Ricardo Scholz

Raman and infrared spectroscopic characterization of the phosphate mineral paravauxite Fe2+Al2(PO4)2(OH)2⋅8H2O

We have undertaken a vibrational spectroscopic study of paravauxite the Siglo XX mine, Bustillo Province, northern of Potosí department, Bolivia. This mine 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 of the studied sample was determined as Fe(2+)(0.9)5, Al(0.07)Σ1.02 (Al)2.09 (PO4)1:97 (OH)1.98 · 7.90(H2O). The Raman spectrum is dominated by an intense Raman band at 1020 cm(-1) assigned to the PO4(3-) ν1 symmetric stretching mode. Low intensity Raman bands found at 1058, 1115 and 1148 cm(-1) are assigned to the PO4(3-) ν3 antisymmetric stretching vibrations. Raman bands of paravauxite at 537, 570, 609 and 643 cm(-1) are assigned to the ν4 PO4(3-) bending modes whilst the Raman bands at 393 and 420 cm(-1) are due to the ν2 PO4(3-) bending modes. The Raman spectral profile of paravauxite in the hydroxyl stretching region is broad with component bands resolved at 3086, 3215, 3315, 3421, 3505 and 3648 cm(-1). Vibrational spectroscopy enables the assessment of the molecular structure of paravauxite to be undertaken.

A vibrational spectroscopic study of the phosphate mineral whiteite CaMn++Mg2Al2(PO4)4(OH)2 8(H2O).

Vibrational spectroscopy enables subtle details of the molecular structure of whiteite to be determined. Single crystals of a pure phase from a Brazilian pegmatite were used. The infrared and Raman spectroscopy were applied to compare the molecular structure of whiteite with that of other phosphate minerals. The Raman spectrum of whiteite shows an intense band at 972 cm(-1) assigned to the ν1PO4(3-) symmetric stretching vibrations. The low intensity Raman bands at 1076 and 1173 cm(-1) are assigned to the ν3PO4(3-) antisymmetric stretching modes. The Raman bands at 1266, 1334 and 1368 cm(-1) are assigned to AlOH deformation modes. The infrared band at 967 cm(-1) is ascribed to the PO4(3-)ν1 symmetric stretching vibrational mode. The infrared bands at 1024, 1072, 1089 and 1126 cm(-1) are attributed to the PO4(3-)ν3 antisymmetric stretching vibrations. Raman bands at 553, 571 and 586 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4(3-) unit. Raman bands at 432, 457, 479 and 500 cm(-1) are attributed to the ν2 PO4 and H2PO4 bending modes. In the 2600 to 3800 cm(-1) spectral range, Raman bands for whiteite are found 3426, 3496 and 3552 cm(-1) are assigned to AlOH stretching vibrations. Broad infrared bands are also found at 3186 cm(-1). Raman bands at 2939 and 3220 cm(-1) are assigned to water stretching vibrations. Raman spectroscopy complimented with infrared spectroscopy has enabled aspects of the structure of whiteite to be ascertained and compared with that of other phosphate minerals.

SEM, EDS and vibrational spectroscopic study of dawsonite NaAl(CO3)(OH)2.

In this work we have studied the mineral dawsonite by using a combination of scanning electron microscopy with EDS and vibrational spectroscopy. Single crystals show an acicular habitus forming aggregates with a rosette shape. The chemical analysis shows a phase composed of C, Al, and Na. Two distinct Raman bands at 1091 and 1068 cm(-1) are assigned to the CO3(2-) ν1 symmetric stretching mode. Multiple bands are observed in both the Raman and infrared spectra in the antisymmetric stretching and bending regions showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the dawsonite structure. Multiple OH deformation vibrations centred upon 950 cm(-1) in both the Raman and infrared spectra show that the OH units in the dawsonite structure are non-equivalent. Raman bands observed at 3250, 3283 and 3295 cm(-1) are assigned to OH stretching vibrations. The position of these bands indicates strong hydrogen bonding of the OH units in the dawsonite structure. The formation of the mineral dawsonite has the potential to offer a mechanism for the geosequestration of greenhouse gases.

A vibrational spectroscopic study of the silicate mineral analcime - Na2(Al4SiO4O12)·2H2O - a natural zeolite.

We have studied the mineral analcime using a combination of scanning electron microscopy with energy dispersive spectroscopy and vibrational spectroscopy. The mineral analcime Na2(Al4SiO4O12)·2H2O is a crystalline sodium silicate. Chemical analysis shows the mineral contains a range of elements including Na, Al, Fe(2+) and Si. The mineral is characterized by intense Raman bands observed at 1052, 1096 and 1125cm(-1). The infrared bands are broad; nevertheless bands may be resolved at 1006 and 1119cm(-1). These bands are assigned to SiO stretching vibrational modes. Intense Raman band at 484cm(-1) is attributed to OSiO bending modes. Raman bands observed at 2501, 3542, 3558 and 3600cm(-1) are assigned to the stretching vibrations of water. Low intensity infrared bands are noted at 3373, 3529 and 3608cm(-1). The observation of multiple water bands indicate that water is involved in the structure of analcime with differing hydrogen bond strengths. This concept is supported by the number of bands in the water bending region. Vibrational spectroscopy assists with the characterization of the mineral analcime.

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 PO4(3-) ν1 symmetric stretching mode. Raman bands at 1057 and 1089 cm(-1) are attributed to the PO4(3-) ν3 antisymmetric stretching modes. Raman bands at 412, 454 and 485 cm(-1) are assigned to the PO4(3-) ν2 bending modes. Raman bands at 536, 546 and 574 cm(-1) are assigned to the PO4(3-) ν4 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.

SEM-EDX, Raman and infrared spectroscopic characterization of the phosphate mineral frondelite (Mn2+)(Fe3+)4(PO4)3(OH)5.

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.

Vibrational spectroscopic study of the natural layered double hydroxide manasseite now defined as hydrotalcite-2H – Mg6Al2(OH)16[CO3]⋅4H2O

Raman and thermo-Raman spectroscopy have been applied to study the mineral formerly known as manasseite now simply renamed as hydrotalcite-2H Mg6Al2(OH)16[CO3]⋅4H2O. The mineral is a member of the homonymous hydrotalcite supergroup. Hydrogen bond distances calculated using a Libowitzky-type empirical function varied between 2.61 and 3.00Å. Stronger hydrogen bonds were formed by water units as compared to the hydroxyl units. Raman spectroscopy enabled the identification of bands attributed to the hydroxyl units. Two Raman bands at 1059 and 1064 cm(-1) are assigned to symmetric stretching modes of the carbonate anion. Thermal treatment shifts these bands to higher wavenumbers indicating a change in the strength of the carbonate bonding.

A vibrational spectroscopic study of the phosphate mineral zanazziite – Ca2(MgFe2+)(MgFe2+Al)4Be4(PO4)6⋅6(H2O)

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piauí 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.

Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O – A mineral found in lithium bearing pegmatites

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)(3)(PO(4))(2)⋅4H(2)O from Boa Vista mine, Galiléia, 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 ν(4)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.

Vibrational spectroscopy of the mineral meyerhofferite CaB3O3(OH)5·H2O--an assessment of the molecular structure.

Meyerhofferite is a calcium hydrated borate mineral with ideal formula: CaB3O3(OH)5·H2O 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.