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Institute
Quantitative thermodynamic and geochemical modeling is today applied in a variety of geological environments from the petrogenesis of igneous rocks to the oceanic realm. Thermodynamic calculations are used, for example, to get better insight into lithosphere dynamics, to constrain melting processes in crust and mantle as well as to study fluid-rock interaction. The development of thermodynamic databases and computer programs to calculate equilibrium phase diagrams have greatly advanced our ability to model geodynamic processes from subduction to orogenesis. However, a well-known problem is that despite its broad application the use and interpretation of thermodynamic models applied to natural rocks is far from straightforward. For example, chemical disequilibrium and/or unknown rock properties, such as fluid activities, complicate the application of equilibrium thermodynamics.
One major aspect of the publications presented in this Habilitationsschrift are new approaches to unravel dynamic and chemical histories of rocks that include applications to chemically open system behaviour. This approach is especially important in rocks that are affected by element fractionation due to fractional crystallisation and fluid loss during dehydration reactions. Furthermore, chemically open system behaviour has also to be considered for studying fluid-rock interaction processes and for extracting information from compositionally zoned metamorphic minerals. In this Habilitationsschrift several publications are presented where I incorporate such open system behaviour in the forward models by incrementing the calculations and considering changing reacting rock compositions during metamorphism. I apply thermodynamic forward modelling incorporating the effects of element fractionation in a variety of geodynamic and geochemical applications in order to better understand lithosphere dynamics and mass transfer in solid rocks.
In three of the presented publications I combine thermodynamic forward models with trace element calculations in order to enlarge the application of geochemical numerical forward modeling. In these publications a combination of thermodynamic and trace element forward modeling is used to study and quantify processes in metamorphic petrology at spatial scales from µm to km. In the thermodynamic forward models I 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.
One of the included publications shows that trace element growth zonations in metamorphic garnet porphyroblasts can be used to get crucial information about the reaction path of the investigated sample. In order to interpret the major and trace element distribution and zoning patterns in terms of the reaction history of the samples, we combined thermodynamic forward models with mass-balance rare earth element calculations. Such combined thermodynamic and mass-balance calculations 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. We can show in that paper that garnet growth and trace element incorporation occurred in near thermodynamic equilibrium with matrix phases during subduction and that the rare earth element patterns in garnet exhibit distinct enrichment zones that fingerprint the minerals involved in the garnet-forming reactions.
In two of the presented publications I illustrate the capacities of combined thermodynamic-geochemical modeling based on examples relevant to mass transfer in subduction zones. 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 and associated transport of B and variations in B concentrations and isotopic compositions in liberated fluids and residual rocks are modeled. I show that, combined with experimental data on elemental partitioning and isotopic fractionation, thermodynamic forward modeling unfolds enormous capacities that are far from exhausted.
In my publications presented in this Habilitationsschrift I compare the modeled results 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 so far.
Thus, the contributions to the science community presented in this Habilitatonsschrift concern the fields of petrology, geochemistry, geochronology but also ore geology that all use thermodynamic and geochemical models to solve various problems related to geo-materials.
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.
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.
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.