TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - Handy, Mark R. A1 - Babist, Jochen A1 - O'Brien, Patrick J. T1 - Thermodynamic modelling of diffusion-controlled garnet growth N2 - 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 Y1 - 2005 SN - 0010-7999 ER - TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - Babist, Jochen A1 - Handy, Mark R. A1 - O'brien, Patrick J. T1 - The physico-chemical properties of a subducted slab from garnet zonation patterns (Sesia Zone, Western Alps) JF - Journal of petrology N2 - 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. KW - dehydration KW - high-pressure metamorphism KW - Sesia Zone KW - subduction KW - thermodynamic modelling Y1 - 2006 U6 - https://doi.org/10.1093/petrology/egl039 SN - 0022-3530 VL - 47 IS - 11 SP - 2123 EP - 2148 PB - Oxford Univ. Press CY - Oxford ER - TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - Zack, Thomas A1 - O'Brien, Patrick J. T1 - Combining thermodynamic and trace element modeling : a tool to quantify mineral reactions and trace element budgets during metamorphism Y1 - 2009 UR - http://www.sciencedirect.com/science/journal/00167037 U6 - https://doi.org/10.1016/j.gca.2009.05.009 SN - 0016-7037 ER - TY - JOUR A1 - Zack, Thomas A1 - Konrad-Schmolke, Matthias T1 - Distinguishing trace element redistribution during mineral reactions from fluid-induced trace element mobility in blueschists Y1 - 2009 UR - http://www.sciencedirect.com/science/journal/00167037 U6 - https://doi.org/10.1016/j.gca.2009.05.019 SN - 0016-7037 ER - TY - JOUR A1 - Wilke, Franziska Daniela Helena A1 - O'Brien, Patrick J. A1 - Altenberger, Uwe A1 - Konrad-Schmolke, Matthias A1 - Khan, M. Ahmed T1 - Multi-stage reaction history in different eclogite types from the Pakistan Himalaya and implications for exhumation processes N2 - 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. Y1 - 2010 UR - http://www.sciencedirect.com/science/journal/00244937 U6 - https://doi.org/10.1016/j.lithos.2009.07.015 SN - 0024-4937 ER - TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - O'Brien, Patrick J. A1 - Zack, Thomas T1 - Fluid Migration above a Subducted Slab-Constraints on Amount, Pathways and Major Element Mobility from Partially Overprinted Eclogite-facies Rocks (Sesia Zone, Western Alps) JF - Journal of petrology N2 - 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. KW - fluid migration KW - subduction KW - fluid-rock interaction KW - Sesia Zone Y1 - 2011 U6 - https://doi.org/10.1093/petrology/egq087 SN - 0022-3530 VL - 52 IS - 3 SP - 457 EP - 486 PB - Oxford Univ. Press CY - Oxford ER - TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - Zack, Thomas A1 - O'Brien, Patrick J. A1 - Barth, Matthias T1 - 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) JF - Earth & planetary science letters N2 - 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. KW - fluid-rock interaction KW - subduction zone KW - fluid migration KW - slab-mantle interface KW - trace element transport Y1 - 2011 U6 - https://doi.org/10.1016/j.epsl.2011.09.025 SN - 0012-821X VL - 311 IS - 3-4 SP - 287 EP - 298 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Scott, James M. A1 - Konrad-Schmolke, Matthias A1 - O'Brien, Patrick J. A1 - Günter, Christina T1 - High-T, low-P formation of rare olivine-bearing symplectites in variscan eclogite JF - Journal of petrology N2 - 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. KW - olivine KW - symplectite KW - eclogite KW - thermodynamics KW - Variscan Y1 - 2013 U6 - https://doi.org/10.1093/petrology/egt015 SN - 0022-3530 SN - 1460-2415 VL - 54 IS - 7 SP - 1375 EP - 1398 PB - Oxford Univ. Press CY - Oxford ER - TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - Halama, Ralf T1 - Combined thermodynamic-geochemical modeling in metamorphic geology: Boron as tracer of fluid-rock interaction JF - Lithos : an international journal of mineralogy, petrology, and geochemistry N2 - 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. KW - Thermodynamic-geochemical modeling KW - Fluid-rock interaction KW - Subduction KW - Dehydration KW - Boron isotopes Y1 - 2014 U6 - https://doi.org/10.1016/j.lithos.2014.09.021 SN - 0024-4937 SN - 1872-6143 VL - 208 SP - 393 EP - 414 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Halama, Ralf A1 - Konrad-Schmolke, Matthias A1 - Sudo, Masafumi A1 - Marschall, Horst R. A1 - Wiedenbeck, Michael T1 - Effects of fluid-rock interaction on Ar-40/Ar-39 geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps) JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - 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. Y1 - 2014 U6 - https://doi.org/10.1016/j.gca.2013.10.023 SN - 0016-7037 SN - 1872-9533 VL - 126 SP - 475 EP - 494 PB - Elsevier CY - Oxford ER -