S. V. Vyatkin, Yu. D. Gritsenko, L. P. Ogorodova, M. F. Vigasina, D. A. Ksenofontov, L. V. Melchakova
{"title":"沃隆伊冻土带(科拉半岛)和桑吉伦高原(图瓦)稀有金属伟晶岩中的安勃芒硝系列矿物的 EPR 光谱和量热研究","authors":"S. V. Vyatkin, Yu. D. Gritsenko, L. P. Ogorodova, M. F. Vigasina, D. A. Ksenofontov, L. V. Melchakova","doi":"10.1134/S0016702924700344","DOIUrl":null,"url":null,"abstract":"<p>The paper reports the first comprehensive physicochemical study of minerals of the amblygonite LiAlPO<sub>4</sub>F–montebrasite LiAlPO<sub>4</sub>(OH) series. An EPR spectroscopic and calorimetric study of montebrasite LiAlPO<sub>4</sub>(OH)<sub>0.9</sub>F<sub>0.1</sub> from the Shuk-Byul rare-metal granite pegmatites (Sangilen Highlands, Tuva) and amblygonite LiAlPO<sub>4</sub>F<sub>0.5</sub>(OH)<sub>0.5</sub> from pegmatites of the Voron’i Tundras (Kola Peninsula) was carried out. Using the EPR method, the radiation-sensitive paramagnetic O<sup>–</sup> centers were discovered. They were formed without participation of impurity elements in the regular sites of crystal lattice. The possibility use of minerals of the amblygonite–montebrasite series for EPR geochronometry has been demonstrated for the first time. Using the method of high-temperature melt dissolution calorimetry on a Tian-Calvét microcalorimeter, the enthalpies of formation from elements <span>\\({{\\Delta }_{f}}H_{{{\\text{el}}}}^{0}\\)</span> (298.15 K) = –2326.3 ± 2.2 kJ/mol for montebrasite with the composition LiAl(PO<sub>4</sub>)(OH)<sub>0.9</sub>F<sub>0.1</sub> and for amblygonite with the composition LiAl(PO<sub>4</sub>)F<sub>0.5</sub>(OH)<sub>0.5</sub> (‒2347.9 ± 3.1 kJ/mol) are obtained; and the values of this parameter are calculated for the end members with an ideal composition of the series: for montebrasite (–2315.5 ± 2.2 kJ/mol) and for amblygonite (–2401.6 ± 3.1 kJ/mol). The values of the standard entropy <i>S</i><sup>0</sup> (298.15 K) and the Gibbs energy of formation <span>\\({{\\Delta }_{f}}G_{{{\\text{el}}}}^{0}\\)</span> (298.15 K) for intermediate and end members of the amblygonite–montebrasite series are estimated.</p>","PeriodicalId":12781,"journal":{"name":"Geochemistry International","volume":"62 7","pages":"748 - 759"},"PeriodicalIF":0.7000,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"EPR Spectroscopic and Calorimetric Study of Minerals of the Amblygonite–Montebrasite Series from Rare-Metal Pegmatite of the Voron’i Tundras (Kola Peninsula) and Sangilen Highlands (Tuva)\",\"authors\":\"S. V. Vyatkin, Yu. D. Gritsenko, L. P. Ogorodova, M. F. Vigasina, D. A. Ksenofontov, L. V. Melchakova\",\"doi\":\"10.1134/S0016702924700344\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The paper reports the first comprehensive physicochemical study of minerals of the amblygonite LiAlPO<sub>4</sub>F–montebrasite LiAlPO<sub>4</sub>(OH) series. An EPR spectroscopic and calorimetric study of montebrasite LiAlPO<sub>4</sub>(OH)<sub>0.9</sub>F<sub>0.1</sub> from the Shuk-Byul rare-metal granite pegmatites (Sangilen Highlands, Tuva) and amblygonite LiAlPO<sub>4</sub>F<sub>0.5</sub>(OH)<sub>0.5</sub> from pegmatites of the Voron’i Tundras (Kola Peninsula) was carried out. Using the EPR method, the radiation-sensitive paramagnetic O<sup>–</sup> centers were discovered. They were formed without participation of impurity elements in the regular sites of crystal lattice. The possibility use of minerals of the amblygonite–montebrasite series for EPR geochronometry has been demonstrated for the first time. Using the method of high-temperature melt dissolution calorimetry on a Tian-Calvét microcalorimeter, the enthalpies of formation from elements <span>\\\\({{\\\\Delta }_{f}}H_{{{\\\\text{el}}}}^{0}\\\\)</span> (298.15 K) = –2326.3 ± 2.2 kJ/mol for montebrasite with the composition LiAl(PO<sub>4</sub>)(OH)<sub>0.9</sub>F<sub>0.1</sub> and for amblygonite with the composition LiAl(PO<sub>4</sub>)F<sub>0.5</sub>(OH)<sub>0.5</sub> (‒2347.9 ± 3.1 kJ/mol) are obtained; and the values of this parameter are calculated for the end members with an ideal composition of the series: for montebrasite (–2315.5 ± 2.2 kJ/mol) and for amblygonite (–2401.6 ± 3.1 kJ/mol). The values of the standard entropy <i>S</i><sup>0</sup> (298.15 K) and the Gibbs energy of formation <span>\\\\({{\\\\Delta }_{f}}G_{{{\\\\text{el}}}}^{0}\\\\)</span> (298.15 K) for intermediate and end members of the amblygonite–montebrasite series are estimated.</p>\",\"PeriodicalId\":12781,\"journal\":{\"name\":\"Geochemistry International\",\"volume\":\"62 7\",\"pages\":\"748 - 759\"},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2024-08-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Geochemistry International\",\"FirstCategoryId\":\"89\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S0016702924700344\",\"RegionNum\":4,\"RegionCategory\":\"地球科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"GEOCHEMISTRY & GEOPHYSICS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Geochemistry International","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1134/S0016702924700344","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"GEOCHEMISTRY & GEOPHYSICS","Score":null,"Total":0}
EPR Spectroscopic and Calorimetric Study of Minerals of the Amblygonite–Montebrasite Series from Rare-Metal Pegmatite of the Voron’i Tundras (Kola Peninsula) and Sangilen Highlands (Tuva)
The paper reports the first comprehensive physicochemical study of minerals of the amblygonite LiAlPO4F–montebrasite LiAlPO4(OH) series. An EPR spectroscopic and calorimetric study of montebrasite LiAlPO4(OH)0.9F0.1 from the Shuk-Byul rare-metal granite pegmatites (Sangilen Highlands, Tuva) and amblygonite LiAlPO4F0.5(OH)0.5 from pegmatites of the Voron’i Tundras (Kola Peninsula) was carried out. Using the EPR method, the radiation-sensitive paramagnetic O– centers were discovered. They were formed without participation of impurity elements in the regular sites of crystal lattice. The possibility use of minerals of the amblygonite–montebrasite series for EPR geochronometry has been demonstrated for the first time. Using the method of high-temperature melt dissolution calorimetry on a Tian-Calvét microcalorimeter, the enthalpies of formation from elements \({{\Delta }_{f}}H_{{{\text{el}}}}^{0}\) (298.15 K) = –2326.3 ± 2.2 kJ/mol for montebrasite with the composition LiAl(PO4)(OH)0.9F0.1 and for amblygonite with the composition LiAl(PO4)F0.5(OH)0.5 (‒2347.9 ± 3.1 kJ/mol) are obtained; and the values of this parameter are calculated for the end members with an ideal composition of the series: for montebrasite (–2315.5 ± 2.2 kJ/mol) and for amblygonite (–2401.6 ± 3.1 kJ/mol). The values of the standard entropy S0 (298.15 K) and the Gibbs energy of formation \({{\Delta }_{f}}G_{{{\text{el}}}}^{0}\) (298.15 K) for intermediate and end members of the amblygonite–montebrasite series are estimated.
期刊介绍:
Geochemistry International is a peer reviewed journal that publishes articles on cosmochemistry; geochemistry of magmatic, metamorphic, hydrothermal, and sedimentary processes; isotope geochemistry; organic geochemistry; applied geochemistry; and chemistry of the environment. Geochemistry International provides readers with a unique opportunity to refine their understanding of the geology of the vast territory of the Eurasian continent. The journal welcomes manuscripts from all countries in the English or Russian language.