Characterization of the sulphate mineral amarantite Fe3 2 3+ (SO4)O 7H2O using infrared, Raman spectroscopy and thermogravimetry

The mineral amarantite Fe23+(SO4)O∙7H2O has been studied using a combination of techniques including thermogravimetry, electron probe analyses and vibrational spectroscopy. Thermal analysis shows decomposition steps at 77.63, 192.2, 550 and 641.4°C. The Raman spectrum of amarantite is dominated by an intense band at 1017 cm-1 assigned to the SO42- ν1 symmetric stretching mode. Raman bands at 1039, 1054, 1098, 1131, 1195 and 1233 cm-1 are attributed to the SO42- ν3 antisymmetric stretching modes. Very intense Raman band is observed at 409 cm-1 with shoulder bands at 399, 451 and 491 cm-1 are assigned to the v2 bending modes. A series of low intensity Raman bands are found at 543, 602, 622 and 650 cm-1 are assigned to the v4 bending modes. A very sharp Raman band at 3529 cm-1 is assigned to the stretching vibration of OH units. A series of Raman bands observed at 3025, 3089, 3227, 3340, 3401 and 3480 cm-1 are assigned to water bands. Vibrational spectroscopy enables aspects of the molecular structure of the mineral amarantite to be ascertained.

Characterization of the sulphate mineral coquimbite, a secondary iron sulphate from Javier Ortega mine, Lucanas Province, Peru – Using infrared, Raman spectroscopy and thermogravimetry

The mineral coquimbite has been analysed using a range of techniques including SEM with EDX, thermal analytical techniques and Raman and infrared spectroscopy. The mineral originated from the Javier Ortega mine, Lucanas Province, Peru. The chemical formula was determined as ðFe3þ 1:37; Al0:63ÞP2:00ðSO4Þ3 9H2O. Thermal analysis showed a total mass loss of 73.4% on heating to 1000 C. A mass loss of 30.43% at 641.4 C is attributed to the loss of SO3. Observed Raman and infrared bands were assigned to the stretching and bending vibrations of sulphate tetrahedra, aluminium oxide/hydroxide octahedra, water molecules and hydroxyl ions. The Raman spectrum shows well resolved bands at 2994, 3176, 3327, 3422 and 3580 cm 1 attributed to water stretching vibrations. Vibrational spectroscopy combined with thermal analysis provides insight into the structure of coquimbite.

Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14•13H2O

Raman spectra of jáchymovite, (UO2)8(SO4)(OH)14•13H2O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO2)6(SO4)O2(OH)6(H2O)6] •6H2O. Bands related to the stretching and bending vibrations of (UO2)2+, (SO4)2-, (OH)- and water molecules were assigned. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Raman spectroscopy of stercorite H(NH4)Na(PO4)•4H2O – a cave mineral from Petrogale Cave, Madura, Eucla, Western Australia

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the mineral stercorite H(NH4)Na(PO4)·4H2O. The mineral stercorite originated from the Petrogale Cave, Madura, Eucla, Western Australia. This cave is one of many caves in the Nullarbor Plain in the South of Western Australia. These caves have been in existence for eons of time and have been dated at more than 550 million years old. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm−1 defines the presence of phosphate in the mineral. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm−1. Raman spectroscopy shows the mineral is based upon the phosphate anion and not the hydrogen phosphate anion. Raman and infrared bands are found and assigned to PO43−, H2O, OH and NH stretching vibrations. The detection of stercorite by Raman spectroscopy shows that the mineral can be readily determined; as such the application of a portable Raman spectrometer in a ‘cave’ situation enables the detection of minerals, some of which may remain to be identified.

Raman spectroscopy of synthetic CaHPO4•2H2O– and in comparison with the cave mineral brushite

The mineral brushite has been synthesised by mixing calcium ions and hydrogen phosphate anions to mimic the reactions in a Cave. The vibrational spectra of the synthesised brushite were compared with that of the natural Cave mineral. Bands attributable to the PO43- and HPO42- anions are observed. Brushite, both synthetic and natural, is characterised by an intense sharp band at 985 cm-1 with a shoulder at 1000 cm-1. Characteristic bending modes are observed in the 300 to 600 cm-1 region. The spectra of the synthesised brushite matches very well the spectrum of brushite from the Moorba Cave, Western Australia.

Vibrational spectroscopy of the phosphate mineral kovdorskite – Mg2PO4(OH)⋅3H2O

The mineral kovdorskite Mg2PO4(OH)�3H2O was studied by electron microscopy, thermal analysis and vibrational spectroscopy. A comparison of the vibrational spectroscopy of kovdorskite is made with other magnesium bearing phosphate minerals and compounds. Electron probe analysis proves the mineral is very pure. The Raman spectrum is characterized by a band at 965 cm�1 attributed to the PO3� 4 m1 symmetric stretching mode. Raman bands at 1057 and 1089 cm�1 are attributed to the PO3�4 m3 antisymmetric stretching modes. Raman bands at 412, 454 and 485 cm�1 are assigned to the PO3�4 m2 bending modes. Raman bands at 536, 546 and 574 cm�1 are assigned to the PO3�4 m4 bending modes. The Raman spectrum in the OH stretching region is dominated by a very sharp intense band at 3681 cm�1 assigned to the stretching vibration of OH units. Infrared bands observed at 2762, 2977, 3204, 3275 and 3394 cm�1 are attributed to water stretching bands. Vibrational spectroscopy shows that no carbonate bands are observed in the spectra; thus confirming the formula of the mineral as Mg2PO4(OH)�3H2O.

Vibrational spectroscopy of the phosphate mineral lazulite – (Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm-1 assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO2/4- units. Two Raman bands at 1102 and 1137 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm-1 are attributed to the m1 PO3/4- symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm-1 are assigned to the v3PO3/4- antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm-1 are assigned to the m4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm-1 are attributed to the m2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm-1 are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood.

Infrared and Raman spectroscopic characterization of the arsenate mineral ceruleite Cu2Al7(AsO4)4(OH)13⋅11.5(H2O)

The molecular structure of the arsenate mineral ceruleite has been assessed using a combination of Raman and infrared spectroscopy. The most intense band observed at 903 cm-1 is assigned to the (AsO4)3- symmetric stretching vibrational mode. The infrared spectrum shows intense bands at 787, 827 and 886 cm-1, ascribed to the triply degenerate m3 antisymmetric stretching vibration. Raman bands observed at 373, 400, 417 and 430 cm-1 are attributed to the m2 vibrational mode. Three broad bands for ceruleite found at 3056, 3198 and 3384 cm-1 are assigned to water OH stretching bands. By using a Libowitzky empirical equation, hydrogen bond distances of 2.65 and 2.75 Å are calculated. Vibrational spectra enable the molecular structure of the ceruleite mineral to be determined and whilst similarities exist in the spectral patterns with the roselite mineral group, sufficient differences exist to be able to determine the identification of the minerals.

Raman and infrared spectroscopic characterization of the phosphate mineral Lithiophilite—LiMnPO4

The metal lithium is very important in industry, including lithium batteries. An important source of lithium besides continental brines is granitic pegmatites as in Australia. Lithiophilite is a lithium and manganese phosphate with chemical formula LiMnPO4 and forms a solid solution with triphylite, its Fe analog, and belongs to the triphylite group that includes karenwebberite, natrophilite, and sicklerite. The mineral lithiophilite was characterized by chemical analysis and spectroscopic techniques. The chemical is: Li1.01(Mn0.60, Fe0.41, Mg0.01, Ca0.01)(PO4)0.99 and corresponds to an intermediate member of the triphylite-lithiophilite series, with predominance of the lithiophilite member. The mineral lithiophilite is readily characterized by Raman and infrared spectroscopy.

A Raman spectroscopic study of the arsenate mineral chenevixite Cu2Fe23+(AsO4)2(OH)4⋅H2O

We have studied the mineral chenevixite from Manto Cuba Mine, San Pedro de Cachiyuyo District, Inca de Oro, Chañaral Province, Atacama Region, Chile, using a combination of scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDX) and vibrational spectroscopy. Qualitative chemical analysis shows a homogeneous composition, with predominance of As, Fe, Al, Cu, Fe and Cu. Minor amounts of Si were also observed. Raman spectroscopy complimented with infrared spectroscopy has been used to assess the molecular structure of the arsenate minerals chenevixite. Characteristic Raman and infrared bands of the (AsO4)3− stretching and bending vibrations are identified and described. The observation of multiple bands in the (AsO4)3− bending region offers support for the loss of symmetry of the arsenate anion in the structure of chenevixite. Raman bands attributable to the OH stretching vibrations of water and hydroxyl units were analysed. Estimates of the hydrogen bond distances were made based upon the OH stretching wavenumbers.

Raman spectroscopy of the molybdate minerals chillagite (tungsteinian wulfenite-I4), stolzite, scheelite, wolframite and wulfenite

Raman spectra of chillagite, wulfenite, stolzite, scheelite and wolframite were obtained at 298 and 77 K using a Raman microprobe in combination with a thermal stage. Chillagite is a solid solution of wulfenite and stolzite. The spectra of these molybdate minerals are orientation dependent. The band at 695 cm-1 is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The bands at 790 and 881 cm-1 are associated with the antisymmetric and symmetric Ag modes of terminal WO2 whereas the origin of the 806 cm-1 band remains unclear. The 4(Eg) band was absent for scheelite. The bands at 353 and 401 cm-1 are assigned as either deformation modes or as r(Bg) and (Ag) modes of terminal WO2. The band at 462 cm-1 has an equivalent band in the infrared at 455 cm-1 assigned as as(Au) of the (W2O4)n chain. The band at 508 cm-1 is assigned as sym(Bg) of the (W2O4)n chain.

Raman spectroscopy of kaolinites using different excitation wavelengths

The Raman spectra of both low- and high-defect kaolinites in the hydroxyl stretching and low-wavenumber region were obtained with excitation at three visible wavelengths of 633, 514 and 442 nm and a UV wavelength of 325 nm. The UV-excited spectra were comparable to those excited by the visible wavelengths. The Raman spectra show hydroxyl stretching bands at 3621 cm-1 attributed to the inner hydroxyl, at 3692 and 3684 cm-1 attributed to the longitudinal and transverse optic modes of the inner surface hydroxyls and at 3668 and 3653 cm-1 assigned to the out-of phase vibrations of the inner surface hydroxyls. Two bands were observed in the spectral profile at 3695 cm-1 for the high-defect kaolinite at 3698 and 3691 cm-1 and were assigned to TO/LO splitting. An increase in relative intensity of the transverse optic mode is observed with decrease in laser wavelength. The intensity of the out-of-phase vibrations at 3668 and 3653 cm-1 of the inner surface hydroxyls shows a linear relationship with the longitudinal and transverse optic modes. In the low-wavenumber region excellent correlation was found between the experimentally determined and the calculated band positions.

Raman spectroscopy of the copper chloride minerals nantokite, eriochalcite and claringbullite - implications for copper corrosion

The application of Raman spectroscopy to the study of the copper chloride minerals nantokite, eriochalcite and claringbullite has enabled the vibrational modes for the CuCl, CuOH and CuOH2 to be determined. Nantokite is characterised by bands at 205 and 155 cm-1 attributed to the transverse and longitudinal optic vibrations. Nantokite also has an intense band at 463 cm-1, eriochalcite at 405 and 390 cm-1 and claringbullite at 511 cm-1. These bands are attributed to CuO stretching modes. Water librational bands at around 672 cm-1 for eriochalcite have been identified and hydroxyl deformation modes of claringbullite at 970, 906 and 815 cm-1 are observed. Spectra of the three minerals are so characteristically different that the minerals are readily identified by Raman spectroscopy. The minerals are often determined in copper corrosion products by X-ray diffraction. Raman spectroscopy offers a rapid, in-situ technique for the identification of these corrosion products.

Prehistoric hand stencils at Fern Cave, North Queensland (Australia): environmental and chronological implications of Raman spectroscopy and FT-IR imaging results

Raman spectroscopy and FT-IR imaging analyses of cave wall pigment samples from north Queensland (Australia) indicate that some hand stencils were undertaken during a dry environmental phase indicating late Holocene age. Other, earlier painting episodes also took place during dry environmental periods of the terminal Pleistocene and/or early Holocene. These results represent a rare opportunity to attain chronological information for rock art in conditions where insufficient carbon is present for radiocarbon dating.