Molecular and structural investigation of yukonite (synthetic & natural) and its relation to arseniosiderite

作者:Gomez M A*; Becze L; Blyth R I R; Cutler J N; Demopoulos G P
来源:Geochimica et Cosmochimica Acta, 2010, 74(20): 5835-5851.
DOI:10.1016/j.gca.2010.07.023

摘要

This paper describes the first synthesis method of yukonite, its thorough molecular and structural analysis along with natural specimens originating from Tagish Lake (Canada) and Grotta della Monaca (Italy) for comparison, and its structural relation to arseniosiderite. The synthetic and natural yukonites were found to have a range of composition according to the general formula Ca(2)Fe(3-5)(AsO(4))(3)(OH)(4-10)center dot xH(2)O where x = 2-11. The synthetic yukonite was found to be equivalent at the atomic, molecular and structural level to the Tagish Lake yukonite. At the molecular level, arseniosiderite, via vibrational spectroscopy, was found to have a H-bonding system as in scorodite and exhibit an extra arsenate mode indicative of HAsO(4)(2-) groups. Heating experiments along with ATR-IR analysis indicated the presence of structural water and hydroxyl units in arseniosiderite. In yukonite in contrast, a wide diffuse H-bonding environment was observed with only arsenate groups. The presence of both structural water and hydroxyl groups was further verified via ATR-IR spectroscopy. The As K, Fe 2p and Ca 2p XANES spectra of yukonite and arseniosiderite were found to be identical, confirming that the local nature of the As, Fe and Ca atoms in these structures is the same. Diffraction analysis (X-ray and electron) showed that yukonite consist of nano-crystalline domains while in the case of arseniosiderite micro-size single crystal domains exist.

  • 出版日期2010-10-15