Erica Bittarello

Self-assembled nanocrystals of barium carbonate in biomineral-like structures

“Silica Biomorphs” are self-assembled nanocrystals of barium carbonate that form in silica-rich environments. Their morphologies are highly reminiscent of the shapes of primitive life (discovered in Archean cherts), but the precipitates are clearly inorganic and form without intervention of any organic material. The concept of morphology and symmetry has always been used to divide the world into two large groups: the realm of the inanimate and the realm of the living. The object of this study is not to debate the truthfulness of the microfossils, but to understand the laws that control the formation and the shape of polycrystalline structures and to underline the false notion that the living and abiotic realms can be distinguished on the basis of their morphology.

Arsenic-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: I. Grandaite, Sr2Al(AsO4)2(OH), description and crystal structure

Abstract The new mineral species grandaite, ideally Sr2Al(AsO4)2(OH), has been discovered on the dump of Valletta mine, Maira Valley, Cuneo province, Piedmont, Italy. Its origin is related to the reaction between the ore minerals and hydrothermal solutions. It occurs in thin masses of bright orange to salmon to brown coloured crystals, or infrequently as fan-like aggregates of small (<1 mm) crystals, with reddish-brown streak and waxy to vitreous lustre. Grandaite is associated with aegirine, baryte, braunite, hematite, tilasite, quartz, unidentified Mn oxides and Mn silicates under study. Grandaite is biaxial (+) with refractive indices α = 1.726(1), β = 1.731(1), γ = 1.752(1). Its calculated density is 4.378 g/cm3. Grandaite is monoclinic, space group P21/m, with a = 7.5764(5), b = 5.9507(4), c = 8.8050(6) Å, β = 112.551(2)°, V = 366.62(4) Å3 and Z = 2. The eight strongest diffraction lines of the observed X-ray powder diffraction pattern are [d in Å, (I), (hkl)]: 3.194 (100)(2̄11), 2.981 (50.9)(020), 2.922 (40.2)(1̄03), 2.743 (31.4)(120), 2.705 (65.2)(112), 2.087 (51.8) (1.23), 1.685 (24.5)(321), 1.663 (27.7)(132). Chemical analyses by electron microprobe gave (wt.%) SrO 29.81, CaO 7.28, BaO 1.56, Al2O3 7.07, Fe2O3 2.34, Mn2O3 1.88, MgO 1.04, PbO 0.43, As2O5 44.95, V2O5 0.50, P2O5 0.09, sum 96.95; H2O 1.83 wt.% was calculated by stoichiometry from the results of the crystal-structure analysis. Raman and infrared spectroscopies confirmed the presence of (AsO4)3- and OH groups. The empirical formula calculated on the basis of 9 O a.p.f.u., in agreement with the structural results, is (Sr1.41Ca0.64Ba0.05Pb0.01)Σ=2.11(Al0.68Fe3+0.14Mn3+0.12Mg0.13)Σ=1.07 [(As0.96V0.01)Σ=0.97O4]2(OH), the simplified formula is (Sr,Ca)2(Al,Fe3+)(AsO4)2(OH) and the ideal formula is Sr2Al(AsO4)2(OH). The crystal structure was solved by direct methods and found to be topologically identical to that of arsenbrackebuschite. The structure model was refined on the basis of 1442 observed reflections to R1 = 2.78%. In the structure of grandaite, chains of edge-sharing M3+ octahedra run along [010] and share vertices with T5+ tetrahedra, building up [M3+(T5+O4)2(OH, H2O)] units, which are connected through interstitial divalent cations. Grandaite is named after the informal appellation of the province where the type locality is located. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA2013-059). The discovery of grandaite and of other members of the group (description still in progress) opens up the possibility of exploring the crystal chemistry of the brackebuschite supergroup.

As-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: II. Braccoite, NaMn2+5[Si5AsO17(OH)](OH), description and crystal structure

Abstract The new mineral species braccoite, ideally NaMn2+5 [Si5AsO17(OH)](OH), has been discovered in the Valletta mine dumps, in Maira Valley, Cuneo province, Piedmont, Italy. Its origin is probably related to the reaction between ore minerals and hydrothermal fluids. It occurs as subhedral crystals in brown-red coloured thin masses, with a pale-yellow streak and vitreous to resinous lustre. Braccoite is associated with tiragalloite, for which new data are provided, as well as gamagarite, hematite, manganberzeliite, palenzonaite, quartz, saneroite, tokyoite, unidentified Mn oxides, organic compounds, and Mn arsenates and silicates under study. Braccoite is biaxial positive with refractive indices α = 1.749(1), β = 1.750(1), γ = 1.760(1). It is triclinic, space group P1̄ , with a = 9.7354(4), b = 9.9572(3), c = 9.0657(3) Å, α = 92̄691(2), β = 117.057(4), γ = 105.323(3)°, V = 740.37(4) Å3 and Z = 2. Its calculated density is 3.56 g/cm3. The ten strongest diffraction lines of the observed powder X-ray diffraction (XRD) pattern are [d in Å, (I), (hkl)]: 3.055 (69)(22̄1), 3.042 (43)(102), 3.012 (65)(32̄1̄ ), 2.985 (55)(23̄1̄ ), 2.825 (100)(213̄), 2.708 (92)(220), 2.627 (43)(23̄2̄), 2.381 (58)(41̄1̄ ), 2.226 (25)(214̄) and 1.680 (433̄)(36). Chemical analyses by wavelength-dispersive spectroscopy electron microprobe gave (wt.%): Na2O 4.06, CaO 0.05, MnO 41.76, MgO 0.96, Al2O3 0.04, CuO 0.02, SiO2 39.73, As2O5 6.87, V2O5 1.43, SO3 0.01 and F 0.04. H2O 2.20 was calculated on the basis of 2OH groups p.f.u. Raman spectroscopy confirmed the presence of (SiO4)4-, (AsO4)3- and OH groups. The empirical formula, calculated on the basis of Σ cations-(Na,K) = 11 p.f.u., in agreement with the results of the crystal structure, is Na1.06(Mn2+4.46Mn3+0.32Mg0.19V3+0.01Al0.01Ca0.01)[Si5(As0.48Si0.37V5+0.15)O17(OH)](OH0.98F0.02); the simplified formula is Na(Mn,Mg,Al,Ca)5[Si5(As,V,Si)O17(OH)](OH,F). Single-crystal XRD allowed the structure to be solved by direct methods and revealed that braccoite is the As-dominant analogue of saneroite. The structure model was refined on the basis of 4389 observed reflections to R1 = 3.47%. Braccoite is named in honour of Dr Roberto Bracco (b. 1959), a systematic minerals collector with a special interest in manganese minerals. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2013-093).

As-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: III. Canosioite, Ba2Fe3+(AsO4)2(OH), description and crystal structure

Abstract The newmineral species canosioite, ideally Ba2Fe3+(AsO4)2(OH), has been discovered in the dump of Valletta mine, Maira Valley, Cuneo Province, Piedmont, Italy. Its origin is probably related to the reaction between ore minerals and hydrothermal fluids. It occurs in reddish-brown granules, subhedralmillimetre-size crystals,with a pale yellow streak and vitreous lustre. Canosioite is associated with aegirine, baryte, calcite, hematite, bronze Mn-bearing muscovite, unidentified Mn oxides and unidentified arsenates. Canosioite is biaxial (+) with a 2Vmeas = 84(2)°. It is weakly pleochroic with X = brownish yellow, Y = brown, Z = reddish brown, Z > Y > X. Canosioite is monoclinic, P21/m, with a = 7.8642(4), b = 6.1083(3), c = 9.1670(5) Å, β = 112.874(6)°, V = 405.73(4) Å3 and Z = 2. Calculated density is 4.943 g cm-3. The seven strongest diffraction lines of the observed powder X-ray diffraction pattern are [d in Å, (I) (hkl)]: 3.713 (18)(111̄), 3.304 (100)(211̄), 3.058 (31)(020), 3.047 (59)(103̄), 2.801 (73)(112), 2.337 (24)(220), 2.158 (24)(123̄). Electron microprobe analyses gave (wt.%): Na2O 0.06, MgO 0.43, CaO 0.02, NiO 0.02, CuO 0.03, SrO 0.42, BaO 49.36, PbO 1.69, Al2O3 1.25,Mn2O3 3.89, Fe2O3 6.95, Sb2O3 0.01, SiO2 0.03, P2O5 0.02,V2O5 10.88, As2O5 24.64, SO3 0.01, F 0.02, H2O 1.61 was calculated on the basis of 1 (OH,F,H2O) group per formula unit. Infrared spectroscopy confirmed the presence of OH. The empirical formula calculated on the basis of 9 O apfu, is (Ba1.92Pb0.05Sr0.02Na0.01)∑2.00(Fe3+0.52Mn3+0.29Al0.15Mg0.06)Σ1.02[(As0.64V0.36)Σ1.00O4]2[(OH0.92F0.01)(H2O)0.07] and the ideal formula is Ba2Fe3+(AsO4)2(OH). The crystal structure was solved by direct methods and found to be isostructural to that of arsenbrackebuschite. The structure model was refined (R1 = 2.6%) on the basis of 1245 observed reflections. Canosioite is named after the small municipality of Canosio, where the type locality, the Valletta mine, is situated. The new mineral and name were approved by the International Mineralogical Association Commission on New Minerals and Mineral Names (IMA2015-030).

“Mohsite” of Colomba: Identification as Dessauite-(Y)

During a reorganization of the mineralogical collection of Turin University, old samples of the so-called mohsite of Colomba were found. “Mohsite” was discredited in 1979 by Kelly et al., as a result of some analyses performed on the equivalent material coming from the French region of Hautes-Alpes, but the original samples found in similar geological setting in Italy were lost and never analysed with modern equipment. After more than a century, the rediscovered samples of Professor Colomba were analysed by means of SEM-EDS analysis, microRaman spectroscopy, and X-ray diffraction. The results have demonstrated that the historical samples studied by Colomba are Pb-free dessauite-(Y), and pointed to an idealized crystal chemical formula (Sr0.70Na0.25Ca0.09)Σ=1.04 (Y0.62U0.18Yb0.09Sc0.08)Σ=0.97 (Ti12.66)Σ=17.70O38 and unit-cell parameters a = 10.376(3) A, c = 20.903(6) A, and V = 1949(1) A3.