OH defects in quartz in granitic systems doped with spodumene, tourmaline and/or apatite: experimental investigations at 5–20 kbar

Frigo, Corinne; Stalder, Roland; Hauzenberger, Christoph

doi:10.1007/s00269-016-0828-3

Cited by 26 publications

(55 citation statements)

References 23 publications

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“…Müller et al [26] have already shown that igneous quartz preferentially incorporates H + as a charge-balancing cation in lieu of Li, K and Na. Similar findings have been made more recently for pegmatite quartz [27,28].…”

Section: Trace Element Incorporation Into Quartzsupporting

confidence: 90%

Trace Element Compositions and Defect Structures of High-Purity Quartz from the Southern Ural Region, Russia

et al. 2017

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Abstract:Quartz samples of different origin from 10 localities in the Southern Ural region, Russia have been investigated to characterize their trace element compositions and defect structures. The analytical combination of cathodoluminescence (CL) microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and trace-element analysis by inductively coupled plasma mass spectrometry (ICP-MS) revealed that almost all investigated quartz samples showed very low concentrations of trace elements (cumulative concentrations of <50 ppm with <30 ppm Al and <10 ppm Ti) and low abundances of paramagnetic defects, defining them economically as "high-purity" quartz (HPQ) suitable for high-tech applications. EPR and CL data confirmed the low abundances of substitutional Ti and Fe, and showed Al to be the only significant trace element structurally bound in the investigated quartz samples. CL microscopy revealed a heterogeneous distribution of luminescence centres (i.e., luminescence active trace elements such as Al) as well as features of deformation and recrystallization. It is suggested that healing of defects due to deformation-related recrystallization and reorganization processes of the quartz lattice during retrograde metamorphism resulted in low concentrations of CL activator and other trace elements or vacancies, and thus are the main driving processes for the formation of HPQ deposits in the investigated area.

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Section: Trace Element Incorporation Into Quartzsupporting

confidence: 90%

Trace Element Compositions and Defect Structures of High-Purity Quartz from the Southern Ural Region, Russia

et al. 2017

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“…Al concentrations in coesite and stishovite are in all cases about two orders of magnitude higher than H concentrations (Fig. 9), as already observed for quartz synthesized from the same starting material (Frigo et al 2016).…”

Section: Mechanism Of Trace Elements Incorporationsupporting

confidence: 60%

“…Similarly to quartz, trace elements may be incorporated by coupled substitutions of Si 4+ by one trivalent (M 3+ ) and one monovalent (M + ) cation Frigo et al 2016). In fact, concentrations of M 3+ (i.e.…”

Section: Mechanism Of Trace Elements Incorporationmentioning

confidence: 99%

“…The experimental condition chosen here is based on natural examples such as the Dora Maira (Chopin 2003) and the Kokchetav (Zhang et al 1997) massifs. Finally, the results from the present study are compared to the defect inventory of quartz synthesized previously from the same starting material (Frigo et al 2016), to evaluate the potential of silica polymorphs as carrier for light elements (H, B, and Li) to the Earth's interior.…”

Section: Introductionmentioning

confidence: 99%

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OH defects in coesite and stishovite during ultrahigh-pressure metamorphism of continental crust

2018

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The high-pressure silica polymorphs coesite and stishovite were synthesized under water-saturated conditions from a natural granitic composition doped with Li and B. Experiments were performed in a Multi-Anvil apparatus between 4 and 9.1 GPa and 900 and 950 °C, based on the conditions of a subducting continental crust as realistic for the ultrahigh-pressure metamorphic units Dora Maira and Kochetav massifs. Run products consisted of coesite/stishovite + kyanite ± phengite ± omphacite, and quench material. The synthesized silica polymorphs were successively analyzed by infrared spectroscopy, electron microprobe, and Secondary-Ion Mass Spectrometry (SIMS). No hydrous defects were observed in coesite synthesized at 4 GPa and 900 °C, whereas coesite grown at higher pressures revealed a triplet of infrared absorptions bands at 3575, 3523, and 3459 cm − 1 , two minor bands at 3535 and 3502 cm − 1 , and a small band at 3300 cm − 1 that was only visible at 7.7 GPa. The total amount of Al was charge-balanced by H and the other monovalent cations. However, the band triplet could not be associated with AlOH defects, while the band doublet was inferred to BOH defects and the small band probably corresponded to interstitial H. Stishovite displayed one dominant band at 3116 cm − 1 with a shoulder at 3170 cm − 1 , and a minor band at 2665 cm − 1 , probably all associated with AlOH defects. BOH defects were not observed in stishovite, and LiOH defects were neither observed in coesite nor stishovite, probably because of preferentially partition of Li in other phases such as omphacite. The total amount of defect protons increased with pressure and with metal impurity concentrations. The general increase in OH defects in silica polymorphs with increasing pressure (this study) contrasted the negative pressure trend of OH in quartz observed previously from the same starting material, and revealed an incorporation minimum of OH in silica polymorphs around the quartz/coesite phase transition.

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“…Many calibrations have been proposed to determine the water content in quartz using IR spectroscopy (Kats 1962;Paterson 1982;Aines et al 1984;Nakashima et al 1995;Libowitzky and Rossman 1997;Stipp et al 2006;Thomas et al 2009), and they have been discussed recently in connection with studies concerning the crystallographic orientations of quartz and the orientations of irradiated polarized IR light (e.g., Stalder and Konzett 2012;Baron et al 2015;Frigo et al 2016). The calibrations of Paterson (1982) and Libowitzky and Rossman (1997) do not require information on the mineral species, and they assume that the absorption coefficients increase linearly with wave number.…”

Section: Differences Among the Ir Calibrationsmentioning

confidence: 99%

Water distribution in quartz schists of the Sanbagawa Metamorphic Belt, Japan: infrared spectroscopic mapping and comparison of the calibrations proposed for determining water contents

Fukuda

Shimizu

2019

Earth Planets Space

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We evaluated water distributions in deformed quartz in schists along the Asemi River, Central Shikoku, in the Sanbagawa Metamorphic Belt, Japan, using infrared spectroscopic (IR) mapping. The water trapped in quartz as molecular H 2 O showed a broad IR absorption band at 2800-3750 cm −1. A necessary step before assessing the quartz water content was to evaluate and compare six previously proposed IR calibrations in terms of the molar absorption coefficients of H 2 O (L/mol H 2 O cm 2). The coefficients vary from 24,100 to 89,000 L/mol H 2 O cm 2 , and the values of the coefficients show a rough increase with increasing component of structural-OH in the IR spectra. We used Paterson's calibration, which does not require input regarding the mineral species, but which was modified in his paper for measurements of molecular H 2 O in quartz. The absorption coefficient is 38,000 L/mol H 2 O cm 2. IR mapping was performed on Sanbagawa metamorphic rocks with increasing grades of metamorphism, where the mean grain size of quartz increases from ~ 40 to ~ 120 µm. The absorption bands that are only from the quartz can be distinguished on the basis of microstructural observations and the corresponding mapping results. The IR spectra of quartz commonly show dominant molecular H 2 O bands at 2800-3750 cm −1 with no additional bands associated with crystalline-OH when only quartz is measured. The water contents of quartz in all our samples were 40-310 ppm, and these values are about one-third of previously reported values measured using point analyses with the unified Paterson's calibration. This difference seems to reflect the incorporation of phyllosilicates in previous measurements that showed a broad band around 3600 cm −1. The lowest and highest water contents in our quartz samples are associated with intragranular water and grain boundary water, respectively. We estimated the grain boundary widths to be at most ~ 10 nm on the basis of the water contents at grain boundaries.

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OH defects in quartz in granitic systems doped with spodumene, tourmaline and/or apatite: experimental investigations at 5–20 kbar

Abstract: detectable only in quartz crystals grown from middle and upper crustal sections (such as hydrothermal quartz) and not in quartz from deep roots of orogenic granitoids.

Cited by 26 publications

References 23 publications

Trace Element Compositions and Defect Structures of High-Purity Quartz from the Southern Ural Region, Russia

Trace Element Compositions and Defect Structures of High-Purity Quartz from the Southern Ural Region, Russia

OH defects in coesite and stishovite during ultrahigh-pressure metamorphism of continental crust

Water distribution in quartz schists of the Sanbagawa Metamorphic Belt, Japan: infrared spectroscopic mapping and comparison of the calibrations proposed for determining water contents

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