We measured the visible to near-infrared (IR) spectra of 176 synthetic and natural samples of Fe oxides, oxyhydroxides and an oxyhydroxysulfate (here collectively called “Fe oxides”), and of 56 soil samples ranging widely in goethite/hematite and goethite/lepidocrocite ratios. The positions of the second-derivative minima, corresponding to crystal-field bands, varied substantially within each group of the Fe oxide minerals. Because of overlapping band positions, goethite, maghemite and schwertmannite could not be discriminated. Using the positions of the 4T1←6A1, 4T2←6A1, (4E;4A1)←6A1 and the electron pair transition (4T1+4T1)←(6A1+6A1), at least 80% of the pure akaganeite, feroxyhite, ferrihydrite, hematite and lepidocrocite samples could be correctly classified by discriminant functions. In soils containing mixtures of Fe oxides, however, only hematite and magnetite could be unequivocally discriminated from other Fe oxides. The characteristic features of hematite are the lower wavelengths of the 4T1 transition (848–906 nm) and the higher wavelengths of the electron pair transition (521–565 nm) as compared to the other Fe oxides (909–1022 nm and 479–499 nm, resp.). Magnetite could be identified by a unique band at 1500 nm due to Fe(II) to Fe(III) intervalence charge transfer. As the bands of goethite and hematite are well separated, the goethite/hematite ratio of soils not containing other Fe oxides could be reasonably predicted from the amplitude of the second-derivative bands. The detection limit of these 2 minerals in soils was below 5 g kg−1, which is about 1 order of magnitude lower than the detection limit for routine X-ray diffraction (XRD) analysis. This low detection limit, and the little time and effort involved in the measurements, make second-derivative diffuse reflectance spectroscopy a practical means of routinely determining goethite and hematite contents in soils. The identification of other accessory Fe oxide minerals in soils is, however, very restricted.

The ideal formula for members of the cerchiaraite group is Ba4M4(Si4O12)O2(OH)4Cl2[Si2O3(OH)4], where M represents Mn3+, Fe3+ or Al in the octahedral site. A suffix-based naming scheme is used in which the original cerchiaraite is renamed cerchiaraite-(Mn) and two new minerals are named cerchiaraite-(Fe) and cerchiaraite-(Al). The type localities for cerchiaraite-(Fe) are the Cerchiara mine, Liguria, Italy and the Esquire No. 7 and No. 8 claims, Big Creek, Fresno County, California, USA. The type localities for cerchiaraite-(Al) are the Esquire No. 1 claim, Rush Creek, Fresno County, California, USA and the Esquire No. 7 and No. 8 claims noted above. At the Cerchiara mine, cerchiaraite-(Fe) occurs in small fractures and veinlets in a Jurassic ophiolitic sequence. It is of secondary hydrothermal origin and occurs as tan to brown thin prisms and matted fibres. Cerchiaraite(Fe) and cerchiaraite-(Al) from the Esquire No. 1, No. 7 and No. 8 claims occur in parallel-bedded quartz-sanbornite vein assemblages which formed as a result of fluid interaction along the margin of the vein. At the Esquire No. 1, No. 7 and No. 8 claims, both cerchiaraite-(Fe) and cerchiaraite-(Al) occur as subparallel aggregates of blue to bluish green irregular prisms. Both minerals are transparent with a vitreous lustre, Mohs hardness ~4½ , brittle tenacity, irregular fracture and no cleavage. The calculated density of cerchiaraite-(Fe) is 3.710 g cm-3; the measured density of cerchiaraite-(Al) is 3.69(3) g cm-3and the calculated density is 3.643 g cm-3. Cerchiaraite-(Fe) is uniaxial (+), with ω = 1.741(2) and ε = 1.768(2); it is weakly pleochroic and O is colourless and E is yellow. Cerchiaraite-(Al) is uniaxial (-), with ω = 1.695(2) and e = 1.677(2); it is strongly pleochroic and O is colourless and E is blue. Electron-microprobe analyses yielded empirical formulae ranging from (Ba3.82Na0.02Ca0.04)Σ3.88(Fe3+3.42Ti4+0.27Al3+0.25Mn3+0.04Mg0.02)Σ4.00Si5.62O15.47(OH)9.31Cl2.22 (Cerchiara mine) to Ba4.00(Al3+2.40Fe3+1.12Mg0.15Fe2+0.12Mn2+0.06)Σ3.85Si5.78O15.34(OH)8.75Cl2.91 (Esquire No. 1 claim). Cerchiaraite is tetragonal with Z = 2 and crystallizes in space group I4/mmm. The cell parameters for cerchiaraite-(Fe) are a = 14.3554(12), c = 6.0065(5) Å and V = 1237.80(5) Å3; those for cerchiaraite(Al) are a = 14.317(4), c = 6.0037(18) Å and V = 1230.6(6) Å3. In the cerchiaraite-(Fe) structure, SiO4 tetrahedra share corners forming a four-membered Si4O12 ring. The ring is corner-linked to an edgesharing chain of Fe3+ O6 octahedra running parallel to c. A Cl site alternates along c with the Si4 O12 ring. A large channel in the framework contains Ba atoms around its periphery and statistically distributed Si2 O7 silicate dimers and Cl atoms. The strong blue pleochroic colour is attributed to Fe2+ - Fe3+intervalence charge transfer along the octahedral chain.