{"title":"Oxidation processes and thermal stability of actinolite","authors":"Constanze Rösche, Naemi Waeselmann, Nadia Petrova, Thomas Malcherek, Jochen Schlüter, Boriana Mihailova","doi":"10.1007/s00269-022-01223-4","DOIUrl":null,"url":null,"abstract":"<div><p>Understanding the thermal behaviour of iron-containing amphiboles (AB<sub>2</sub>C<sub>5</sub>T<sub>8</sub>O<sub>22</sub>W<sub>2</sub>, C<sub>5</sub> = <i>M</i>(1)<sub>2</sub><i> M</i>(2)<sub>2</sub><i> M</i>(3)) at atomic-level scale may have important implications in several fields, including metamorphic petrology, geophysics, and environmental sciences. Here, the thermally induced oxidation and decomposition of actinolite are studied by in situ high-temperature Raman spectroscopy and complementary thermogravimetric/mass-spectrometry analyses as well as X-ray diffraction of the products of amphibole decomposition. The effect of <sup>C</sup>Fe<sup>2+</sup> on dehydrogenation/dehydroxylation is followed by comparing the results on actinolite with those for tremolite. We show that mobile charge carriers, namely polarons (conduction electrons coupled to FeO<sub>6</sub> phonons) and H<sup>+</sup> cations, exist in actinolite at elevated temperatures ~ 1150–1250 K. The temperature-induced actinolite breakdown is a multistep process, involving (i) delocalization of <i>e</i><sup>−</sup> from <sup>C</sup>Fe<sup>2+</sup> as well as of H<sup>+</sup> from hydroxyl groups shared by Fe-containing <i>M</i>(1)<i>M</i>(1)<i>M</i>(3) species, which, however, remain in the crystal bulk; (ii) dehydrogenation and ejection of <i>e</i><sup>−</sup> between 1250 and 1350 K, where actinolite can be considered as “oxo-actinolite”, as H<sup>+</sup> also from hydroxyl groups next to <sup><i>M</i>(1,3)</sup>(MgMgMg) configurations become delocalized and mostly remain in the crystal bulk; (iii) complete dehydroxylation and consequent structure collapse above 1350 K, forming an Fe<sup>3+</sup>-bearing defect-rich augitic pyroxene. The dehydrogenation of tremolite occurs at 1400 K, triggering immediately a disintegration of the silicate double-chain into single SiO<sub>4</sub>-chains and followed by a rearrangement of the amphibole octahedral strips and <sup>B</sup>Ca<sup>2+</sup> cations into pyroxene-type octahedral sheets at 1450 K. The result of tremolite decomposition is also a single-phase defect-rich clinopyroxene with an intermediate composition on the diopside–clinoenstatite join.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2022-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-022-01223-4.pdf","citationCount":"3","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physics and Chemistry of Minerals","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1007/s00269-022-01223-4","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 3
Abstract
Understanding the thermal behaviour of iron-containing amphiboles (AB2C5T8O22W2, C5 = M(1)2 M(2)2 M(3)) at atomic-level scale may have important implications in several fields, including metamorphic petrology, geophysics, and environmental sciences. Here, the thermally induced oxidation and decomposition of actinolite are studied by in situ high-temperature Raman spectroscopy and complementary thermogravimetric/mass-spectrometry analyses as well as X-ray diffraction of the products of amphibole decomposition. The effect of CFe2+ on dehydrogenation/dehydroxylation is followed by comparing the results on actinolite with those for tremolite. We show that mobile charge carriers, namely polarons (conduction electrons coupled to FeO6 phonons) and H+ cations, exist in actinolite at elevated temperatures ~ 1150–1250 K. The temperature-induced actinolite breakdown is a multistep process, involving (i) delocalization of e− from CFe2+ as well as of H+ from hydroxyl groups shared by Fe-containing M(1)M(1)M(3) species, which, however, remain in the crystal bulk; (ii) dehydrogenation and ejection of e− between 1250 and 1350 K, where actinolite can be considered as “oxo-actinolite”, as H+ also from hydroxyl groups next to M(1,3)(MgMgMg) configurations become delocalized and mostly remain in the crystal bulk; (iii) complete dehydroxylation and consequent structure collapse above 1350 K, forming an Fe3+-bearing defect-rich augitic pyroxene. The dehydrogenation of tremolite occurs at 1400 K, triggering immediately a disintegration of the silicate double-chain into single SiO4-chains and followed by a rearrangement of the amphibole octahedral strips and BCa2+ cations into pyroxene-type octahedral sheets at 1450 K. The result of tremolite decomposition is also a single-phase defect-rich clinopyroxene with an intermediate composition on the diopside–clinoenstatite join.
期刊介绍:
Physics and Chemistry of Minerals is an international journal devoted to publishing articles and short communications of physical or chemical studies on minerals or solids related to minerals. The aim of the journal is to support competent interdisciplinary work in mineralogy and physics or chemistry. Particular emphasis is placed on applications of modern techniques or new theories and models to interpret atomic structures and physical or chemical properties of minerals. Some subjects of interest are:
-Relationships between atomic structure and crystalline state (structures of various states, crystal energies, crystal growth, thermodynamic studies, phase transformations, solid solution, exsolution phenomena, etc.)
-General solid state spectroscopy (ultraviolet, visible, infrared, Raman, ESCA, luminescence, X-ray, electron paramagnetic resonance, nuclear magnetic resonance, gamma ray resonance, etc.)
-Experimental and theoretical analysis of chemical bonding in minerals (application of crystal field, molecular orbital, band theories, etc.)
-Physical properties (magnetic, mechanical, electric, optical, thermodynamic, etc.)
-Relations between thermal expansion, compressibility, elastic constants, and fundamental properties of atomic structure, particularly as applied to geophysical problems
-Electron microscopy in support of physical and chemical studies
-Computational methods in the study of the structure and properties of minerals
-Mineral surfaces (experimental methods, structure and properties)