@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{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{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} } @article{HalamaKonradSchmolkeSudoetal.2014, author = {Halama, Ralf and Konrad-Schmolke, Matthias and Sudo, Masafumi and Marschall, Horst R. and Wiedenbeck, Michael}, title = {Effects of fluid-rock interaction on Ar-40/Ar-39 geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)}, series = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, volume = {126}, journal = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, publisher = {Elsevier}, address = {Oxford}, issn = {0016-7037}, doi = {10.1016/j.gca.2013.10.023}, pages = {475 -- 494}, year = {2014}, abstract = {In situ UV laser spot Ar-40/Ar-39 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 Ar-40/Ar-39 ages of phengite cores span a range of similar to 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 (similar to 36 mu g/g) than the older ones (similar to 43-48 mu g/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable delta B-11 values (-18 parts per thousand to -10 parts per thousand), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent Ar-40/Ar-39 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 delta B-11 values (-15 parts per thousand to -9 parts per thousand), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger Ar-40/Ar-39 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 Ar-40/Ar-39 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-delta B-11 fluid (delta B-11 = + 7 +/- 4 parts per thousand). 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 Ar-40/Ar-39 data in partially metasomatized rocks.}, language = {en} } @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{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{ScottKonradSchmolkeO'Brienetal.2013, author = {Scott, James M. and Konrad-Schmolke, Matthias and O'Brien, Patrick J. and G{\"u}nter, Christina}, title = {High-T, low-P formation of rare olivine-bearing symplectites in variscan eclogite}, series = {Journal of petrology}, volume = {54}, journal = {Journal of petrology}, number = {7}, publisher = {Oxford Univ. Press}, address = {Oxford}, issn = {0022-3530}, doi = {10.1093/petrology/egt015}, pages = {1375 -- 1398}, year = {2013}, abstract = {Extremely rare veinlets and reaction textures composed of symplectites of olivine (similar to Fo(43-55)) + plagioclase +/- spinel +/- ilmenite, associated with more common pyroxene + plagioclase and amphibole + plagioclase varieties, are preserved within eclogites and garnet pyroxenites in the Moldanubian Zone of the Bohemian Massif. Thermodynamic modelling integrated with conventional geothermometry conducted on an eclogite reveals that the symplectite-forming stage occurred at high T (similar to 850 degrees C) and low P (< 6 and > 2 center dot 5 kbar). The development of the different symplectite types reflects reactions that took place in micro-scale domains. The breakdown of high-P garnet controlled the formation of olivine-bearing and amphibole + plagioclase symplectites, whereas breakdown of high-P omphacite led to formation of pyroxene + plagioclase symplectites. In addition, post-eclogite facies but pre-symplectite stage porphyroblastic amphibole and phlogopite were also replaced by olivine-bearing symplectites. Material transfer calculations and thermodynamic modelling indicate that the formation of different symplectite types was linked despite their different bulk compositions. For example, the olivine-bearing symplectites gained Fe +/- Mg, whereas adjacent amphibole + plagioclase and pyroxene + plagioclase symplectites show losses in Fe and Mg; Al, Si and Ca were also variably exchanged. The olivine-bearing symplectites were particularly sensitive to Na despite the small concentration of this element. In eclogites where Na was readily available, the plagioclase composition in the olivine-bearing symplectites shifted from pure anorthite to bytownite, with the less calcic feldspar partitioning Si and inhibiting the formation of orthopyroxene. This regional high-T, low-P granulite-facies symplectite overprint may have been caused by advective heat loss from rapidly exhumed high-T, high-P granulitic bodies (Gfohl Unit) that were emplaced into and over the middle crust (Monotonous and Varied Series) during Carboniferous continent-continent collision.}, 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{HalamaGlodnyKonradSchmolkeetal.2018, author = {Halama, Ralf and Glodny, Johannes and Konrad-Schmolke, Matthias and Sudo, Masafumi}, title = {Rb-Sr and in situ Ar-40/Ar-39 dating of exhumation-related shearing and fluid-induced recrystallization in the Sesia zone (Western Alps, Italy)}, series = {Geosphere}, volume = {14}, journal = {Geosphere}, number = {4}, publisher = {American Institute of Physics}, address = {Boulder}, issn = {1553-040X}, doi = {10.1130/GES01521.1}, pages = {1425 -- 1450}, year = {2018}, abstract = {The Sesia zone in the Italian Western Alps is a piece of continental crust that has been subducted to eclogite-facies conditions and records a complex metamorphic history. The exact timing of events and the significance of geochronological information are debated due to the interplay of tectonic, metamorphic, and metasomatic processes. Here we present new geochronological data using Rb-Sr internal mineral isochrons and in situ Ar-40/Ar-39 laser ablation data to provide constraints on the relative importance of fluid-mediated mineral replacement reactions and diffusion for the interpretation of radiogenic isotope signatures, and on the use of these isotopic systems for dating metamorphic and variably deformed rocks. Our study focuses on the shear zone at the contact between two major lithological units of the Sesia zone, the eclogitic micaschists and the gneiss minuti. Metasedimentary rocks of the eclogitic micaschists unit contain phengite with step-like zoning in major element chemistry as evidence for petrologic disequilibrium. Distinct Ar-40/Ar-39 spot ages of relict phengite cores and over-printed rims demonstrate the preservation of individual age domains in the crystals. The eclogitic micaschists also show systematic Sr isotope disequilibria among different phengite populations, so that minimum ages of relict assemblage crystallization can be differentiated from the timing of late increments of deformation. The preservation of these disequilibrium features shows the lack of diffusive re-equilibration and underpins that fluid-assisted dissolution and recrystallization reactions are the main factors controlling the isotope record in these subduction-related metamorphic rocks. Blueschist-facies mylonites record deformation along the major shear zone that separates the eclogitic micaschists from the gneiss minuti. Two Rb-Sr isochrones that comprise several white mica fractions and glaucophane constrain the timing of this deformation and accompanying near-complete blueschist-facies re-equilibration of the Rb-Sr system to 60.1 +/- 0.9 Ma and 60.9 +/- 2.1 Ma, respectively. Overlapping ages in eclogitic micaschists of 60.1 +/- 1.1 (Rb-Sr isochron of sheared matrix assemblage), 58.6 +/- 0.8, and 60.9 +/- 0.4 Ma (white mica Ar-40/Ar-39 inverse isochron ages) support the significance of this age and show that fluid-rock interaction and partial re-equilibration occurred as much as several kilometers away from the shear zone. An earlier equilibration during high-pressure conditions in the eclogitic mica schists is recorded in minimum Rb-Sr ages for relict assemblages (77.2 +/- 0.8 and 72.4 +/- 1.1 Ma) and an Ar-40/Ar-39 inverse isochron age of 75.4 +/- 0.8 Ma for white mica cores, again demonstrating that the two isotope systems provide mutually supporting geochronological information. Local reactivation and recrystallization along the shear zone lasted >15 m.y., as late increments of deformation are recorded in a greenschist-facies mylonite by a Rb-Sr isochron age of 46.5 +/- 0.7 Ma.}, 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} }