Original paper
Ferrirockbridgeite, ( Fe 0.67 3 + □0.33)2(Fe3+)3(PO4)3(OH)4(H2O), and the oxidation mechanism for rockbridgeite-group minerals
Grey, Ian Edward; Kampf, Anthony R.; Keck, Erich; Cashion, John D.; MacRae, Colin M.; Gozukara, Yesim; Shanks, Finlay L.
European Journal of Mineralogy Volume 31 Number 3 (2019), p. 585 - 594
26 references
published: Jul 9, 2019
published online: Mar 30, 2019
manuscript accepted: Feb 22, 2019
manuscript revision received: Jan 21, 2019
manuscript received: Jan 11, 2019
Abstract
Ferrirockbridgeite, ideally ( Fe 0.67 3 + □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 Mössbauer spectroscopy for FeO and thermogravimetric analysis (TGA) for H2O gives the empirical formula Mn 0.31 2 + Fe 0.08 2 + Mg 0.01 Zn 0.03 Ca 0.05 Fe 4.18 3 + P 2.87 O 17 H 6.11 . Ferrirockbridgeite is orthorhombic, space group Bbmm with a = 13.853(1), b = 16.928(1), c = 5.1917(5) Å and Z = 4. Optically, ferrirockbridgeite is biaxial (–), with α = 1.875(5), β = 1.890(calc), γ = 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+ + □] + 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.
Keywords
ferrirockbridgeite • new mineral • rockbridgeite group • oxidation mechanism • crystal structure • Mössbauer