TY - JOUR A1 - Sokol, Krzysztof A1 - Halama, Ralf A1 - Meliksetian, Khachatur A1 - Savov, Ivan P. A1 - Navasardyan, Gevorg A1 - Sudo, Masafumi T1 - Alkaline magmas in zones of continental convergence BT - the Tezhsar volcano-intrusive ring complex, Armenia JF - Lithos : an international journal of mineralogy, petrology, and geochemistry N2 - Alkaline igneous rocks are relatively rare in settings of tectonic convergence and little is known about their petrogenesis in these settings. This study aims to contribute to a better understanding of the formation of alkaline igneous rocks by an investigation of the Tezhsar volcano-intrusive alkaline ring complex (TAC) in the Armenian Lesser Caucasus, which is located between the converging Eurasian and Arabian plates. We present new petrological, geochemical and Sr Nd isotope data for the TAC to constrain magma genesis and magma source characteristics. Moreover, we provide a new Ar-40/Ar-39 age of 41.0 +/- 0.5 Ma on amphibole from a nepheline syenite that is integrated into the regional context of ongoing regional convergence and widespread magmatism. The TAC is spatially concentric and measures similar to 10 km in diameter representing the relatively shallow plumbing system of a major stratovolcano juxtaposed by ring faulting with its extrusive products. The plutonic units comprise syenites and nepheline syenites, whereas the extrusive units are dominated by trachytic-phonolitic rocks. The characteristic feature of the TAC is the development of pseudomorphs after leucite in all types of the volcanic, subvolcanic and intrusive alkaline rocks. Whole-rock major element data show a metaluminous (Alkalinity Index = 0-0.1), alkalic and silica-undersaturated (Feldspathoid Silica-Saturation Index <0) character of the TAC. The general trace element enrichment and strong fractionation of REEs (La-N/Yb-N up to 70) indicate a relatively enriched magma source and small degrees of partial melting. All TAC rocks show a negative Nb Ta anomalies typical of subduction zone settings. The initial 87Sr/85Sr ratios (0.704-0.705) and positive sNd values (+3 to +5) indicate an isotopically depleted upper mantle and lack of significant crustal influence, which in turn suggests the TAC magma has formed via differentiation from lithospheric mantle melts. KW - Alkaline igneous rocks KW - Ring complex KW - Armenia KW - Geochemistry KW - Ar-40/Ar-39 dating KW - Pseudoleucite Y1 - 2018 U6 - https://doi.org/10.1016/j.lithos.2018.08.028 SN - 0024-4937 SN - 1872-6143 VL - 320 SP - 172 EP - 191 PB - Elsevier CY - Amsterdam 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 - Läger, Kathrin A1 - Halama, Ralf A1 - Hansteen, Thor A1 - Savov, Ivan P. A1 - Murcia, Hugo F. A1 - Cortes, Gloria P. A1 - Garbe-Schönberg, Dieter T1 - Crystallization conditions and petrogenesis of the lava dome from the similar to 900 years BP eruption of Cerro Machin Volcano, Colombia JF - Journal of South American earth sciences N2 - The last known eruption at Cerro Machin Volcano (CMV) in the Central Cordillera of Colombia occurred 900 years BP and ended with the formation of a dacitic lava dome. The dome rocks contain both normally and reversely zoned plagioclase (An(24-54)), unzoned and reversely zoned amphiboles of dominantly tschermakite and pargasite/magnesio-hastingsite composition and olivine xenocrysts (Fo = 85-88) with amphibole/clinopyroxene overgrowth, all suggesting interaction with mafic magma at depth. Plagioclase additionally exhibits complex oscillatory zoning patterns reflecting repeated replenishment, fractionation and changes in intrinsic conditions in the magma reservoir. Unzoned amphiboles and cores of the reversely zoned amphiboles give identical crystallization conditions of 910 +/- 30 degrees C and 360 +/- 70 MPa, corresponding to a depth of about 13 +/- 2 km, at moderately oxidized conditions (f(O2) = +0.5 +/- 0.2 Delta NNO). The water content in the melt, calculated based on amphibole chemistry, is 7.1 +/- 0.4 wt.%. Rims of the reversely zoned amphiboles are relatively enriched in MgO and yield higher crystallization temperatures (T = 970 +/- 25 degrees C), slightly lower melt H2O contents (6.1 +/- 0.7 wt.%) and overlapping pressures (410 +/- 100 MPa). We suggest that these rims crystallized following an influx of mafic melt into a resident magma reservoir at mid-crustal depths, further supported by the occurrence of xenocrystic olivine. Crystallization of biotite, albite-rich plagioclase and quartz occurred at comparatively low temperatures (probably <800 degrees C) during early stages of ascent or storage at shallower levels. Based on amphibole mineral chemistry, the felsic resident melt had a rhyolitic composition (71 +/- 2 wt.% SiO2), whereas the hybrid magma, from which the amphibole rims crystallized, was dacitic (64 +/- 3 wt.% SiO2). The bulk rock chemistry of the CMV lava dome dacites is homogenous. They have elevated (La/Nb)(N) ratios of 3.8-4.5, typical for convergent margin magmas, and display several geochemical characteristics, of adakites. Both Sr and Nd isotope compositions (Sr-87/Sr-86 similar to 0.70497, Nd-143/Nd-144 similar to 0.51267) are among the most radiogenic observed for the Northern Volcanic Zone of the Andes. They are distinct from oceanic crust that has been subducted in the region, pointing to a continental crustal control on the isotope composition and hence the adakitic signature, possibly in a crustal "hot zone". KW - Colombian Andes KW - Cerro Machin Volcano KW - Magma mixing KW - Amphibole geothermobarometry KW - Trace element geochemistry Y1 - 2013 U6 - https://doi.org/10.1016/j.jsames.2013.09.009 SN - 0895-9811 VL - 48 IS - 12 SP - 193 EP - 208 PB - Elsevier CY - Oxford 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 - TY - INPR A1 - Freundt, A. A1 - Halama, Ralf A1 - Suess, E. A1 - Voelker, D. T1 - Introduction to the special issue on SFB 574 "Volatiles and fluids in subduction zones: climate feedback and trigger mechanisms for natural disasters" T2 - International journal of earth sciences Y1 - 2014 U6 - https://doi.org/10.1007/s00531-014-1059-9 SN - 1437-3254 SN - 1437-3262 VL - 103 IS - 7 SP - 1729 EP - 1731 PB - Springer CY - New York ER - TY - JOUR A1 - Halama, Ralf A1 - Glodny, Johannes A1 - Konrad-Schmolke, Matthias A1 - Sudo, Masafumi T1 - 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) JF - Geosphere N2 - 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. Y1 - 2018 U6 - https://doi.org/10.1130/GES01521.1 SN - 1553-040X VL - 14 IS - 4 SP - 1425 EP - 1450 PB - American Institute of Physics CY - Boulder ER - TY - JOUR A1 - Halama, Ralf A1 - Konrad-Schmolke, Matthias T1 - Retrograde metasomatic effects on phase assemblages in an interlayered blueschist-greenschist sequence (Coastal Cordillera, Chile) JF - Lithos : an international journal of mineralogy, petrology, and geochemistry N2 - 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. KW - Fluid-rock interaction KW - Metasomatism KW - Element mobility KW - Pseudo-binary phase diagrams KW - Coastal Cordillera (Chile) Y1 - 2015 U6 - https://doi.org/10.1016/j.lithos.2014.12.004 SN - 0024-4937 SN - 1872-6143 VL - 216 SP - 31 EP - 47 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Konrad-Schmolke, Matthias A1 - Halama, Ralf A1 - Manea, Vlad C. T1 - Slab mantle dehydrates beneath KamchatkaYet recycles water into the deep mantle JF - Geochemistry, geophysics, geosystems N2 - 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. KW - rainfall-runoff KW - scaling KW - heterogeneity in soil hydraulic properties KW - surface sealing KW - run-on KW - patched vegetation cover Y1 - 2016 U6 - https://doi.org/10.1002/2016GC006335 SN - 1525-2027 VL - 17 SP - 2987 EP - 3007 PB - American Geophysical Union CY - Washington ER - TY - JOUR A1 - Freundt, A. A1 - Grevemeyer, I. A1 - Rabbel, W. A1 - Hansteen, T. H. A1 - Hensen, C. A1 - Wehrmann, H. A1 - Kutterolf, S. A1 - Halama, Ralf A1 - Frische, M. T1 - Volatile (H2O, CO2, Cl, S) budget of the Central American subduction zone JF - International journal of earth sciences N2 - After more than a decade of multidisciplinary studies of the Central American subduction zone mainly in the framework of two large research programmes, the US MARGINS program and the German Collaborative Research Center SFB 574, we here review and interpret the data pertinent to quantify the cycling of mineral-bound volatiles (H2O, CO2, Cl, S) through this subduction system. For input-flux calculations, we divide the Middle America Trench into four segments differing in convergence rate and slab lithological profiles, use the latest evidence for mantle serpentinization of the Cocos slab approaching the trench, and for the first time explicitly include subduction erosion of forearc basement. Resulting input fluxes are 40-62 (53) Tg/Ma/m H2O, 7.8-11.4 (9.3) Tg/Ma/m CO2, 1.3-1.9 (1.6) Tg/Ma/m Cl, and 1.3-2.1 (1.6) Tg/Ma/m S (bracketed are mean values for entire trench length). Output by cold seeps on the forearc amounts to 0.625-1.25 Tg/Ma/m H2O partly derived from the slab sediments as determined by geochemical analyses of fluids and carbonates. The major volatile output occurs at the Central American volcanic arc that is divided into ten arc segments by dextral strike-slip tectonics. Based on volcanic edifice and widespread tephra volumes as well as calculated parental magma masses needed to form observed evolved compositions, we determine long-term (10(5) years) average magma and K2O fluxes for each of the ten segments as 32-242 (106) Tg/Ma/m magma and 0.28-2.91 (1.38) Tg/Ma/m K2O (bracketed are mean values for entire Central American volcanic arc length). Volatile/K2O concentration ratios derived from melt inclusion analyses and petrologic modelling then allow to calculate volatile fluxes as 1.02-14.3 (6.2) Tg/Ma/m H2O, 0.02-0.45 (0.17) Tg/Ma/m CO2, and 0.07-0.34 (0.22) Tg/Ma/m Cl. The same approach yields long-term sulfur fluxes of 0.12-1.08 (0.54) Tg/Ma/m while present-day open-vent SO2-flux monitoring yields 0.06-2.37 (0.83) Tg/Ma/m S. Input-output comparisons show that the arc water fluxes only account for up to 40 % of the input even if we include an "invisible" plutonic component constrained by crustal growth. With 20-30 % of the H2O input transferred into the deeper mantle as suggested by petrologic modeling, there remains a deficiency of, say, 30-40 % in the water budget. At least some of this water is transferred into two upper-plate regions of low seismic velocity and electrical resistivity whose sizes vary along arc: one region widely envelopes the melt ascent paths from slab top to arc and the other extends obliquely from the slab below the forearc to below the arc. Whether these reservoirs are transient or steady remains unknown. KW - Subduction input KW - Forearc dewatering KW - Arc magmatism KW - Subduction fluids Y1 - 2014 U6 - https://doi.org/10.1007/s00531-014-1001-1 SN - 1437-3254 SN - 1437-3262 VL - 103 IS - 7 SP - 2101 EP - 2127 PB - Springer CY - New York ER -