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Piccoliite, NaCaMn3+2(AsO4)2O(OH), a new arsenate from the manganese deposits of Montaldo di Mondovì and Valletta, Piedmont, Italy
- Fernando Cámara, Cristian Biagioni, Marco E. Ciriotti, Ferdinando Bosi, Uwe Kolitsch, Werner H. Paar, Ulf Hålenius, Giovanni O. Lepore, Günter Blass, Erica Bittarello
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- Journal:
- Mineralogical Magazine / Volume 87 / Issue 2 / April 2023
- Published online by Cambridge University Press:
- 28 November 2022, pp. 204-217
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Piccoliite, ideally NaCaMn3+2(AsO4)2O(OH), is a new mineral discovered in the Fe–Mn ore hosted in metaquartzites of the Montaldo di Mondovì mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as small and rare black crystals and aggregates hosted by a matrix of quartz, associated with calcite and berzeliite/manganberzeliite. It has been also found in the Valletta mine near Canosio, Maira Valley, Cuneo Province, Piedmont, Italy, where it occurs embedded in quartz associated with grandaite, hematite, tilasite/adelite and rarely thorianite. The mineral is opaque (thin splinters may be very dark red), with brown streak and has a resinous to vitreous lustre. It is brittle with irregular fracture. No cleavage has been observed. The measured Mohs hardness is ~5–5.5. Piccoliite is non fluorescent. The calculated density is 4.08 g⋅cm–3. Chemical spot analyses by electron microprobe analysis using wavelength dispersive spectroscopy resulted in the empirical formula (based on 10 anions per formula unit) (Na0.64Ca0.35)Σ0.99(Ca0.75Na0.24)Σ0.99(Mn3+1.08Fe3+0.59Mg0.20Ca0.10)Σ1.97(As2.03V0.03Si0.01)Σ2.07O9(OH) and (Na0.53Ca0.47)Σ1.00(Ca0.76Na0.23Sr0.01)Σ1.00(Mn3+0.63Fe3+0.49Mg0.48Mn4+0.34Ca0.06)Σ2.00(As1.97P0.01Si0.01)Σ1.99O9(OH) for the Montaldo di Mondovì and Valletta samples, respectively. The mineral is orthorhombic, Pbcm, with single-crystal unit-cell parameters a = 8.8761(9), b = 7.5190(8), c = 11.689(1) Å and V = 780.1(1) Å3 (Montaldo di Mondovì sample) and a = 8.8889(2), b = 7.5269(1), c = 11.6795(2) Å, V = 781.43(2) Å3 (Valletta sample) with Z = 4. The seven strongest powder X-ray diffraction lines for the sample from Montaldo di Mondovì are [d Å (Irel; hkl)]: 4.85 (57; 102), 3.470 (59; 120, 113), 3.167 (100; 022), 2.742 (30; 310, 213), 2.683 (53; 311, 023), 2.580 (50; 222, 114) and 2.325 (19; 320, 214, 223). The crystal structure (R1 = 0.0250 for 1554 unique reflections for the Montaldo di Mondovì sample and 0.0260 for 3242 unique reflections for the Valletta sample) has MnO5(OH) octahedra forming edge-shared dimers; these dimers are connected through corner-sharing, forming two-up-two-down [[6]M2([4]TO4)4φ2] chains [M = Mn; T = As; φ = O(OH)] running along [001]. These chains are bonded in the a and b directions by sharing corners with AsO4 tetrahedra, giving rise to a framework of tetrahedra and octahedra hosting seven-coordinated Ca2+ and Na+ cations. The crystal structure of piccoliite is closely related to that of pilawite-(Y) as well as to carminite-group minerals that also show the same type of chains but with different linkage. The mineral is named after the mineral collectors Gian Paolo Piccoli and Gian Carlo Piccoli (father and son) (1926–1996 and b. 1953, respectively), the latter having discovered the type material at the Montaldo di Mondovì mine.
As-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: IV. Lombardoite, Ba2Mn3+(AsO4)2(OH) and aldomarinoite, Sr2Mn3+(AsO4)2(OH), description and crystal structure
- Fernando Cámara, Lisa Baratelli, Marco E. Ciriotti, Fabrizio Nestola, Gian Carlo Piccoli, Ferdinando Bosi, Erica Bittarello, Ulf Hålenius, Corrado Balestra
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- Journal:
- Mineralogical Magazine / Volume 86 / Issue 3 / June 2022
- Published online by Cambridge University Press:
- 07 April 2022, pp. 447-458
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Lombardoite, ideally Ba2Mn3+(AsO4)2(OH), and aldomarinoite, ideally Sr2Mn3+(AsO4)2(OH), are two new minerals of the arsenbrackebuschite group in the brackebuschite supergroup, discovered in Fe–Mn ore in metaquartzites of the abandoned mine of Valletta, Canosio, Val Maira, Cuneo Province, Piedmont, Italy. They occur as red–brown and orange brown, respectively, as subhedral crystals (< 0.5 mm) in thin masses, associated with quartz, aegirine, baryte, calcite, hematite, muscovite and Mn minerals such as cryptomelane, braunite and manganberzeliite. Both minerals are translucent, have yellow–orange streak and vitreous lustre. Both are brittle. Estimated Mohs hardness is 6–6½ for lombardoite (by analogy to canosioite), and 4½–5 for aldomarinoite (by analogy to tokyoite). Calculated densities are 5.124 g/cm3 for lombardoite and 4.679 g/cm3 for aldomarinoite. Both minerals are biaxial (+). Lombardoite shows 2Vz(meas.) = 78(4)° and is pleochroic with X = yellowish brown, Y = brown and Z = reddish brown (Z > Y > X). Aldomarinoite has 2Vz(meas.) = 67.1(1)°, and is pleochroic with X = brown, Y = brownish orange and Z = yellowish brown (Z > Y > X). Point analyses by electron microprobe using wavelength dispersive spectroscopy resulted in the empirical formula (based on 9 O anions): (Ba1.96Sr0.17Pb0.04Na0.02Ca0.02)Σ2.21(Mn3+0.62Fe3+0.13Al0.06Mg0.11)Σ0.92[(As0.87V0.12P0.01)Σ1.00O4]2(OH) for lombardoite, and (Sr1.93Ca0.21Ba0.04Pb0.01)Σ2.19(Mn3+0.48Al0.35Fe3+0.21Mg0.01)Σ1.05[(As0.92V0.03)Σ0.95O4]2(OH) for aldomarinoite. The absence of H2O was confirmed by Raman spectroscopy and infrared spectroscopy. Both minerals are monoclinic, P21/m, with unit-cell parameters a = 7.8636(1) Å, b = 6.13418(1) Å, c = 9.1197(1) Å, β = 112.660(2)° and V = 405.94(1) Å3, for lombardoite and a = 7.5577(4) Å, b = 5.9978(3) Å, c = 8.7387(4) Å, β = 111.938(6)° and V = 367.43(3) Å3, for aldomarinoite. The eight strongest powder X-ray diffraction lines are [d, Å (Irel) (hkl)]: 6.985 (39) (10$\bar{1}$), 3.727 (33) (111), 3.314 (100) (21$\bar{1}$), 3.073 (24) (020), 3.036 (33) (21$\bar{2}$, 10$\bar{3}$), 2.810 (87) (12$\bar{1}$, 112), 2.125 (20) (301, 11$\bar{4}$) and 1.748 (24) (321) for lombardoite and 3.191 (89) (21$\bar{1}$), 2.997 (45) (020), 2.914 (47) (21$\bar{2}$, 10$\bar{3}$), 2.715 (100) (112), 2.087 (39) (12$\bar{3}$, 1.833 (32) (31$\bar{4}$), 1.689 (36) (321), 1.664 (21) (132) for aldomarinoite. The minerals are isostructural with brackebuschite: infinite chains of edge sharing octahedra running parallel to the b axis and decorated with AsO4 groups are connected along the a and c axes through Ba and Sr atoms in lombardoite and aldomarinoite, respectively. The minerals are named after Bruno Lombardo (1944–2014), geologist and petrologist at C.N.R. (National Research Council of Italy), and Aldo Marino (b. 1942) the mineral collector and founding member of the AMI – Italian Micromineralogical Association.
Armellinoite-(Ce), Ca4Ce4+(AsO4)4⋅H2O, a new mineral species isostructural with pottsite, (Pb3Bi)Bi(VO4)4⋅H2O
- Fernando Cámara, Marco E. Ciriotti, Uwe Kolitsch, Ferdinando Bosi, Erica Bittarello, Piero Brizio, Pietro Vignola, Günter Blaß
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- Journal:
- Mineralogical Magazine / Volume 85 / Issue 6 / December 2021
- Published online by Cambridge University Press:
- 13 December 2021, pp. 901-909
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Armellinoite-(Ce), ideally Ca4Ce4+(AsO4)4⋅H2O, is a new mineral discovered in Fe–Mn ore in metaquartzites of the Montaldo mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as very small and rare, pale yellow to brown–yellow pseudo-octahedral translucent crystals hosted by a matrix of quartz, hematite, cryptomelane/hollandite, tilasite, muscovite, braunite and montmorillonite. The mineral is translucent, with white streak and has a resinous to vitreous lustre. It is brittle with irregular fracture and fair cleavage parallel to {110} and {100}. Estimated Mohs hardness is ~3–3.5. Calculated density is 4.29 g⋅cm–3. Armellinote-(Ce) is uniaxial (–), ω = 1.795(5), ɛ = 1.765(5) (white light), non-pleochroic and non-fluorescent. Chemical point analyses by WDS-EPMA yielded the empirical formula (based on 17 O+F anions): A(Ca3.89Th0.08Sr0.02La0.03)Σ4.02B(Ce4+0.76Nd0.13Y0.08Gd0.03Sm0.02Pr0.01Dy0.01Ho0.01)Σ1.05[(As4.00P0.01)Σ4.01O4]4⋅(H2O0.85F0.15)Σ2.00. The presence of H2O was confirmed by Raman spectroscopy. The mineral is tetragonal, I41/a, with single-crystal unit-cell parameters a = 10.749(2), c = 12.030(2) Å and V = 1390.0(6) Å3, with Z = 4. The eight strongest X-ray powder diffraction lines are [d Å (Irel; hkl)]: 7.983 (36; 101), 4.443 (23; 2̄11), 2.957 (100; 3̄12), 2.398 (14; 420), 1.875 (22; 424, 325), 1.728 (19; 3̄16), 1.612 (13; 613) and 1.475 (26; 712, 552). The crystal structure (R1 = 0.0284 for 1275 unique reflections) has isolated TO4 (T = As5+) tetrahedra that link Ca2+- or Ce4+-centred polyhedra via common oxygen ligands to form 2D blocks or double-layered (DL) structural units parallel to (001). Armellinoite-(Ce) is isostructural with pottsite, ideally (Pb3Bi)Bi(VO4)4⋅H2O, and closely related to a larger number of anhydrous synthetic compounds. The mineral is named after the mineral collector Gianluca Armellino (b. 1962), who collected the discovery sample.
Mn-bearing purplish-red tourmaline from the Anjanabonoina pegmatite, Madagascar
- Ferdinando Bosi, Beatrice Celata, Henrik Skogby, Ulf Hålenius, Gioacchino Tempesta, Marco E. Ciriotti, Erica Bittarello, Alessandra Marengo
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- Journal:
- Mineralogical Magazine / Volume 85 / Issue 2 / April 2021
- Published online by Cambridge University Press:
- 01 March 2021, pp. 242-253
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A gem-quality purplish-red tourmaline sample of alleged liddicoatitic composition from the Anjanabonoina pegmatite, Madagascar, has been fully characterised using a multi-analytical approach to define its crystal-chemical identity. Single-crystal X-ray diffraction, chemical and spectroscopic analysis resulted in the formula: X(Na0.41□0.35Ca0.24)Σ1.00Y(Al1.81Li1.00Fe3+0.04Mn3+0.02Mn2+0.12Ti0.004)Σ3.00ZAl6 [T(Si5.60B0.40)Σ6.00O18] (BO3)3 (OH)3W[(OH)0.50F0.13O0.37]Σ1.00 which corresponds to the tourmaline species elbaite having the typical space group R3m and relatively small unit-cell dimensions, a = 15.7935(4) Å, c = 7.0860(2) Å and V = 7.0860(2) Å3.
Optical absorption spectroscopy showed that the purplish-red colour is caused by minor amounts of Mn3+ (Mn2O3 = 0.20 wt.%). Thermal treatment in air up to 750°C strongly intensified the colour of the sample due to the oxidation of all Mn2+ to Mn3+ (Mn2O3 up to 1.21 wt.%). Based on infrared and Raman data, a crystal-chemical model regarding the electrostatic interaction between the X cation and W anion, and involving the Y cations as well, is proposed to explain the absence or rarity of the mineral species ‘liddicoatite’.
Arsenic-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: I. Grandaite, Sr2Al(AsO4)2(OH), description and crystal structure
- F. Cámara, M. E. Ciriotti, E. Bittarello, F. Nestola, F. Massimi, F. Radica, E. Costa, P. Benna, G. C. Piccoli
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- Mineralogical Magazine / Volume 78 / Issue 3 / June 2014
- Published online by Cambridge University Press:
- 05 July 2018, pp. 757-774
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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)(11), 2.981 (50.9)(020), 2.922 (40.2)(03), 2.743 (31.4)(120), 2.705 (65.2)(112), 2.087 (51.8) (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)∑=2.11(Al0.68Fe0.143+Mn0.123+Mg0.13)∑=1.07 [(As0.96V0.01)∑=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: III. Canosioite, Ba2Fe3+(AsO4)2(OH), description and crystal structure
- F. Cámara, E. Bittarello, M. E. Ciriotti, F. Nestola, F. Radica, F. Massimi, C. Balestra, R. Bracco
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- Mineralogical Magazine / Volume 81 / Issue 2 / April 2017
- Published online by Cambridge University Press:
- 02 January 2018, pp. 305-317
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The new mineral 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, subhedral millimetre-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)(111), 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, H2O1.61 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(Fe0.523+Mn0.293+Al0.15Mg0.06)∑1.02[(As0.64V0.36)∑1.00O4]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).
As-bearing new mineral species from Valletta mine, Maira Valley, Piedmont, Italy: II. Braccoite, NaMn2+5 [Si5AsO17(OH)](OH), description and crystal structure
- Fernando Cámara, Erica Bittarello, Marco E. Ciriotti, Fabrizio Nestola, Francesco Radica, Marco Marchesini
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- Mineralogical Magazine / Volume 79 / Issue 1 / February 2015
- Published online by Cambridge University Press:
- 02 January 2018, pp. 171-189
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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 = 92.691(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, SiO239.73, 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).