Ferrirockbridgeite, (Fe0.673+□0.33)2(Fe3+)3(PO4)3(OH)4(H2O), and the oxidation (Fe 3+mechanism for rockbridgeite-group minerals

Ferrirockbridgeite, ideally (Fe-0.67(3+)square(0.33))(2)(Fe3+)(3)(PO4)(3)(OH)(4)(H2O), is a new member of the rockbridgeite group. The type specimen is from the Palermo No. 1 pegmatite in North Groton, Grafton County, New Hampshire, USA. Electron microprobe analysis, coupled with Mossbauer spectroscopy for FeO and thermogravimetric analysis (TGA) for H2O gives the empirical formula Mn2o3 Fe2o-PosMgo oiZno 03Cao 05Fe43 P - 2 87017146 H. Ferrirockbridgeite is orthorhombic, space group Bbmm with a = 13.853(1), b = 16.928(1), c = 5.1917(5) angstrom and Z = 4. Optically, ferrirockbridgeite is biaxial (-), with alpha = 1.875(5), beta = 1.890(calc), gamma = 1.900(5) (measured in white light) and 2V (meas) is 78(1) from extinction data. The dispersion is strong, with r > v. The optical orientation is X = c, Y = a, Z = b. The pleochroism is X = yellow brown, Y = olive brown, Z = dark olive green; Z > Y > X. Crystal structure refinements on ferrirockbridgeite and other oxidized rockbridgeite-group species, including type rockbridgeite and type frondelite, show that oxidation is accompanied by loss of Fe2+ from the M2 site according to the reaction [3Fe2+] -> [2Fe3+ + LI] + Fe2+(removed) + 2e-. A variable portion of the Fe removed from the M2 site becomes trapped at M3 site vacancies. A general formula for oxidized rockbridgeite-group minerals is presented.