Calderonite, a new lead-iron-vanadate of the brackebuschite group (original) (raw)

2003, American Mineralogist

Calderonite, ideally Pb 2 Fe 3+ (VO 4) 2 (OH), a new member of the brackebuschite group, has been found in the upper oxidation zone of two Pb-Zn hydrothermal deposits located at Santa Marta and Azuaga, Badajoz province, Spain. Brackebuschite and calderonite probably form a complete solid solution, locally with important substitution of Cu and Zn for Fe and Mn. The monoclinic cell parameters derived from powder X-ray diffraction (XRD) data are: a = 7.647(5) Å, b = 6.094(1) Å, c = 8.900(2) Å, b = 112.0(2)∞ and V = 384.5(4) Å 3 , and the six strongest lines, d-spacing (Å),(I),(hkl), are: 4.893(4)(011), 4.166(3)(002), 3.242(10) (-211), 3.058(3)(020), 2.980(5) (-103) and 2.746(5)(003). Electron microprobe analyses (EMPA) show a certain degree of compositional variation not only between the Santa Marta and Azuaga samples but also among grains from the same locality. A representative formula of Santa Marta calderonite, determined from EMPA, based on 9 O atoms: is (Pb 1.950 Ca 0.004 Ba 0.015) 1.969 (Fe 3 0 + .892 Cu 0.059 Zn 0.008 Al 0.015) 0.974 (V 1.847 As 0.008 Si 0.039 P 0.057) 1.951 O 7.507 (OH) 1.493. Fe 3+ is principally substituted by Cu 2+ , and V 5+ by Si 4+. r c = 6.05 g/cm 3. The thermogravimetric analysis yields a weight loss of 1.91%, which corresponds to the 1.493 H needed to maintain the charge balance. Differential thermal analysis shows endothermic effects at 279 and 663 ∞C due to dehydroxylation. A single-crystal XRD refinement was carried out on a selected crystal with cationic content determined by EMPA and starting atomic positions from brackebuschite. Final R-value of 5.81% based on 952 reflections with I > 2s I , assuming P2 1 /m symmetry, the cell dimensions are a = 7.649 Å, b = 6.101 Å, c = 8.904 Å, b = 112.23∞. Calderonite is red orange to red brown, semitransparent to translucent with vitreous luster and red streak and powder. The fracture is splintery. Optically, it is biaxial positive, with a 2V X = 86∞ and strong dispersion. In plane-polarized light, it is strongly pleochroic (X = light greenish brown, Y = brown, Z = reddish brown).