Search

We have studied the borate mineral szaibelyite MgBO 2 (OH) using electron microscopy and vibrational spectroscopy. EDS spectra show a phase composed of Mg with minor amounts of Fe. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm −1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1099 cm −1 with a shoulder band at 1093 cm −1 is assigned to BO stretching vibration. Raman bands at 1144, 1157, 1229, 1318 cm −1 are attributed to the BOH in-plane bending modes. Raman bands at 836 and 988 cm −1 are attributed to the antisymmetric stretching modes of tetrahedral boron. The infrared bands at 3559 and 3547 cm −1 are assigned to hydroxyl stretching vibrations. Broad infrared bands at 3269 and 3398 cm −1 are assigned to water stretching vibrations. Infrared bands at 1306, 1352, 1391, 1437 cm −1 are assigned to the antisymmetric stretching vibrations of trigonal boron. Vibrational spectroscopy enables aspects of the molecular structure of the borate mineral szaibelyite to be assessed.

The mineral ushkovite has been analyzed using a combination of electron microscopy with EDX and vibrational spectroscopy. Chemical analysis shows the mineral contains P, Mg with very minor Fe. Thus, the formula of the studied ushkovite is Mg3 2+(PO4)2 8H2O. The Raman spectrum shows an intense band at 953 cm 1 assigned to the m1 symmetric stretching mode. In the infrared spectra complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong infrared bands around 827 cm 1 are attributed to water librational modes. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 2881, 2998, 3107, 3203, 3284 and 3457 cm 1. The wavenumber band at 3457 cm 1 is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH bending modes where a strong infrared band centered around 1653 cm 1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH bending bands from strongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. Vibrational spectroscopy enhances our knowledge of the molecular structure of ushkovite.

We have studied the boron containing mineral ezcurrite Na4B10O17·7H2O using electron microscopy and vibrational spectroscopy. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm−1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1037 cm−1 is assigned to BO stretching vibration. Raman bands at 1129, 1163, 1193 cm−1 are attributed to BO stretching vibration of the tetrahedral units. The Raman band at 947 cm−1 is attributed to the antisymmetric stretching modes of tetrahedral boron. The sharp Raman peak at 1037 cm−1 is from the 11-B component such a mode, then it should have a smaller 10-B satellite near (1.03) × (1037) = 1048 cm−1, and indeed a small peak at 1048 is observed. The broad Raman bands at 3186, 3329, 3431, 3509, 3547 and 3576 cm−1 are assigned to water stretching vibrations. Broad infrared bands at 3170, 3322, 3419, 3450, 3493, 3542, 3577 and 3597 cm−1 are also assigned to water stretching vibrations. Infrared bands at 1330, 1352, 1389, 1407, 1421 and 1457 cm−1 are assigned to the antisymmetric stretching vibrations of trigonal boron. The observation of so many bands suggests that there is considerable variation in the structure of ezcurrite. Infrared bands at 1634, 1646 and 1681 cm−1 are assigned to water bending modes. The number of water bending modes is in harmony with the number of water stretching vibrations.

There are a large number of boron-containing minerals, of which vonsenite is one. Some discussion about the molecular structure of vonsenite exists in the literature. Whether water is involved in the structure is ill-determined. The molecular structure of vonsenite has been assessed by the combination of Raman and infrared spectroscopy. The Raman spectrum is characterized by two intense broad bands at 997 and 1059 cm−1 assigned to the BO stretching vibrational mode. A series of Raman bands in the 1200–1500 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. No Raman spectrum of water in the OH stretching region could be obtained. The infrared spectrum shows a series of overlapping bands with bands identified at 3037, 3245, 3443, 3556, and 3614 cm−1. It is important to understand the structure of vonsenite in order to form nanomaterials based on its structure. Vibrational spectroscopy ena...

Cesarferreiraite, Fe2+Fe23+(AsO4)2(OH)2·8H2O, is a new laueite-group mineral (IMA 2012-099) of triclinic symmetry, from Eduardo pegmatite mine, Conselheiro Pena municipality, Minas Gerais, Brazil. Intimately associated minerals are pharmacosiderite, scorodite, and earlier arsenopyrite, and probably cesarferreiraite replaces the latter. It occurs as fibrous-to-tabular aggregates up to 2 mm. Single crystals, up to 10 μm long with a thickness of about 1–2 μm, are elongated along [001] and flattened on (100). The fibers have almost rectangular cross-section apparently bound by the {100} and {010} pinacoid forms. Color and streak are pale to greenish yellow. Luster is vitreous; individual crystals are transparent and masses are translucent. Cleavage is distinct, presumably on {010} and {100}. Calculated density is 2.934 g/cm3. The mineral is biaxial (+), n (min) = 1.747(3), n (max) = 1.754(3) (589 nm). IR spectrum of cesarferreiraite is unique and can be used for the identification of the mineral. Chemical composition ( n = 4, WDS, calculated for the condition Fe2+:Fe3+ = 1:2, H2O for the ideal structural formula, wt%) is: FeO 11.50, Fe2O3 25.56, CaO 15.41, As2O5 33.51, H2O 26.01, total 100.12. The empirical formula (based on 18 O apfu) is Fe2+0.98Fe3+1.96[(AsO4)1.79(PO4)0.31](OH)1.52·8.08H2O. The strongest eight X-ray powder-diffraction lines [ d in A( I )( hkl )] are: 9.85(95)(010), 6.35(100)(001), 3.671(29)(121), 3.158(32)(130), 2.960(39)(022), 2.884(35)(131), 2.680(29)(211), and 2.540(23)(210). Unit-cell parameters refined from powder data indexed by analogy with related laueite-group minerals (space group: P 1) are: a = 5.383(2), b = 10.363(3), c = 6.878(2) A, α = 96.42(4), β = 109.19(3), γ = 102.30(2)°, V = 347.1(2) A3, and Z = 1. Gladstone-Dale compatibility is −0.020 (excellent). Cesarferreiraite is the arsenate analog of ferrolaueite.

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 HOPO3(3-) and PO4(3-) 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 10,194 and 10,329 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 mineral natrodufrenite 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 (Na 0.88 Ca 0.12 ) ∑1.00 ( Fe 0.72 2 + Mn 0.11 Mg 0.08 Ca 0.04 Zr 0.01 Cu 0.01 ) ∑0.97 ( Fe 4.89 3 + Al 0.02 ) ∑4.91 (PO 4 ) 3.96 (OH 6.15 F 0.07 ) 6.22 ⋅2.05(H 2 O). Raman spectroscopy identifies an intense peak at 1003 cm −1 assigned to the PO 4 3 - ν 1 symmetric stretching mode. Raman bands are observed at 1059 and 1118 cm −1 and are attributed to the PO 4 3 - ν 3 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 ν 4 PO 4 3 - bending modes and Raman bands at 425, 444, 477 and 507 cm −1 are due to the ν 2 PO 4 3 - 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 natrodufrenite to be assessed.

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 (CO3)^2- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of (CO3)^2- symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 1091 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 1091 cm^-1 assigned to the m3 (CO3)^2- antisymmetric stretching mode. The observation of additional Raman bands for the m3 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 1091 cm^-1 and assigned to the (CO3)^2- m2 bending modes. Raman bands are observed for huanghoite at around 627 1091 cm^-1 and are assigned to the (CO3)^2- m4 bending modes. Raman bands are observed for the carbonate m4 in phase bending modes at 722 1091 cm^-1 for bastnasite, 736 and 684 1091 cm^-1 for parisite, 714 1091 cm^-1 for northupite. Raman bands for huanghoite observed at 3259, 3484 and 3589 1091 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.

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.

An assessment of the molecular structure of carletonite a rare phyllosilicate mineral with general chemical formula given as KNa4Ca4Si8O18(CO3)4(OH,F).H2O has been undertaken using vibrational spectroscopy. Carletonite has a complex layered structure. Within one period of c, it contains a silicate layer of composition NaKSi8O18 H2O, a carbonate layer of composition NaCO3 0.5H2O and two carbonate layers of composition NaCa2CO3(F,OH)0.5. Raman bands are observed at 1066, 1075 and 1086 cm 1. Whether these bands are due to the CO2 3 m1 symmetric stretching mode or to an SiO stretching vibration is open to question. Multiple bands are observed in the 300–800 cm 1 spectral region, making the attribution of these bands difficult. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate and carbonate surfaces.

We have analyzed a frondelite mineral sample from the Cigana mine, located in the municipality of Conselheiro Pena, a well-known pegmatite in Brazil. In the Cigana pegmatite, secondary phosphates, namely eosphorite, fairfieldite, fluorapatite, frondelite, gormanite, hureaulite, lithiophilite, reddingite and vivianite are common minerals in miarolitic cavities and in massive blocks after triphylite. The chemical formula was determined as (Mn0.68, Fe0.32)(Fe(3+))3,72(PO4)3.17(OH)4.99. The structure of the mineral was assessed using vibrational spectroscopy. Bands attributed to the stretching and bending modes of PO4(3-) and HOPO3(3-) units were identified. The observation of multiple bands supports the concept of symmetry reduction of the phosphate anion in the frondelite structure. Sharp Raman and infrared bands at 3581 cm(-1) is assigned to the OH stretching vibration. Broad Raman bands at 3063, 3529 and 3365 cm(-1) are attributed to water stretching vibrational modes.

Colemanite CaB 3 O 4 (OH) 3 ·H 2 O is a secondary borate mineral formed from borax and ulexite in evaporate deposits of alkaline lacustrine sediments. The basic structure of colemanite contains endless chains of interlocking BO 2 (OH) triangles and BO 3 (OH) tetrahedrons with the calcium, water and extra hydroxide units interspersed between these chains. The Raman spectra of colemanite is characterized by an intense band at 3605 cm −1 assigned to the stretching vibration of OH units and a series of bands at 3182, 3300, 3389 and 3534 cm −1 assigned to water stretching vibrations. Infrared bands are observed in similar positions. The BO stretching vibrations of the trigonal and tetrahedral boron are characterized by Raman bands at 876, 1065 and 1084 cm −1 . The OBO bending mode is defined by the Raman band at 611 cm −1 . It is important to characterize the very wide range of borate minerals including colemanite because of the very wide range of applications of boron containing minerals.

Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the phosphate mineral fairfieldite. The Raman phosphate (PO4)(3-) stretching region shows strong differences between the fairfieldite phosphate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (PO4)2- 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 600 cm(-1) are assigned to ν4 phosphate bending modes. Multiple bands in the 400-450 cm(-1) region assigned to ν2 phosphate bending modes provide further evidence of symmetry reduction of the phosphate anion. Three broadbands for fairfieldite are found at 3040, 3139 and 3271 cm(-1) and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.658 and 2.730Å are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piaui mine, located in Itinga, Minas Gerais. The mineral was studied by electron microprobe, Raman and infrared spectroscopy. The chemical formula can be expressed as Ca 2.00 (Mg 3.15 ,Fe 0.78 ,Mn 0.16 ,Zn 0.01 ,Al 0.26 ,Ca 0.14 )Be 4.00 (PO 4 ) 6.09 (OH) 4.00 ⋅5.69(H 2 O) and shows an intermediate member of the zanazziite–greinfeinstenite series, with predominance of zanazziite member. The molecular structure of the mineral zanazziite has been determined using a combination of Raman and infrared spectroscopy. A very intense Raman band at 970 cm −1 is assigned to the phosphate symmetric stretching mode whilst the Raman bands at 1007, 1047, 1064 and 1096 cm −1 are attributed to the phosphate antisymmetric stretching mode. The infrared spectrum is broad and the antisymmetric stretching bands are prominent. Raman bands at 559, 568, 589 cm −1 are assigned to the ν 4 out of plane bending modes of the PO 4 and HPO 4 units. The observation of multiple bands supports the concept that the symmetry of the phosphate unit in the zanazziite structure is reduced in symmetry. Raman bands at 3437 and 3447 cm −1 are attributed to the OH stretching vibrations; Raman bands at 3098 and 3256 are attributed to water stretching vibrations. The width and complexity of the infrared spectral profile in contrast to the well resolved Raman spectra, proves that the pegmatitic phosphates are better studied with Raman spectroscopy.

Bermanite Mn(2+)Mn(2)(3+)(PO(4))(2)(OH)(2)·4(H(2)O) is a mixed valent hydrated hydroxy phosphate mineral. The mineral is reddish-brown and occurs in crystal aggregates and as lamellar masses. Bermanite is a common mineral in granitic pegmatites. The chemical composition of bermanite was obtained using EDS techniques. We have studied the molecular structure of bermanite using vibrational spectroscopy. The mineral is characterized by a Raman doublet at 991 and 999 cm(-1) attributed to the phosphate stretching mode of two non-equivalent phosphate units. Raman bands at 1071, 1117 and 1142 cm(-1) are assigned to the phosphate antisymmetric stretching modes. The hydroxyl stretching spectral region is complex with overlapping bands attributed to water and hydroxyl stretching vibrations. Vibrational spectroscopy proves most useful for the study of the mineral bermanite.

The secondary phosphate mineral sigloite Fe3+Al2(PO4)2(OH)3·7H2O is the exception to the rule that phosphate mineral paragenesis is related to the final phase of hydrothermal mineralization at low temperatures. Sigloite was formed as an oxidation pseudomorph after paravauxite, during the last supergene paragenetic stage. We have studied the secondary phosphate mineral sigloite Fe3+Al2(PO4)2(OH)3·7H2O using vibrational spectroscopic techniques. Because the mineral is a phosphate mineral, it is readily studied by spectroscopic techniques as the phosphate and hydrogen phosphate units are readily measured. Indeed, sigloite shows the presence of both phosphate and hydrogen phosphate units in its structure. Raman bands at 1009 cm−1 with shoulders at 993 and 1039 cm−1 are assigned to stretching vibrations of PO 4 3 - and HPO 4 2 - units. The Raman band at 993 cm−1 is assigned to the ν1 symmetric stretching mode of the POH units, whereas the Raman band at 1009 cm−1 is assigned to the ν1 PO 4 3 - symmetric stretching mode. Raman bands observed at 506, 528, 571, 596, 619 and 659 cm−1 are attributed to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The Raman bands at 2988, 3118 and 3357 cm−1 are assigned to water stretching vibration. The series of bands at 3422, 3449, 3493, 3552 and 3615 cm−1 are assigned to the OH stretching vibrations of the hydroxyl units. The observation of multiple bands gives credence to the non-equivalence of the OH units in the sigloite structure.

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O from Boa Vista mine, Galileia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm−1 are assigned to the symmetric stretching mode of HOPO 3 2 - and PO 4 3 - units. Raman bands at 548, 564, 599 and 634 cm−1 are assigned to the ν4 PO 4 3 - bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm−1 and infrared bands at 2623, 2838, 3136 and 3185 cm−1 are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed.

In this research, we have used vibrational spectroscopy to study the phosphate mineral kosnarite KZr2(PO4)3. Interest in this mineral rests with the ability of zirconium phosphates (ZP) to lock in radioactive elements. ZP have the capacity to concentrate and immobilize the actinide fraction of radioactive phases in homogeneous zirconium phosphate phases. The Raman spectrum of kosnarite is characterized by a very intense band at 1,026 cm−1 assigned to the symmetric stretching vibration of the PO4 3− ν1 symmetric stretching vibration. The series of bands at 561, 595 and 638 cm−1 are assigned to the ν4 out-of-plane bending modes of the PO4 3− units. The intense band at 437 cm−1 with other bands of lower wavenumber at 387, 405 and 421 cm−1 is assigned to the ν2 in-plane bending modes of the PO4 3− units. The number of bands in the antisymmetric stretching region supports the concept that the symmetry of the phosphate anion in the kosnarite structure is preserved. The width of the infrared spectral profile and its complexity in contrast to the well-resolved Raman spectrum show that the pegmatitic phosphates are better studied with Raman spectroscopy.

Detailed investigation of an intermediate member of the reddingite–phosphoferrite series, using infrared and Raman spectroscopy, scanning electron microcopy and electron microprobe analysis, has been carried out on a homogeneous sample from a lithium-bearing pegmatite named Cigana mine, near Conselheiro Pena, Minas Gerais, Brazil. The determined formula is \( ({\text{Mn}}_{1.60} {\text{Fe}}_{1.21} {\text{Ca}}_{0.01} {\text{Mg}}_{0.01} )_{\sum 2.83} ({\text{PO}}_{4} )_{2.12} \cdot ({\text{H}}_{2} {\text{O}}_{2.85} {\text{F}}_{0.01} )_{\sum 2.86} \), indicating predominance in the reddingite member. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of reddingite-phosphoferrite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of reddingite–phosphoferrite.

The composition, structure, X-ray powder diffraction pattern, optical properties, density, infrared, Raman and Mössbauer spectra, and thermal properties of a homogeneous sample of metavivianite from the Boa Vista pegmatite, near Galiléia, Minas Gerais, Brazil are reported for the first time. Metavivianite is biaxial (+) with α = 1.600(3), β = 1.640(3), γ = 1.685(3) and 2Vmeas = 85(5)°. The measured and calculated densities are Dmeas = 2.56(2) and Dcalc = 2.579 g cm–3. The chemical composition, based on electronmicroprobe analyses, Mössbauer spectroscopy (to determine the Fe2+:Fe3+ ratio) and gas chromatography (to determine H2O) is MgO 0.70, MnO 0.92, FeO 17.98, Fe2O3 26.60, P2O5 28.62, H2O 26.5; total 101.32 wt.%. The empirical formula is (Fe3+1.64Fe2+1.23Mg0.085Mn0.06)Σ3.015(PO4)1.98(OH)1.72·6.36H2O. Metavivianite is triclinic, P, a = 7.989(1), b = 9.321(2), c = 4.629(1) Å, α = 97.34(1), β = 95.96(1), γ = 108.59(2)°, V = 320.18(11) Å3 and Z = 1. The crystal structure was solved using a single-crystal techniques to an agreement index R = 6.0%. The dominant cations in the independent sites are Fe2+ and Fe3+, with multiplicities of 1 and 2, respectively. The simplified crystal-chemical formula for metavivianite is Fe2+ (Fe3+, Fe2+)2(PO4)2(OH,H2O)2·6H2O; the endmember formula is Fe2+Fe3+2(PO4)2(OH)2·6H2O, which is dimorphous with ferrostrunzite.

Sidorenkite is a very rare low-temperature hydrothermal mineral, formed very late in the crystallization of hyperagpaitic pegmatites in a differentiated alkalic massif (Mt. Alluaiv, Kola Peninsula, Russia). Sidorenkite Na3Mn(PO4)(CO3) is a phosphate-carbonate of sodium and manganese. Such a formula with two oxyanions lends itself to vibrational spectroscopy. The sharp Raman band at 959 cm(-1) and 1012 cm(-1) are assigned to the PO4(3-) stretching modes, whilst the Raman bands at 1044 cm(-1) and 1074 cm(-1) are attributed to the CO3(2-) stretching modes. It is noted that no Raman bands at around 800 cm(-1) for sidorenkite were observed. The infrared spectrum of sidorenkite shows a quite intense band at 868 cm(-1) with other resolved component bands at 850 and 862 cm(-1). These bands are ascribed to the CO3(2-) out-of-plane bend (ν2) bending mode. The series of Raman bands at 622, 635, 645 and 704 cm(-1) are assigned to the ν4 phosphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the carbonate anion from D3h or even C2v.

We have studied the phosphate mineral vantasselite Al₄(PO₄)₃(OH)₃·9H₂O using a combination of SEM with EDX and Raman and infrared spectroscopy. Qualitative chemical analysis shows Al, Fe and P. Raman bands at 1013 and 1027 cm(-1) are assigned to the PO₄(3-)ν₁ symmetric stretching mode. The observation of two bands suggests the non-equivalence of the phosphate units in the vantasselite structure. Raman bands at 1051, 1076 and 1090 cm(-1) are attributed to the PO₄(3-)ν₃ antisymmetric stretching vibration. A comparison is made with the spectroscopy of wardite. Strong infrared bands at 1044, 1078, 1092, 1112, 1133, 1180 and 1210 cm(-1) are attributed to the PO₄(3-)ν₃ antisymmetric stretching mode. Some of these bands may be due to δAl₂OH deformation modes. Vibrational spectroscopy offers a mechanism for the study of the molecular structure of vantasselite.

We have undertaken a vibrational spectroscopic study of vauxite from Llallagua, Bolivia. This source is important source for rare and unusual secondary phosphate minerals and is the type locality for a number of rare phosphates such as vauxite, sigloite, metavauxite and for jeanbandyite. The chemical formula was determined as (Fe 0.98 Mn 0.01 ) ∑0.99 (Al 2.00 )(PO 4 ) ∑2.03 (OH) 1.98 ·5.95(H 2 O). The Raman spectrum is dominated by intense Raman bands at 978, 1000, 1009, 1027 cm −1 assigned to the PO 4 3− and HPO 4 2− stretching modes. Low intensity Raman bands are found at 1046, 1059, 1070, 1105, 1122, 1134 and 1150 cm −1 and are assigned to the PO 4 3− ν 3 antisymmetric stretching vibrations. Raman bands of at 498, 502, 517, 523 and 535 cm −1 are assigned to the ν 4 PO 4 3− bending modes while the Raman bands at 418, 451, 461 and 470 cm −1 are due to the ν 2 PO 4 3− bending modes. The Raman spectral profile of vauxite in the hydroxyl stretching region is broad with component bands resolved at 2918, 3103, 3328, 3402, 3555 and 3648 cm −1 . Vibrational spectroscopy enables the assessment of the molecular structure of vauxite to be undertaken.

The mineral lulzacite from Saint-Aubin des Chateaux mine, France, with theoretical formula Sr(2)Fe(2+)(Fe(2+),Mg)(2)Al(4)(PO(4))(4)(OH)(10) has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Chemical analysis shows a Sr, Fe, Al phosphate with minor amounts of Ga, Ba and Mg. Raman spectroscopy identifies an intense band at 990cm(-1) with an additional band at 1011cm(-1). These bands are attributed to the PO4(3-)ν1 symmetric stretching mode. The ν3 antisymmetric stretching modes are observed by a large number of Raman bands. The Raman bands at 1034, 1051, 1058, 1069 and 1084 together with the Raman bands at 1098, 1116, 1133, 1155 and 1174cm(-1) are assigned to the ν3 antisymmetric stretching vibrations of PO4(3-) and the HOPO3(2-) units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of lulzacite. The series of Raman bands at 567, 582, 601, 644, 661, 673 and 687cm(-1) are assigned to the PO4(3-)ν2 bending modes. The series of Raman bands at 437, 468, 478, 491, 503cm(-1) are attributed to the PO4(3-) and HOPO3(2-)ν4 bending modes. No Raman bands of lulzacite which could be attributed to the hydroxyl stretching unit were observed. Infrared bands at 3511 and 3359cm(-1) are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299cm(-1) are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral lulzacite.

In this paper, we have investigated on the natural wendwilsonite mineral with the formulae Ca 2 (Mg,Co)(AsO 4 ) 2 ⋅2(H 2 O). 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 Ca 2 B(AsO 4 ) 2 ⋅2H 2 O (where B may be Co, Fe 2+ , 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 (AsO 4 ) 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 (AsO 4 ) 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 ν 4 bending modes. Multiple bands in the 350–300 cm −1 region assigned to ν 2 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 A 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.

Meyerhofferite is a calcium hydrated borate mineral with ideal formula: CaB 3 O 3 (OH) 5 ·H 2 O and occurs as white complex acicular to crude crystals with length up to ∼4 cm, in fibrous divergent, radiating aggregates or reticulated and is often found in sedimentary or lake-bed borate deposits. The Raman spectrum of meyerhofferite is dominated by intense sharp band at 880 cm −1 assigned to the symmetric stretching mode of trigonal boron. Broad Raman bands at 1046, 1110, 1135 and 1201 cm −1 are attributed to BOH in-plane bending modes. Raman bands in the 900–1000 cm −1 spectral region are assigned to the antisymmetric stretching of tetrahedral boron. Distinct OH stretching Raman bands are observed at 3400, 3483 and 3608 cm −1 . The mineral meyerhofferite has a distinct Raman spectrum which is different from the spectrum of other borate minerals, making Raman spectroscopy a very useful tool for the detection of meyerhofferite in sedimentary and lake bed deposits.

The mineral weloganite Na2Sr3Zr(CO3)6·3H2O has been studied by using vibrational spectroscopy and a comparison is made with the spectra of weloganite with other carbonate minerals. Weloganite is member of the mckelveyite group that includes donnayite-(Y) and mckelveyite-(Y). The Raman spectrum of weloganite is characterized by an intense band at 1082 cm−1 with shoulder bands at 1061 and 1073 cm−1, attributed to the CO 3 2 - symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of CO 3 2 - symmetric stretching vibration varies with mineral composition. The Raman bands at 1350, 1371, 1385, 1417, 1526, 1546, and 1563 cm−1 are assigned to the ν3 (CO3)2− antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for weloganite is significant in that it shows distortion of the carbonate anion in the mineral structure. The Raman band observed at 870 cm−1 is assigned to the (CO3)2− ν2 bending mode. Raman bands observed for weloganite at 679, 682, 696, 728, 736, 749, and 762 cm−1 are assigned to the (CO3)2− ν4 bending modes. A comparison of the vibrational spectra is made with that of the rare earth carbonates decrespignyite, bastnasite, hydroxybastnasite, parisite, and northupite.

This research was done on hureaulite samples from the Cigana claim, a lithium bearing pegmatite with triphylite and spodumene. The mine is located in Conselheiro Pena, east of Minas Gerais. Chemical analysis was carried out by Electron Microprobe analysis and indicated a manganese rich phase with partial substitution of iron. The calculated chemical formula of the studied sample is: (Mn3.23, Fe1.04, Ca0.19, Mg0.13)(PO4)2.7(HPO4)2.6(OH)4.78. The Raman spectrum of hureaulite is dominated by an intense Sharp band at 959 cm−1 assigned to PO stretching vibrations of HPO4 2− units. The Raman band at 989 cm−1 is assigned to the PO4 3− stretching vibration. Raman bands at 1007, 1024, 1047, and 1083 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations of HPO4 2− and PO4 3− units. A set of Raman bands at 531, 543, 564 and 582 cm−1 are assigned to the _4 bending modes of the HPO4 2− and PO4 3− units. Raman bands observed at 414, and 455 cm−1 are attributed to the _2 HPO4 2− and PO4 3− units. The intense A series of Raman and infrared bands in the OH stretching region are assigned to water stretching vibrations. Based upon the position of these bands hydrogen bond distances are calculated. Hydrogen bond distances are short indicating very strong hydrogen bonding in the hureaulite structure. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral hureaulite to be understood.

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 HPO4(2-) 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 ν1PO4(3-) symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm(-1) are assigned to the ν3PO4(3-) 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 ν4 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 ν2 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.

The mineral beryllonite has been characterized by the combination of Raman spectroscopy and infrared spectroscopy. SEM–EDX was used for the chemical analysis of the mineral. The intense sharp Raman band at 1011 cm−1, was assigned to the phosphate symmetric stretching mode. Raman bands at 1046, 1053, 1068 and the low intensity bands at 1147, 1160 and 1175 cm−1 are attributed to the phosphate antisymmetric stretching vibrations. The number of bands in the antisymmetric stretching region supports the concept of symmetry reduction of the phosphate anion in the beryllonite structure. This concept is supported by the number of bands found in the out-of-plane bending region. Multiple bands are also found in the in-plane bending region with Raman bands at 399, 418, 431 and 466 cm−1. Strong Raman bands at 304 and 354 cm−1 are attributed to metal oxygen vibrations. Vibrational spectroscopy served to determine the molecular structure of the mineral. The pegmatitic phosphate minerals such as beryllonite are more readily studied by Raman spectroscopy than infrared spectroscopy.