehydration behavior of the slab mantle beneath Kamchatka can be directly linked to compositional features in arc volcanic rocks. Depending on hydration depth of the slab mantle, our models yield water recycling rates between 1.1 × 103 and 7.4 × 103 Tg/Ma/km corresponding to values between 0.75 × 106 and 5.2 × 106 Tg/Ma for the entire Kamchatkan subduction zone. These values are up to one order of magnitude lower than previous estimates for Kamchatka, but clearly show that subducted hydrated slab mantle significantly contributes to the water budget in the Kamchatkan subduction zone.}, language = {en} } @article{HalamaKonradSchmolke2015, author = {Halama, Ralf and Konrad-Schmolke, Matthias}, title = {Retrograde metasomatic effects on phase assemblages in an interlayered blueschist-greenschist sequence (Coastal Cordillera, Chile)}, series = {Lithos : an international journal of mineralogy, petrology, and geochemistry}, volume = {216}, journal = {Lithos : an international journal of mineralogy, petrology, and geochemistry}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0024-4937}, doi = {10.1016/j.lithos.2014.12.004}, pages = {31 -- 47}, year = {2015}, 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 01B-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. (C) 2014 Elsevier B.V. All rights reserved.}, language = {en} }