Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods |
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| Authors: | M Koch-Müller I Abs-Wurmbach D Rhede V Kahlenberg S Matsyuk |
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| Institution: | (1) Department 4, Chemie der Erde, GeoForschungsZentrum Potsdam, Telegrafenberg, 14473 Potsdam, Germany;(2) Institute of Applied Geoscience, Technical University Berlin, 10623 Berlin, Germany;(3) Institute of Mineralogy and Petrography, University of Innsbruck, 6020 Innsbruck, Austria;(4) Institute of Geochemistry and Ore Formation, Ukrainian Academy of Science, Kiev, 22 142, Ukraine |
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| Abstract: | A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe2+ at M1 as well as at M2, and in a first approach assigned Fe3+ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε i,tot = 65,000 ± 3,000 lmolH2O ?1 cm?2. Using this new ε i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H2O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe3+ (<0.1 Fe3+ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al3+ at the tetrahedral site (OH bands around 3,525 cm?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe3+-rich sample (0.2 Fe3+ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm?1 plus shoulder at 3,450 cm?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe3+ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe2+ and combined with increase in Fe3+. That dehydration is correlated with oxidation of Fe2+ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH? content and giving no indication of Fe2+-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe2+ at M2 and low-water concentrations, i.e., at a ratio of Fe2+ M2/H > 10 dehydration occurs by iron oxidation of Fe2+ exclusively at the M2 site following the reaction: \( {\left {{\text{Fe}}^{{{\text{2 + M2]}}}}{\text{OH}}^{ - } } \right]} = {\left {{\text{Fe}}^{{{\text{3 + M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe2+ at M2 but high-water concentrations, i.e., ratio of Fe2+ M2/H < 5.0 dehydration occurs through oxidation of Fe2+ at M1. |
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| Keywords: | Natural omphacite OH incorporation Dehydration Infrared spectroscopy X-ray structure refinement M?ssbauer spectroscopy UV/VIS spectroscopy Secondary ion mass spectrometry IR absorption coefficient for water |
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