A new occurrence of austinite, CaZnAsO4(OH), conichalcite, CaCuAsO4(OH), and zincolivenite, CuZnAsO4(OH), is described from the Tripi mine, Peloritani Mountains, Sicily, Italy. These species have been observed in euhedral crystals in vugs of a calcite vein and were characterised using single-crystal X-ray diffraction, electron microprobe analysis and micro-Raman spectroscopy. Austinite and conichalcite have isotypic relations, both crystallising in space group P212121. Unit-cell parameters of austinite are a = 7.4931(5), b = 9.0256(6), c = 5.9155(4) Å, V = 400.06(5) Å3; its crystal structure was refined on the basis of 1210 unique reflections with Fo > 4σ(Fo) and 77 least-square parameters to R1 = 0.0236. Conichalcite has unit-cell parameters a = 7.419(10), b = 9.111(11), c = 5.867(7) Å and V = 396.6(1.4) Å3; the diffraction quality of its available grains was not good enough to allow a high-quality structural refinement. Chemical formulae of austinite and conichalcite are Ca1.04(1)Zn0.86(4)Cu0.09(4)As0.98(2)P0.02(1)O4(OH)0.98 and Ca0.98(1)Fe2+0.02(4)Cu0.69(10)Zn0.30(6)As0.97(2)P0.03(1)O4(OH)0.98, respectively. The new chemical data on the austinite–conichalcite isotypic pair, coupled with previous analyses, supports a possible miscibility gap between the compositions (Zn0.25Cu0.75) and (Zn0.50Cu0.50). Zincolivenite has unit-cell parameters a = 8.4594(9), b = 8.5324(8), c = 5.9893(6) Å, V = 432.30(12) Å3 and space group Pnnm; its crystal structure was refined to R1 = 0.0230 for 523 unique reflections with Fo > 4σ(Fo) and 47 least-square parameters. Its chemical composition is Cu0.73(5)Zn1.25(5)As1.01(1)O4(OH)1.01. The refinement of the crystal structure supports the ordering of Cu and Zn in two different crystallographic sites. Micro-Raman spectra of austinite, conichalcite and zincolivenite are discussed, with a focus on the O–H stretching region where local Zn and Cu arrangements affect the position of Raman bands in zincolivenite. These arsenates probably play an environmental role in the Peloritani area, where the occurrence of high contents of some potentially toxic elements in soils and stream sediments has been reported.

In the arid, Late Precambrian terrain of southern Israel, a complex suite of minerals and amorphous species were deposited in host gneiss from fluids under near-neutral conditions within 1 m of the surface. The morphology of secondary gold appears to relate to its host mineral (skeletal-dendritic with quartz; multi-faceted crystals with arsenates; spherical droplets with iron oxide). The gold is very fine-grained, and was most likely complexed as a thiosulphate.

Three amorphous phases are present (iron oxide, chrysocolla, Cu-Mn-(Fe-As) silicate). At least in part, gold and baryte appear to have crystallized out of a metal-Fe-oxide gel. Other minerals, including apatite, anglesite, and conichalcite, may have grown from appropriate crystallites present in the gel.

The conichalcite occurs mainly as bladed to acicular radial spherulites. In the presence of lead, a solid solution phase between duftite and conichalcite (‘Pb-conichalcite’) was formed.

Duftite, PbCu(AsO4)(OH) is orthorhombic, space group P212121 with a = 7.768(1), b = 9. 211(1), c = 5.999(1) Å, Z = 4; the structure has been refined to R = 4.6% and Rw = 6.5% using 640 observed reflections [F> 2σ(F)]. The structure consists of chains of edge-sharing CuO6 ‘octahedra’, parallel to c; which are linked via AsO4 tetrahedra and Pb atoms in distorted square antiprismatic co-ordination to form a three dimensional network. The CuO6 ‘octahedra’ show Jahn-Teller distortion with the elongation running approximately along <627>. The hydrogen bonding network in the structure was characterized using bond valence calculations. ‘β-duftite’ is an intermediate in the duftite-conichalcite series, which has a modulated structure based on the intergrowth of the two structures in domains of approximately 50 Å. The origin of the modulation is thought to be associated with displacements in the oxygen lattice and is related to the orientation of the Jahn-Teller distortion of CuO6 ‘octahedra’. Approximately half of the strips show an elongation parallel to <627> while the other strips are elongated parallel to [010]. This ordering results in an increase in the b cell repeat compared to duftite and conichalcite.

The mineral conichalcite from the western part of Bagdad mine, Bagdad, Eureka District, Yavapai County, Arizona, USA has been characterized by electronic, near-infrared (NIR), Raman and infrared (IR) spectroscopy. Scanning electron microscopy (SEM) images show that the mineral consists of bundles of fibres. Calculations based on the results of the energy dispersive X-ray analyses on a stoichiometric basis show the substitution of arsenate by 12 wt.% of phosphate in the mineral. Raman and IR bands are assigned in terms of the fundamental modes of AsO43− and PO43− molecules and are related to the mineral structure. Near-IR reflectance spectroscopy shows the presence of adsorbed water and hydroxyl units in the mineral. The Cu(II) coordination polyhedron in conichalcite can have at best pseudo-tetragonal geometry. The crystal field and tetragonal field parameters of the Cu(II) complex were calculated and found to agree well with the values reported for known tetragonal distortion octahedral complexes.