Infrared and Raman spectroscopic characterization of the carbonate mineral huanghoite - and in comparison with selected rare earth carbonates

Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral huanghoite with possible formula given as BaCe(CO3)2F and compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of huanghoite displays three bands are at 1072, 1084 and 1091 cm−1 attributed to the symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 cm−1. No Raman bands of huanghoite were observed in these positions. Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm−1 assigned to the ν3 (CO3)2− antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands for huanghoite are observed at 687, 704, 718 and 730 cm−1and assigned to the (CO3)2− ν2 bending modes. Raman bands are observed for huanghoite at around 627 cm−1 and are assigned to the (CO3)2− ν4 bending modes. Raman bands are observed for the carbonate ν4 in phase bending modes at 722 cm−1 for bastnasite, 736 and 684 cm−1 for parisite, 714 cm−1 for northupite. Raman bands for huanghoite observed at 3259, 3484 and 3589 cm−1 are attributed to water stretching bands. Multiple bands are observed in the OH stretching region for bastnasite and parisite indicating the presence of water and OH units in their mineral structure. Vibrational spectroscopy enables new information on the structure of huanghoite to be assessed.

Vibrational spectroscopy of the borate mineral pinnoite MgB2O(OH)6

There is a large number of boron containing minerals with water and/or hydroxyl units of which pinnoite MgB2O(OH)6 is one. Some discussion about the molecular structure of pinnoite exists in the literature. Whether water is involved in the structure is ill-determined. The molecular structure of pinnoite has been assessed by the combination of Raman and infrared spectroscopy. The Raman spectrum is characterized by an intense band at 900 cm−1 assigned to the BO stretching vibrational mode. A series of bands in the 1000–1320 cm−1 spectral range are attributed to BO antisymmetric stretching modes and in-plane bending modes. The infrared spectrum shows complexity in this spectral range. Multiple Raman OH stretching vibrations are found at 3179, 3399, 3554 and 3579 cm−1. The infrared spectrum shows a series of overlapping bands with bands identified at 3123, 3202, 3299, 3414, 3513 and 3594 cm−1. By using a Libowitzky type function, hydrogen bond distances were calculated. Two types of hydrogen bonds were identified based upon the hydrogen bond distance. It is important to understand the structure of pinnoite in order to form nanomaterials based upon the pinnoite structure.

Vibrational spectroscopic study of the uranyl selenite mineral derriksite Cu4UO2(SeO3)2(OH)6⋅H2O

Raman spectrum of the mineral derriksite Cu4UO2(SeO3)2(OH)6⋅H2O was studied and complemented by the infrared spectrum of this mineral. Both spectra were interpreted and partly compared with the spectra of demesmaekerite, marthozite, larisaite, haynesite and piretite. Observed Raman and infrared bands were attributed to the (UO2)2+, (SeO3)2−, (OH)− and H2O vibrations. The presence of symmetrically distinct hydrogen bonded molecule of water of crystallization and hydrogen bonded symmetrically distinct hydroxyl ions was inferred from the spectra in the derriksite unit cell. Approximate U–O bond lengths in uranyl and O–H⋯O hydrogen bond lengths were calculated from the Raman and infrared spectra of derriksite.

Assessment of the molecular structure of natrodufrénite – NaFe2+Fe3+5(PO4)4(OH)6•2(H2O), a secondary pegmatite phosphate mineral from Minas Gerais, Brazil

The mineral natrodufrénite a secondary pegmatite phosphate mineral from Minas Gerais, Brazil, has been studied by a combination of scanning electron microscopy and vibrational spectroscopic techniques. Electron probe analysis shows the formula of the studied mineral as (Na0.88Ca0.12)∑1.00(Mn0.11Mg0.08Ca0.04Zr0.01Cu0.01)∑0.97(Al0.02)∑4.91(PO4)3.96(OH6.15F0.07)6.22⋅2.05(H2O). Raman spectroscopy identifies an intense peak at 1003 cm−1 assigned to the ν1 symmetric stretching mode. Raman bands are observed at 1059 and 1118 cm−1 and are attributed to the ν3 antisymmetric stretching vibrations. A comparison is made with the spectral data of other hydrate hydroxy phosphate minerals including cyrilovite and wardite. Raman bands at 560, 582, 619 and 668 cm−1 are assigned to the ν4 bending modes and Raman bands at 425, 444, 477 and 507 cm−1 are due to the ν2 bending modes. Raman bands in the 2600–3800 cm−1 spectral range are attributed to water and OH stretching vibrations. Vibrational spectroscopy enables aspects of the molecular structure of natrodufrénite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral barbosalite Fe2+Fe3+2(PO4)2(OH)2 : implications for the molecular structure

Natural single-crystal specimens of barbosalite from Brazil, with general formula Fe2+Fe3+ 2 (PO4)2(OH)2 were investigated by Raman and infrared spectroscopy. The mineral occurs as secondary products in granitic pegmatites. The Raman spectrum of barbosalite is characterized by bands at 1020, 1033 and 1044 cm−1 cm−1, assigned to ν1 symmetric stretching mode of the HOPO3- 3 and PO3- 4 units. Raman bands at around 1067, 1083 and 1138 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 575, 589 and 606 cm−1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. Raman bands at 439, 461, 475 and 503 cm−1 are attributed to the ν2 PO4 and H2PO4 bending modes. Strong Raman bands observed at 312, 346 cm−1 with shoulder bands at 361, 381 and 398 cm−1 are assigned to FeO stretching vibrations. No bands which are attributable to water vibrations were found. Vibrational spectroscopy enables aspects of the molecular structure of barbosalite to be assessed.

The molecular structure of the borate mineral inderite Mg(H4B3O7)(OH)⋅5H2O – A vibrational spectroscopic study

We have undertaken a study of the mineral inderite Mg(H4B3O7)(OH)⋅5H2O a hydrated hydroxy borate mineral of magnesium using scanning electron microscopy, thermogravimetry and vibrational spectroscopic techniques. The structure consists of [B3O3(OH)5]2-[B3O3(OH)5]2- soroborate groups and Mg(OH)2(H2O)4 octahedra interconnected into discrete molecules by the sharing of two OH groups. Thermogravimetry shows a mass loss of 47.2% at 137.5 °C, proving the mineral is thermally unstable. Raman bands at 954, 1047 and 1116 cm−1 are assigned to the trigonal symmetric stretching mode. The two bands at 880 and 916 cm−1 are attributed to the symmetric stretching mode of the tetrahedral boron. Both the Raman and infrared spectra of inderite show complexity. Raman bands are observed at 3052, 3233, 3330, 3392 attributed to water stretching vibrations and 3459 cm−1 with sharper bands at 3459, 3530 and 3562 cm−1 assigned to OH stretching vibrations. Vibrational spectroscopy is used to assess the molecular structure of inderite.

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, infrared and near-infrared spectroscopic characterization of the herderite-hydroxylherderite mineral series

Natural single-crystal specimens of the herderite-hydroxylherderite series from Brazil, with general formula CaBePO4(F,OH), were investigated by electron microprobe, Raman, infrared and near-infrared spectroscopies. The minerals occur as secondary products in granitic pegmatites. Herderite and hydroxylherderite minerals show extensive solid solution formation. The Raman spectra of hydroxylherderite are characterized by bands at around 985 and 998 cm-1, assigned to ν1 symmetric stretching mode of the HOPO33- and PO43- units. Raman bands at around 1085, 1128 and 1138 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 563, 568, 577, 598, 616 and 633 cm-1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The OH Raman stretching vibrations of hydroxylherderite were observed ranging from 3626 cm-1 to 3609 cm-1. The infrared stretching vibrations of hydroxylherderites were observed between 3606 cm-1 and 3599 cm-1. By using a Libowitzky type function, hydrogen bond distances based upon the OH stretching bands were calculated. Characteristic NIR bands at around 6961 and 7054 cm-1 were assigned to the first overtone of the fundamental, whilst NIR bands at 10194 and 10329 cm-1 are assigned to the second overtone of the fundamental OH stretching vibration. Insight into the structure of the herderite-hydroxylherderite series is assessed by vibrational spectroscopy.

The spectroscopic characterization of the sulphate mineral ettringite from Kuruman manganese deposits, South Africa

The mineral ettringite has been studied using a number of techniques, including XRD, SEM with EDX, thermogravimetry and vibrational spectroscopy. The mineral proved to be composed of 53% of ettringite and 47% of thaumasite in a solid solution. Thermogravimetry shows a mass loss of 46.2% up to 1000 °C. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1072 cm−1 attributed to a carbonate symmetric stretching mode, confirming the presence of thaumasite. The observation of multiple bands in the ν4 spectral region between 700 and 550 cm−1 offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3629 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3487 cm−1 to water stretching bands. Vibrational spectroscopy enables an assessment of the molecular structure of natural ettringite to be made.

Structural characterization and vibrational spectroscopy of the arsenate mineral wendwilsonite

In this paper, we have investigated on the natural wendwilsonite mineral with the formulae Ca2(Mg,Co)(AsO4)2⋅2(H2O). Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the wendwilsonite arsenate mineral. A comparison is made with the roselite mineral group with formula Ca2B(AsO4)2⋅2H2O (where B may be Co, Fe2+, Mg, Mn, Ni, Zn). The Raman spectra of the arsenate related to tetrahedral arsenate clusters with stretching region shows strong differences between that of wendwilsonite and the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. The Raman arsenate (AsO4)3− stretching region shows strong differences between that of wendwilsonite and the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists of multiple to tetrahedral (AsO4)3− clusters with antisymmetric stretching vibrations observed indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 450 cm−1 are assigned to ν4 bending modes. Multiple bands in the 350–300 cm−1 region assigned to ν2 bending modes provide evidence of symmetry reduction of the arsenate anion. Three broad bands for wendwilsonite found at 3332, 3119 and 3001 cm−1 are assigned to OH stretching bands. By using a Libowitzky empirical equation, hydrogen bond distances of 2.65 and 2.75 Å are estimated. Vibrational spectra enable the molecular structure of the wendwilsonite 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.

Vibrational spectroscopy of the silicate mineral plumbotsumite Pb5(OH)10Si4O8 : an assessment of the molecular structure

We have used scanning electron microscopy with energy dispersive X-ray analysis to determine the precise formula of plumbotsumite, a rare lead silicate mineral of formula Pb5(OH)10Si4O8. This study forms the first systematic study of plumbotsumite from the Bigadic deposits, Turkey. Vibrational spectroscopy was used to assess the molecular structure of plumbotsumite as the structure is not known. The mineral is characterized by sharp Raman bands at 1047, 1055 and 1060 cm−1 assigned to SiO stretching vibrational modes and sharp Raman bands at 673, 683 and 697 cm−1 assigned to OSiO bending modes. The observation of multiple bands offers support for a layered structure with variable SiO3 structural units. Little information may be obtained from the infrared spectra because of broad spectral profiles. Intense Raman bands at 3510, 3546 and 3620 cm−1 are ascribed to OH stretching modes. Evidence for the presence of water in the plumbotsumite structure was inferred from the infrared spectra.

Vibrational spectroscopy of the borate mineral gaudefroyite Ca4Mn3+3-x(BO3)3(CO3)(O,OH) from N’Chwaning II mine, Kalahari, Republic of South Africa

Gaudefroyite Ca4Mn3+3-x(BO3)3(CO3)(O,OH)3 is an unusual mineral containing both borate and carbonate groups and is found in the oxidation zones of manganese minerals, and it is black in color. Vibrational spectroscopy has been used to explore the molecular structure of gaudefroyite. Gaudefroyite crystals are short dipyramidal or prismatic with prominent pyramidal terminations, to 5 cm. Two very sharp Raman bands at 927 and 1076 cm-1are assigned to trigonal borate and carbonate respectively. Broad Raman bands at 1194, 1219 and 1281 cm-1 are attributed to BOH in-plane bending modes. Raman bands at 649 and 670 cm-1 are assigned to the bending modes of trigonal and tetrahedral boron. Infrared spectroscopy supports these band assignments. Raman bands in the OH stretching region are of a low intensity. The combination of Raman and infrared spectroscopy enables the assessment of the molecular structure of gaudefroyite to be made.

Vibrational spectroscopy of the borate mineral chambersite MnB7O13Cl – Implications for the molecular structure

Chambersite is a manganese borate mineral with formula: MnB7O13Cl and occurs as colorless crystals in the monoclinic pyramidal crystal system. Raman bands at 902, 920, 942 and 963 cm-1 are assigned to the BO stretching vibration of the B7O13 units. Raman bands at 1027, 1045, 1056, 1075 and 1091 cm-1 are attributed to the BCl in-plane bending modes. The intense infrared band at 866 cm-1 is assigned to the trigonal borate stretching modes. The Raman band at 660 cm-1 together with bands at 597, 642 679, 705 and 721 cm-1 are assigned to the trigonal and tetrahedral borate bending modes. The molecular structure of a natural chambersite has been assessed using vibrational spectroscopy.

Vibrational spectroscopic characterization of the phosphate mineral althausite Mg2(PO4)(OH,F,O) – implications for the molecular structure

Natural single-crystal specimens of althausite from Brazil, with general formula Mg2(PO4)(OH,F,O) were investigated by Raman and infrared spectroscopy. The mineral occurs as a secondary product in granitic pegmatites. The Raman spectrum of althausite is characterized by bands at 1020, 1033 and 1044 cm-1, assigned to ν1 symmetric stretching modes of the HOPO33- and PO43- units. Raman bands at around 1067, 1083 and 1138 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 575, 589 and 606 cm-1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. Raman bands at 439, 461, 475 and 503 cm-1 are attributed to the ν2 PO4 and H2PO4 bending modes. Strong Raman bands observed at 312, 346 cm-1 with shoulder bands at 361, 381 and 398 cm-1 are assigned to MgO stretching vibrations. No bands which are attributable to water were found. Vibrational spectroscopy enables aspects of the molecular structure of althausite to be assessed.