Infrared and Raman spectroscopic characterization of the phosphate mineral fairfieldite – Ca2(Mn2+,Fe2+)2(PO4)2·2(H2O)

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 v4 phosphate bending modes. Multiple bands in the 400–450 cm-1 region assigned to m2 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 2.730 A are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

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)(Fe3+)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.

Footemineite, the Mn-analog of atencioite, from the Foote mine, Kings Mountain, Cleveland County, North Carolina, USA, and its relationship with other roscherite-group minerals

Footemineite, ideally Ca2Mn2+square Mn22+Be4(PO4)(6)(OH)(4)-6H(2)O, triclinic, is a new member of the roscherite group. It occurs on thin fractures crossing quartz-microcline-spodumene pegmatite at the Foote mine, Kings Mountain, Cleveland County, North Carolina, U.S.A. Associated minerals are albite, analcime, eosphorite, siderite/rhodochrosite, fairfieldite, fluorapatite, quartz, milarite, and pyrite. Footemineite forms prismatic to bladed generally rough to barrel-shaped crystals up to about 1.5 mm long and I mm in diameter. Its color is yellow, the streak is white, and the luster is vitreous to slightly pearly. Footemineite is transparent and non-fluorescent. Twinning is simple, by reflection, with twin boundaries across the length of the crystals. Cleavage is good on {0 (1) over bar1}) and {100}. Density (calc.) is 2.873 g/cm(3). Footemineite is biaxial (-), n(alpha) = 1.620(2), n(beta) = 1.627(2), n(gamma) = 1.634(2) (white light). 2V(obs) = 80 degrees, 2V(calc) = 89.6 degrees. Orientation: X boolean AND b similar to 12 degrees, Y boolean AND c similar to 15 degrees, Z boolean AND a similar to 15 degrees. Elongation direction is c, dispersion: r > v or r < v, weak. Pleochroism: beta (brownish yellow) > alpha = gamma (yellow). Mossbauer and IR spectra are given. The chemical composition is (EDS mode electron microprobe, Li and Be by ICP-OES, Fe3+:Fe2+ y Mossbauer, H2O by TG data, wt%): Li2O 0.23, BeO 9.54, CaO 9.43, SrO 0.23, BaO 0.24, MgO 0.18, MnO 26.16, FeO 2.77, Fe2O3 0.62, Al2O3 0.14, P2O5 36.58, SiO2 0.42, H2O 13.1, total 99.64. The empirical formula is (Ca1.89Sr0.03Ba0.02)Sigma(1.94)(Mn-0.90(2+)square(0.10))Sigma(1.00)(square 0.78Li0.17Mg0.05) Sigma(1.00)(Mn3.252+Fe0.432+ Fe0.093+Al0.03)Sigma(3.80) Be-4.30(P5.81Si0.08O24)[(OH)3.64(H2O)0.36]Sigma(4.00)center dot 6.00H(2)O . The strongest reflection peaks of the powder diffraction pattern [d, angstrom (1, %) (hkl)] are 9.575 (53) (010), 5.998 (100) (0 (1) over bar1), 4.848 (26) (021), 3.192 (44) (210), 3.003 (14) (0 (2) over bar2), 2.803 (38) ((1) over bar 03), 2.650 (29) ((2) over bar 02), 2.424 (14) (231). Single-crystal unit-cell parameters are a = 6.788(2), b = 9.972(3), c = 10.014(2) A, (x = 73.84(2), beta = 85.34(2), gamma = 87.44(2)degrees,V = 648.74 angstrom(3), Z = 1. The space group is P (1) over bar. Crystal structure was refined to R = 0.0347 with 1273 independent reflections (F > 2(5). Footemineite is dimorphous with roscherite, and isostructural with atencioite. It is identical with the mineral from Foote mine described as ""triclinic roscherite."" The name is for the Foote mine, type locality for this and several other minerals.