Raman spectroscopic study of the hydroxy-phosphate mineral plumbogummite PbAl3(PO4)2(OH,H2O)6

Plumbogummite PbAl3(PO4)2(OH,H2O)6 is a mineral of environmental significance and is a member of the alunite-jarosite supergroup. The molecular structure of the mineral has been investigated by Raman spectroscopy. The spectra of different plumbogummite specimens differ although there are many common features. The Raman spectra prove the spectral profile consisting of overlapping bands and shoulders. Raman bands and shoulders observed at 971, 980, 1002 and 1023 cm−1 (China sample) and 913, 981, 996 and 1026 cm−1 (Czech sample) are assigned to the ν1 symmetric stretching modes of the (PO4)3−, at 1002 and 1023 cm−1 (China) and 996 and 1026 cm−1 to the ν1 symmetric stretching vibrations of the (O3POH)2− units, and those at 1057, 1106 and 1182 (China) and at 1102, 1104 and 1179 cm−1 (Czech) to the ν3 (PO4)3− and ν3 (PO3) antisymmetric stretching vibrations. Raman bands and shoulders at 634, 613 and 579 cm−1 (China) and 611 and 596 cm−1 (Czech) are attributed to the ν4 (δ) (PO4)3− bending vibrations and those at 507, 494 and 464 cm−1 (China) and 505 and 464 cm−1 (Czech) to the ν2 (δ) (PO4)3− bending vibrations. The Raman spectrum of the OH stretching region is complex. Raman bands and shoulders are identified at 2824, 3121, 3249, 3372, 3479 and 3602 cm−1 for plumbogummite from China, and at 3077, 3227, 3362, 3480, 3518 and 3601 cm−1 for the Czech Republic sample. These bands are assigned to the ν OH stretching modes of water molecules and hydrogen ions. Approximate O–H⋯O hydrogen bond lengths inferred from the Raman spectra vary in the range >3.2–2.62 Å (China) and >3.2–2.67 Å (Czech). The minority presence of some carbonate ions in the plumbogummite (China sample) is connected with distinctive intensity increasing of the Raman band at 1106 cm−1, in which may participate the ν1 (CO3)2− symmetric stretching vibration overlapped with phosphate stretching vibrations.

Raman spectroscopic study of the mineral arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6

Arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6 belongs to the crandallite mineral subgroup of the alunite supergroup. Arsenogorceixite forms a continuous series of solid solutions with related minerals including gorceixite, goyazite, arsenogoyazite, plumbogummite and philipsbornite. Two minerals from (a) Germany and (b) from Ashburton Downs, Australia were analysed by Raman spectroscopy. The spectra show some commonality but the intensities of the peaks vary. Sharp intense Raman bands for the German sample, are observed at 972 and 814 cm−1 attributed to the ν1 PO43− and AsO43− symmetric stretching modes. Raman bands at 1014, 1057, 1148 and 1160 cm−1 are attributed to the ν1 PO2 symmetric stretching mode and ν3 PO43− antisymmetric stretching vibrations. Raman bands at 764 and 776 cm−1 and 758 and 756 cm−1 are assigned to the ν3 AsO43− antisymmetric stretching vibrations. For the Australian mineral, the ν1 PO43− band is found at 973 cm−1. The intensity of the arsenate bands observed at 814, 838 and 870 cm−1 is greatly enhanced. Two low intensity Raman bands at 1307 and 1332 cm−1 are assigned to hydroxyl deformation modes. The intense Raman band at 441 cm−1 with a shoulder at 462 cm−1 is assigned to the ν2 PO43− bending mode. Raman bands at 318 and 340 cm−1 are attributed to the (AsO4)3−ν2 bending. The broad band centred at 3301 cm−1 is assigned to water stretching vibrations and the sharper peak at 3473 cm−1 is assigned to the OH stretching vibrations. The observation of strong water stretching vibrations brings into question the actual formula of arsenogorceixite. It is proposed the formula is better written as BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6·xH2O. The observation of both phosphate and arsenate bands provides a clear example of solid solution formation.