Mn-substituted goethite was synthesized and the interaction between arsenite (As(III)) and Mn-substituted goethite was investigated by both solution chemistry and X-ray adsorption near edge structure (XANES) spectroscopy. Results indicate that the oxidation of As(III) is favored by Mn-substituted goethite. This reaction was more sensitive to temperature than to pH. Different reaction mechanisms may account for As(III) oxidation. Since As(III) is more mobile and toxic than As(V), the oxidation reaction of As(III) with Mn-substituted goethite may decrease arsenic toxicity under some conditions.

The As sorption capacity of a natural Mn and Fe mineral-containing sample from the Iron Quadrangle province, Brazil, was investigated. A detailed mineralogical identification was obtained by combining X-ray diffraction analyses (with Rietveld refinement), X-ray fluorescence spectroscopy, optical microscopy, and scanning electron microscopy coupled with X-ray energy dispersive spectrometry-EDS. The oxidation state of the adsorbed As species was determined by X-ray absorption near edge structure spectroscopy. The results demonstrate that the presence of naturally occurring Mn oxides promotes the effective oxidation of As (III) to As(V). Also, the Mn minerals show a significant uptake of both the trivalent and pentavalent As species. This study demonstrates that the combined influences of As(III) depletion by oxidation and adsorption on a natural oxide sample consisting of Mn minerals and Fe oxides may effectively contribute to the reduction the As concentration in waters.

The new mineral bianchiniite, Ba2(Ti4+V3+)(As2O5)2OF, has been discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as brown {001} tabular crystals, up to 1 mm across, with a vitreous lustre. It is brittle, with a perfect {001} cleavage. Streak is brownish. In reflected light, bianchiniite is grey, with orange–yellow internal reflections. It is weakly bireflectant, with a very weak anisotropy in shades of grey. Minimum and maximum reflectance data for COM wavelengths [Rmin/Rmax (%), (λ, nm)] are: 5.0/5.8 (470), 5.7/6.5 (546), 5.7/7.0 (589) and 5.2/6.3 (650). Electron microprobe analyses gave (wt.% – average of 10 spot analyses): TiO2 10.34, V2O3 3.77, Fe2O3 3.76, As2O3 44.36, Sb2O3 0.22, SrO 0.45, BaO 34.79, PbO 0.28, F 1.77, sum 99.74, –O = F –0.75, total 98.99. On the basis of 12 anions per formula unit, the empirical formula of bianchiniite is (Ba2.00Sr0.04Pb0.02)Σ2.06(Ti4+1.14V3+0.44Fe3+0.42)Σ2.00[(As3.96Sb0.02)Σ3.98O10](O1.18F0.82)Σ2.00. Bianchiniite is tetragonal, space group I4/mcm, with unit-cell parameters a = 8.7266(4), c = 15.6777(7) Å, V = 1193.91(12) Å3 and Z = 8. Its crystal structure was refined from single-crystal X-ray diffraction data to R1 = 0.0134 on the basis of 555 unique reflections with Fo > 4σ(Fo) and 34 refined parameters. The crystal structure shows columns of corner-sharing [Ti/(V,Fe)]-centred octahedra running along c, connected along a and b through (As2O5) dimers. A {001} layer of Ba-centred [10+2]-coordinated polyhedra is intercalated between (As2O5) dimers. Bianchiniite has structural relations with fresnoite- and melilite-group minerals. The name honours the two mineral collectors Andrea Bianchini (b. 1959) and Mario Bianchini (b. 1962) for their contribution to the knowledge of the mineralogy of pyrite ± baryte ± iron-oxide ore deposits from the Apuan Alps.

New occurrences of derbylite, Fex2+Fe3+4–2xTi4+3+xSb3+O13(OH), and graeserite, Fex2+Fe3+4–2xTi4+3+xAs3+O13(OH), have been identified in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. Derbylite occurs as prismatic to acicular black crystals in carbonate veins. Iron and Ti are replaced by V (up to 0.29 atoms per formula unit, apfu) and minor Cr (up to 0.04 apfu). Mössbauer spectroscopy confirmed the occurrence of Fe2+ (up to 0.73 apfu), along with Fe3+. The Sb/(As+Sb) atomic ratio ranges between 0.73 and 0.82. Minor Ba and Pb (up to 0.04 apfu) substitute. Derbylite is monoclinic, space group P21/m, with unit-cell parameters a = 7.1690(3), b = 14.3515(7), c = 4.9867(2) Å, β = 104.820(3)° and V = 495.99(4) Å3. The crystal structure was refined to R1 = 0.0352 for 1955 reflections with Fo > 4σ(Fo). Graeserite occurs as prismatic to tabular black crystals, usually twinned, in carbonate veins or as porphyroblasts in schist. Graeserite in the first kind of assemblage is V rich (up to 0.66 apfu), and V poor in the second kind (0.03 apfu). Along with minor Cr (up to 0.06 apfu), this element replaces Fe and Ti. The occurrence of Fe2+ (up to 0.68 apfu) is confirmed by Mössbauer spectroscopy. Arsenic is dominant over Sb and detectable amounts of Ba and Pb have been measured (up to 0.27 apfu). Graeserite is monoclinic, space group C2/m, with unit-cell parameters for two samples: a = 5.0225(7), b = 14.3114(18), c = 7.1743(9) Å, β = 104.878(3)°, V = 498.39(11) Å3; and a = 5.0275(4), b = 14.2668(11), c = 7.1663(5) Å, β = 105.123(4)° and V = 496.21(7) Å3. The crystal structures were refined to R1 = 0.0399 and 0.0237 for 428 and 1081 reflections with Fo > 4σ(Fo), respectively. Derbylite and graeserite are homeotypic. They share the same tunnel structure, characterised by an octahedral framework and cuboctahedral cavities, hosting (As/Sb)O3 groups and (Ba/Pb) atoms.

The new mineral mauriziodiniite (IMA2019-036), NH4(As2O3)2I, was found at the Torrecillas mine, Iquique Province, Chile, where it is a secondary alteration phase associated with calcite, cuatrocapaite-(NH4), lavendulan, magnesiokoritnigite and torrecillasite on matrix consisting of native arsenic, arsenolite and pyrite. Mauriziodiniite occurs as hexagonal tablets up to ~300 μm in diameter. Crystals are colourless and transparent, with pearly to adamantine lustre and white streak. The Mohs hardness is ~1. Tablets are sectile and easily flexible, but not elastic. Fracture is curved, irregular and stepped. Cleavage is perfect on {001}. The calculated density is 3.916 g/cm3. Optically, mauriziodiniite is uniaxial (–) with ω = 2.07(calc) and ɛ = 1.770(5) (white light). The empirical formula, determined from electron microprobe analyses, is (NH4)0.94K0.03(As2O3)2I0.92Cl0.03. Mauriziodiniite is hexagonal, P6/mmm, a = 5.289(2), c = 9.317(2) Å, V = 225.68(18) Å3 and Z = 1. The structure, refined to R1 = 4.16% for 135 Io > 2σI reflections, contains three types of layers: (1) a planar neutral As2O3 (arsenite) sheet; (2) an NH4+ layer that links adjacent arsenite sheets via bonds to their O atoms; and (3) an I– layer that links adjacent arsenite sheets via bonds to their As atoms. The layer sequence is I–As2O3–NH4–As2O3–I. Mauriziodiniite is isostructural with lucabindiite and is structurally related to gajardoite, cuatrocapaite-(NH4), cuatrocapaite-(K) and torrecillasite.

The new minerals cuatrocapaite-(NH4) (IMA2018-083) and cuatrocapaite-(K) (IMA2018-084) are the NH4- and K-dominant members of a series with the general formula (NH4,K)3(NaMg□)(As2O3)6Cl6·16H2O. Both minerals were found at the Torrecillas mine, Iquique Province, Chile, where they occur as secondary alteration phases. Both minerals occur as hexagonal tablets up to ~0.3 mm in diameter. They are transparent, with a vitreous lustre and white streak. For both, the Mohs hardness is ca. 2½, the crystals are somewhat flexible, but not elastic, the fracture is irregular and the cleavage is perfect on {001}. The measured densities are 2.65(2) and 2.76(2) g/cm3 for the NH4- and K-dominant species, respectively. Optically, cuatrocapaite-(NH4) is uniaxial (–) with ω = 1.779(3) and ε = 1.541(3) and cuatrocapaite-(K) is uniaxial (–) with ω = 1.777(3) and ε = 1.539(3) (white light). The minerals are insoluble in acids, but decompose in NaOH(aq). The empirical formulas, determined from electron-microprobe analyses, are (NH4)2.48Na1.66Mg0.87K0.09(As12O18.05)Cl5.88·16.02H2O and K2.68Na1.33Mg0.93(NH4)0.31(As12O18.01)Cl6.16·16.04H2O. The minerals are trigonal, space group R${\bar 3}$m; the cuatrocapaite-(NH4) cell parameters are a = 5.25321(19), c = 46.6882(19) Å, V = 1115.80(9) Å3 and Z = 1; the cuatrocapaite-(K) cell parameters are a = 5.2637(15), c = 46.228(8) Å, V = 1109.2(7) Å3 and Z = 1. The structures, refined for cuatrocapaite-(NH4) to R1 = 1.78% for 544 Io > 2σI reflections, contain four types of layers: (1) a planar neutral As2O3 (arsenite) sheet; (2) an (${\rm NH}_{\rm 4}^{\vskip -2pt\rm \scale65% +} $,K+) layer that links adjacent arsenite sheets; (3) a Cl– layer placed on the As side of each arsenite; and (4) a layer containing partially occupied Na, Mg and H2O sites that is flanked on either side by Cl layers. The layer sequence for the type 1, 2 and 3 layers is identical to the Cl–As2O3–K–As2O3–Cl layer sequence in the structures of lucabindiite and gajardoite.

Cornwall (UK) has suffered extensive arsenic contamination due to the historic mining and processing of mineral ores. Standard procedures for contaminated land risk assessment (DEFRA and Environment Agency, 2002a) are probably unworkable in Cornwall, with a very large number of sites classified as contaminated by arsenic. Methods of measuring the speciation and mobility of arsenic are essential for effective and rapid risk assessments of arsenic contamination.

Three clusters of lysimeters were installed in three different areas of an arsenic-contaminated Cornish site. A novel phosphoric acid microwave extraction technique was applied to the soils removed from the lysimeter holes; HPLC-HG-AFS analysis showed the majority of solid-phase arsenic to be arsenate (AsV). Pore waters obtained from the lysimeters showed variable, relatively low levels of arsenite (AsIII) and arsenate (AsV) to be present (<1–129 μg l–1). Less toxic arsenate predominated in most pore waters, with the presence of minor amounts of arsenite suggesting heterogeneous redox conditions. Pore-water arsenic concentrations were strongly positively related to solid-phase arsenate concentrations.

The use of techniques that assess the speciation of arsenic both in the solid and aqueous phases of a soil provides important information about the mobility of arsenic. The methodology presented in this paper may offer a novel basis for risk assessments of other contaminated sites.

The new mineral torrecillasite (IMA2013-112), Na(As,Sb)43+O6Cl, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, cinnabar, gypsum, halite, lavendulan, magnesiokoritnigite, marcasite, quartz, pyrite, scorodite, wendwilsonite and other potentially new As-bearing minerals. Torrecillasite occurs as thin colourless prisms up to 0.4 mm long in jack-straw aggregates, as very thin fibres in puff balls and as massive intergrowths of needles. Prisms are elongated on [100] with diamond-shaped cross-section and irregular terminations. Crystals are transparent, with adamantine lustre and white streak. The Mohs hardness is 2½, tenacity is brittle and fracture is irregular. Cleavage on (001) is likely. The calculated density is 4.056 g cm−3. Optically, torrecillasite is biaxial (−) with α = 1.800(5), β = 1.96(1), γ = 2.03(calc.) (measured in white light). The measured 2V is 62.1(5)°, no dispersion or pleochroism were observed, the optical orientation is X = c, Y = b, Z = a. The mineral is very slowly soluble in H2O, slowly soluble in dilute HCl and rapidly soluble in concentrated HCl. The empirical formula, determined from electron-microprobe analyses, is (Na1.03Mg0.02)∑1.05(As3.39Sb0.62)∑4.01O6.07Cl0.93. Torrecillasite is orthorhombic, Pmcn, a = 5.2580(9), b = 8.0620(13), c = 18.654(3) Å, V = 790.7(2) Å3 and Z = 4. The eight strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 4.298(33)(111), 4.031(78)(014,020), 3.035(100)(024,122), 2.853(39)(115,123), 2.642(84)(124,200), 2.426(34)(125), 1.8963(32)(225) and 1.8026(29)(0·1·10,233). The structure, refined to R1 = 4.06% for 814 Fo >4σF reflections, contains a neutral, wavy As2O3 layer parallel to (001) consisting of As3+O3 pyramids that share O atoms to form six-membered rings. Successive layers are flipped relative to one another and successive interlayer regions contain alternately either Na or Cl atoms. Torrecillasite is isostructural with synthetic orthorhombic NaAs4O6Br.

The new mineral russoite (IMA2015-105), NH4ClAs23+O3(H2O)0.5, was found at the Solfatara di Pozzuoli, Pozzuoli, Napoli, Italy, as a fumarolic phase associated with alacránite, dimorphite, realgar, mascagnite, salammoniac and an amorphous arsenic sulfide. It occurs as hexagonal plates up to ~300 µm in diameter and 15 µm thick, in rosette-like intergrowths. On the basis of powder X-ray diffraction measurements and chemical analysis, the mineral was recognised to be identical to the corresponding synthetic phase NH4ClAs2O3(H2O)0.5. Crystals are transparent and colourless, with vitreous lustre and white streak. Tenacity is brittle and fracture is irregular. Cleavage is perfect on {001}. The measured density is 2.89(1) g/cm3; the calculated density is 2.911 g/cm3. The empirical formula, (based on 4.5 anions per formula unit) is [(NH4)0.94,K0.06]Σ1.00(Cl0.91,Br0.01)Σ0.92As2.02O3(H2O)0.5. Russoite is hexagonal, space group P622, with a = 5.2411(7), c = 12.5948(25) Å, V = 299.62(8) Å3 and Z = 2. The eight strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 12.63(19)(001), 6.32(100)(002), 4.547(75)(100), 4.218(47)(003), 3.094(45)(103), 2.627(46)(110), 2.428(31)(112) and 1.820(28)(115). The structure, was refined to R = 0.0518 for 311 reflections with I > 2σ(I) and shows a different location of the ammonium cation and water molecules with respect to that reported for the synthetic analogue. The mineral belongs to a small group of phylloarsenite minerals (lucabindiite, torrecillasite and gajardoite). It contains electrically neutral As2O3 layers, topologically identical to those found in lucabindiite and gajardoite between which are ammonium cations and outside of which Cl– anions. Water molecules and additional ammonium cations are located in a layer between two levels of chloride anions.

The crystal structure of karibibite, Fe33+(As3+O2)4(As23+O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3, Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge-sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2)n-n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2)n-n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain.

The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.

The new mineral gajardoite (IMA2015-040), KCa0.5As3+4O6Cl2·5H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with native arsenic, arsenolite,chongite, talmessite and torrecillasite. Gajardoite occurs as hexagonal plates up to ∼100 μm in diameter and 5 μm thick, in rosette-like subparallel intergrowths. Crystals are transparent, with vitreous lustre and white streak. The Mohs hardness is ∼1½, tenacity is brittleand fracture is irregular. Cleavage is perfect on {001}. The measured density is 2.64 g/cm3 and the calculated density is 2.676 g/cm3. Optically, gajardoite is uniaxial (–) with ω = 1.780(3) and ε = 1.570(5) (measured in white light). The mineral is very slowly soluble in H2O and slowly soluble in dilute HCl at room temperature. The empirical formula, determined from electron-microprobe analyses, is (K0.77Ca0.71Na0.05Mg0.05)∑1.58As4O11Cl1.96H9.62.Gajardoite is hexagonal, P6/mmm, a = 5.2558(8), c = 15.9666(18) Å, V = 381.96(13) Å3 and Z = 1. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 16.00(100)(001), 5.31(48)(003),3.466 (31)(103), 3.013(44)(104), 2.624(51)(006,110,111), 2.353(36)(113), 1.8647(21)(116,205) and 1.4605(17) (119,303,216). The structure, refined to R1 = 3.49% for 169 Fo > 4σF reflections, contains two types of layers. One layer of formulaKAs3+4O6Cl2 consists of two neutral As2O3 sheets, between which are K+ cations and on the outside of which are Cl– anions. This layer is topologically identical to a slice of the lucabindiite structureand similar to a slice of the torrecillasite structure. The second layer consists of an edge-sharing sheet of Ca(H2O)6 trigonal pyramids with isolated H2O groups centred in the hexagonal cavities in the sheet.