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Mass transfer and fluid evolution in late-metamorphic veins, Rhenish Massif (Germany): insight from alteration geochemistry and fluid-mineral equilibria modeling

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Abstract

Element mobility and fluid-rock interaction related to the formation of late-metamorphic quartz veins have been studied by combination of mineral chemistry, whole-rock geochemistry, mass balance analysis and fluid-mineral equilibria modeling. The quartz veins are hosted by very low-grade metasedimentary rocks of the fold-and-thrust belt of the Rhenish Massif (Germany). The veins record two stages of evolution, a massive vein filling assemblage with elongate-blocky quartz, chlorite, apatite and albite, and a later open space filling assemblage with euhedral crystals of quartz, ankerite-dolomite and minor calcite and sulfides. Detailed mass balance analysis of an alteration profile adjacent to a representative quartz vein demonstrates that element mobility is restricted to the proximal zone. The most important element changes are gain of Ca, Fe, Mg, Mn, P and CO2, and loss of Si, K and Na. The data demonstrate that wall-rock carbonation is one of the main alteration features, whereas mobility of Si, K and Na are related to dissolution of quartz and destruction of detrital feldspar and muscovite. The whole-rock geochemical data, in conjunction with fluid composition data and pressure-temperature estimates, were used as input for fluid-mineral equilibria modeling in the system Si-Al-Fe-Mg-Ca-Na-K-C-S-O-H-B-F-Cl. Modeling involved calculation of rock-buffered fluid compositions over the temperature interval 100–500 °C, and reaction-path simulations where a rock-buffered high-temperature fluid reacts with fresh host-rocks at temperatures of 400, 300 and 200 °C. Calculated rock-buffered fluid compositions demonstrate that retrograde silica solubility is a strong driving force for quartz leaching in the temperature-pressure window of 380–450 °C and 0.5 kbar. These conditions overlap with the estimated temperatures for the initial stage of vein formation. Reaction-path models show that high-temperature alteration can produce the observed silica leaching, suggesting that fast advection of external hot fluids from deeper crustal levels was essential for the early stage of vein formation. Fluid advection must have occurred as multiple pulses, which allowed for periods of influx of fluids that leached quartz, alternating with periods of cooling and quartz precipitation in the veins. Reaction-path models at high temperatures (300–400 °C) do not produce carbonate alteration, whereas fluid-rock reaction at 200 °C produces carbonate alteration, consistent with the temperature estimates for the late-stage vein carbonate assemblage. Comparison between modeling results and geochemical data suggests that the observed alteration features are the product of fluid-rock reaction under conditions where the external fluid gradually cooled down and evolved with time. The results of this study highlight the importance of late-orogenic fluid migration for the formation of quartz vein arrays in fold-and-thrust belts.

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Acknowledgments

This study was carried out within the framework of the DGMK (German Society for Petroleum and Coal Science and Technology) research project 718 (Mineral Vein Dynamics Modeling), which is funded by the companies ExxonMobil Production Deutschland GmbH, GDF SUEZ E&P Deutschland GmbH, RWE Dea AG and Wintershall Holding GmbH, within the basic research program of the WEG Wirtschaftsverband Erdöl- und Erdgasgewinnung e.V. We thank the companies for their financial support and their permission to publish our results. We thank Lydia Zehnder for help with the XRD and XRF measurements, and Markus Wälle for support during LA-ICPMS analysis. Dan Miron and Stephan Nagel are thanked for the assistance during the preparation of the illite and chlorite crystallinity samples, and the data processing. The authors sincerely thank Chris Heinrich for his outstanding support during this research. We thank an anonymous Mineralogy and Petrology reviewer for constructive comments that have helped to improve this paper.

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  1. ETH Zurich, Department of Earth Sciences, Institute of Geochemistry and Petrology, Clausiusstrasse 25, 8092, Zurich, Switzerland

    Achille Marsala

  2. Department of Geosciences and Geography, Division of Geology and Geochemistry, University of Helsinki, P.O.Box 64, Gustaf Hällströmin katu 2a, FI-00014, Helsinki, Finland

    Thomas Wagner

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Marsala, A., Wagner, T. Mass transfer and fluid evolution in late-metamorphic veins, Rhenish Massif (Germany): insight from alteration geochemistry and fluid-mineral equilibria modeling. Miner Petrol 110, 515–545 (2016). https://doi.org/10.1007/s00710-016-0424-8

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