Aleutite, ideally [Cu5O2](AsO4)(VO4)·(Cu0.5□0.5)Cl, was found in the Yadovitaya fumarole of the Second scoria cone of the Great Fissure Tolbachik eruption, Kamchatka Peninsula, Russia. Aleutite occurs as individual crystals in the masses of polycrystalline anhydrite. Aleutite is monoclinic, C2/m, a = 18.090(2) Å, b = 6.2284(6) Å, c = 8.2465(9) Å, β = 90.597(2)°, V = 929.1(2) Å3 and Z = 4 (from single-crystal X-ray diffraction data). The empirical formula calculated on the basis of (As + V+Mo + Fe3+) = 2 atoms per formula unit is Сu5.40Zn0.05Ca0.01As1.09V0.84Mo0.04Fe0.03K0.05Pb0.02Rb0.01Cs0.01O9.97Cl1.07. The crystal structure was solved by direct methods and refined to an agreement index R1 = 0.066. Aleutite has a new structure type. Aleutite is unique amongst natural and synthetic copper vanadates and arsenates, as it has As5+ and V5+ cations ordered over two tetrahedral sites. The topology of ${}_\infty ^1 [{\rm Cu_5O_2}]^{6 +} $ oxocentred bands in aleutite is novel and has not been described before in minerals and synthetic materials. The structural architecture of the ${}_\infty ^1 [{\rm Cu_5O_2}]^{6 +} $ band in aleutite can be derived from a kagome network and represents a one-dimensional slice from it. In addition, aleutite is an interesting and complex example of a natural salt-inclusion phase.

Obradovicite, ideal formula H4CuFe2(AsO4) (MoO4)5 · 12H2O, occurs as fine pea-green clusters on quartz from Chuquicamata, Chile. Obradovicite is orthorhombic, space group Pcnm; a = 15.046, b = 14.848, c = 11.056 Å, Z = 4. The strongest powder pattern lines are (d Å, I, hkl) 10.565(8)(110), 8.906(10)(101), 7.424(8)(020), 5.733(5)(211), 3.761(3)(400), 3.686(4)(032), 3.466(3)(411), 3.344(4)(420). It is biaxial positive with α = 1.790, β = 1.798, γ = 1.811, 2Vz = 81°, a = Z, b = X, c = Y, with strong dispersion and pale yellow pleochroism. Specific gravity is 3.55 (meas.) or 3.68 (calc.) and the Mohs hardness is 2½ with no obvious cleavage. Obradovicite is similar to betpakdalite and sodium-betpakdalite except that it contains essential Cu and K (K > Na).

Arsenoflorencite-(Ce) has been found at three localities in Australia—two in South Australia, and one in Queensland. It occurs as colourless to light brown scalenohedral crystals and crystal fragments in stream sediments. Electron microprobe analysis gave Ce2O3 12.97, La2O3 8.62, Pr2O3 3.35, Nd2O3 2.40, Gd2O3 1.38, Sm2O3 0.38, SrO 1.99, Al2O3 28.75, As2O5 27.02, P2O5 4.68, SO3 1.21%; calc, H2O 9.36%; total 102.11%. The simplified formula is REAl3(AsO4)2(OH)6, with Ce as the dominant RE element. Arsenoflorencite-(Ce) is rhombohedral, has space group R3m with αhex. 7.029 and chex. 16.517 Å, and Z = 3. Strongest X-ray powder diffraction lines are: 3.513(6)(110), 2.963(10)(113), 2.201(4)(107), 1.905(5)(303) and 1.753 Å(4)(220). Density is 4.096 (meas.) and 4.091 (calc.) g/cm3. Hardness is VHN10 170. Arsenoflorencite-(Ce) is brittle, breaks with a conchoidal fracture, and has no perceptible cleavage. The mineral is colourless in transmitted light, uniaxial positive, and has ω 1.739 and ɛ 1.745 (λ = 589 nm). Arsenoflorencite-(Ce) is the arsenate analogue of florencite-(Ce), and the name was chosen to indicate this relationship.

Solution studies have been carried out on natural and synthetic arsenate minerals, which are often found in the oxide zones of base metal orebodies. Solubility products and free energy of formation data have been derived for the minerals olivenite, cornubite, clinoclase, adamite, legrandite, euchroite, duftite, conichalcite, austinite, bayldonite, and schultenite at 298.2 K (25 °C). The data have been used in turn to construct stability field diagrams illustrating the chemical conditions under which the various species may crystallize from aqueous solution. This equilibrium model is then compared with several natural occurrences of the arsenate suites and it is demonstrated that it can be used to explain a number of observed paragenetic sequences. Descriptions of solution conditions which describe the stabilities of the arsenate minerals with respect to more commonly found secondary minerals of Pb(II), Cu(II), and Zn(II) involve more complex calculations and estimates of the likely levels of various dissolved species, but it is shown how these may be taken into account in the development of a more complex equilibrium model.

Caryinite from Låmgban, Sweden, and arseniopleite from both the Långban and Sjö Mines in Sweden, are re-examined chemically and crystallographically. Both species are monoclinic, with space group C2/c, and similar lattice parameters. The general formula for caryinite is Na4Ca4Ca4(Mn,Mg)8(AsO4)12, and that for arseniopleite is Na4Ca4Mn4(Mn,Mg)8(AsO4)12. The species status of arseniopleite remains uncertain; it may have Mn dominant in the M(1) site.

The crystal chemistry of allactite from Långban, Värmland (Sweden) was investigated by single-crystal X-ray and neutron diffraction, optical absorption spectroscopy, Fourier-transform infra-red spectroscopy (FTIR) and electron microprobe analysis by wavelength-dispersive spectroscopy (EPMA-WDS). The optical spectra indicate the presence of Mn in valence state 2+ only. Assuming 16 O atoms per formula unit, arsenic as As5+ and the (OH) content calculated by charge balance, the resulting formula based on the EPMA-WDS data is (Mn2+ 6.73Ca0.13Mg0.12Zn0.02)∑7.00(As5+)2.00O16H8, very close to the ideal composition Mn7(AsO4)2(OH)8. In the unpolarized FTIR spectrum of allactite, fundamental (OH)-stretching bands are observed at 3236, 3288, 3387, 3446, 3484, 3562 and 3570 cm–1, suggesting that a number of OH environments, with different hydrogen bond strengths, occur in the structure. The neutron structure refinement shows that four independent H sites occur in allactite with full site occupancy, all as members of hydroxyl groups. The complex hydrogen-bonding scheme in the allactite structure is now well defined, with at least nine hydrogen bonds energetically favourable with mono-, bi- and trifurcated configurations.

The systems PbO–Bi2O3–P2O5/As2O5/V2O5 have been studied with respect to their compounds and solid solutions. A number of new compounds, particularly with high-Bi contents were found. Most of them are structurally closely related to the CaF2 and δ-Bi2O3 structures. Several binary and ternary solid solutions with P/As/V substitutions were investigated.

K3Nb3WO9(AsO4)2 has been investigated by means of X-ray powder diffraction. Powder diffraction data were obtained by conventional diffractometer with Kα radiation. Unit-cell dimensions were determined by an indexing program based on variation of parameters by successive dichotomies. An orthorhombic cell (space group Pnma) was found with a=15.001 (1) Å, b=14.814(1) Å, c=7.2374 (8) Å, and V=1608.4 (4) A3. The figures of merit were calculated to be M(20)=35.9 and F(20)=70.8 (0.0055,51).