Copper Minerals at Vesuvius Volcano (Southern Italy): A Mineralogical Review

Balassone, Giuseppina; Petti, Carmela; Mondillo, Nicola; Panikorovskii, Taras L.; Gennaro, Roberto de; Cappelletti, Piergiulio; Altomare, Angela; Corriero, Nicola; Cangiano, Maria; D'Orazio, L.

doi:10.3390/min9120730

Cited by 12 publications

(109 citation statements)

References 69 publications

(109 reference statements)

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“…The other hydrated copper sulfates listed above are usually related to the weathering of Cu ores, although in some case they can be found also as sublimates in fumaroles (e.g. Balassone et al ., 2019).…”

Section: Discussionmentioning

confidence: 99%

Isselite, Cu₆(SO₄)(OH)₁₀(H₂O)₄⋅H₂O, a new mineral species from Eastern Liguria, Italy

Biagioni

Belmonte

Carbone

et al. 2020

MinMag

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The new mineral isselite, Cu6(SO4)(OH)10(H2O)4⋅H2O, has been discovered in the Lagoscuro mine, Monte Ramazzo mining complex, Genoa, Eastern Liguria, Italy. It occurs as sprays of blue acicular crystals, up to 0.1 mm long, associated with brochantite and posnjakite. Streak is light blue and the lustre is vitreous. Isselite is brittle, with irregular fracture and good cleavage on {001} and {100}. Measured density is 3.00(2) g/cm3. Isselite is optically biaxial (–), with α = 1.599(2), β = 1.633(2) and γ = 1.647(2) (determined in white light). The measured 2V is 63.6(5)°. Dispersion is moderate, with r > v. The optical orientation is X = b, Y = c and Z = a. Isselite is pleochroic, with X = light blue, Y = blue, Z = blue; X << Z < Y. Electron microprobe analyses give (wt.%): SO3 11.45(21), MgO 0.31(7), CoO 1.07(14), NiO 9.41(90), CuO 51.29(126), ZnO 1.10(20), H2Ocalc 24.21, total 98.84. The empirical formula of isselite, based on Σ(Mg,Co,Ni,Cu,Zn) = 6 atoms per formula unit, is (Cu4.80Ni0.94Co0.11Zn0.10Mg0.06)Σ6.00(S1.06O4.19)(OH)10⋅5H2O. Isselite is orthorhombic, space group Pmn21, with unit-cell parameters a = 6.8070(14), b = 5.8970(12), c = 20.653(4) Å, V = 829.0(3) Å3 and Z = 2. The crystal structure of isselite was refined from single-crystal X-ray diffraction data to R1 = 0.067 on the basis of 2964 reflections with Fo > 4σ(Fo). It shows a layered structure formed by zig-zag {001} layers of Cu-centred polyhedra. Sulfate groups occur in the interlayer along with one H2O group. Isselite is chemically related to redgillite and montetrisaite.

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Section: Discussionmentioning

confidence: 99%

Isselite, Cu₆(SO₄)(OH)₁₀(H₂O)₄⋅H₂O, a new mineral species from Eastern Liguria, Italy

Biagioni

Belmonte

Carbone

et al. 2020

MinMag

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“…Calcinaksite was first detected in a calcic xenolith hosted by an alkaline basalt at Bellerberg volcano, Eifel, Germany, as the product of contact metamorphism formed during the high-temperature hydrothermal stage (Aksenov et al , 2014; Chukanov et al , 2015). The second worldwide occurrence of this mineral was recorded at Somma–Vesuvius by Balassone et al (2019). Ti-bearing litidionite associations at Somma–Vesuvius are typically found in deep-blue glassy crusts and are characterised by very unusual thermally modified pyroclastic fragments related to the old fumarolic activity from the 1872 eruption (Scacchi, 1880, 1881; Zambonini, 1910, 1935; Pozas et al , 1975).…”

Section: Introductionmentioning

confidence: 95%

“…At present, the litidionite group contains four minerals: litidionite, CuKNaSi 4 O 10 (Pozas et al , 1975), manaksite, MnKNaSi 4 O 10 (Khomyakov et al , 1992), fenaksite, Fe 2+ KNaSi 4 O 10 (Rozhdestvenskaya et al , 2004) and calcinaksite, CaKNaSi 4 O 10 ⋅H 2 O (Chukanov et al , 2015). The litidionite-bearing assemblage is typical of high-temperature alteration processes at the rock-fumaroles interface (Pozas et al , 1975; Balassone et al , 2019). Synthetic analogues of litidionite, manaksite and fenaksite have been obtained under hydrothermal conditions and 230°C (Brandão et al , 2009).…”

Section: Introductionmentioning

confidence: 99%

The complex mechanism of Ti⁴⁺ incorporation into litidionite from the Somma–Vesuvius volcano, Italy

Balassone

Panikorovskii

Pellino

et al. 2022

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For this study, the rare Cu-bearing silicate fumarolic assemblages from the Somma-Vesuvius volcano (Italy), characterized by the rare mineral litidionite, CuKNaSi 4 O 10 , were investigated.Recently other Cu-and Ti-bearing phases were found in these associations and here we report new data about these mineralizations, in which Ti-bearing litidionite occurs together with kamenevite, perovskite and rutile. Ti-bearing litidionite appears on the latest stages of partial crystallization of Ti-bearing silica glass. Incorporation of Ti 4+ into litidionite crystal structure was investigated in detail. The Raman spectra of Ti-bearing litidionite contain intense band at 597 cm −1 related to antisymmetric bending vibrations of Si-O bonds or overlapping stretching vibrations of Ti-O bonds. The bands in the range 350-500 cm −1 correspond to symmetric bending vibrations of O-Si-O bonds and overlapping stretching vibrations of Ti-O bonds. The crystal structure of Ti-litidionite has been refined in the P ̅ space group, a = 6.9699(7), b = 7.9953(10), c = 9.8227(10) Å, α = 105.186(9), β = 99.458(8), γ = 114.489(10) to R 1 = 0.064 for 1726 unique observed reflections. The refinement of the site-occupation factors confirmed the presence of Ti at five-coordinated M-site.The mean bond distance of 2.125 Å of M-site agrees with its refined occupancy (Ti 0.32 Cu 0.30 Ca 0.29 Fe 0.09 ) 1.00 . The incorporation of Ti into litidionite structure is accompanied by the complex heteropolyhedral substitution according to the scheme V Ti 4+ + VII-VIII □ + IV Al 3+ ↔ V Cu 2+ + VII-VIII (Na,K) + + IV Si 4+ . Two possible configurations for the phase with maximal TiO 2 content (12.06 wt% or 0.56 Ti apfu) CuTiK□Na 2 Si 7 AlO 20 (Z = 1) or CuTiK 2 Na□Si 7 AlO 20 (Z = 1) have been proposed.

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“…In stark contrast to the latter, oxidising fumaroles are much less common on Earth and they differ significantly in the number and variety of mineral species. Some of the best-studied fumaroles with oxidising conditions are located at the Vesuvius volcano where they show remarkable copper oxide mineralisation (Balassone et al , 2019). The Vesuvius fumaroles have been known since antiquity.…”

Section: Introductionmentioning

confidence: 99%

Evolution of fumarolic anhydrous copper sulfate minerals during successive hydration/dehydration

Siidra

Borisov

Charkin

et al. 2021

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Hydration processes of primary anhydrous minerals as well as dehydration of the hydrated phases are relevant not only for answering geochemical and petrological questions, but are also interesting in the context of the theory of the ‘Evolution of minerals’. Our study of the evolution of anhydrous exhalative sulfates in hydration and dehydration processes has demonstrated the complexity of the processes for a number of minerals from the active high-temperature fumaroles of Tolbachik volcano (chalcocyanite Cu(SO4), dolerophanite Cu2O(SO4), alumoklyuchevskite K3Cu3AlO2(SO4)4 and itelmenite Na2CuMg2(SO4)4). Hydration and dehydration experiments were carried out for all four minerals using powder X-ray diffraction. A typical structural characteristic of several anhydrous copper sulfate minerals of fumarolic origin is the presence of oxygen-centred OCu4 tetrahedra. These are absent in the structures of all known hydrated minerals or synthetic compounds of the class under consideration. Hydration of minerals initially containing O2– anions as part of oxocomplexes, proceeds with sequential formation of a large series of hydroxysalts. On the contrary, hydration of itelmenite with its relatively complex ‘initial’ structure, but without additional oxygen atoms that are strong Lewis bases, results in formation of simpler hydrates. The lower the temperature and the larger the excess of water, the stronger the tendency of the cations to adopt higher hydration numbers thus outcompeting the sulfate anions as ligands. Ultimately, the water molecules completely expel the bridging sulfate anions from the metal coordination sphere yielding relatively simple fully hydrated structures.

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Copper Minerals at Vesuvius Volcano (Southern Italy): A Mineralogical Review

Cited by 12 publications

References 69 publications

Isselite, Cu₆(SO₄)(OH)₁₀(H₂O)₄⋅H₂O, a new mineral species from Eastern Liguria, Italy

Isselite, Cu₆(SO₄)(OH)₁₀(H₂O)₄⋅H₂O, a new mineral species from Eastern Liguria, Italy

The complex mechanism of Ti⁴⁺ incorporation into litidionite from the Somma–Vesuvius volcano, Italy

Evolution of fumarolic anhydrous copper sulfate minerals during successive hydration/dehydration

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Copper Minerals at Vesuvius Volcano (Southern Italy): A Mineralogical Review

Cited by 12 publications

References 69 publications

Isselite, Cu6(SO4)(OH)10(H2O)4⋅H2O, a new mineral species from Eastern Liguria, Italy

Isselite, Cu6(SO4)(OH)10(H2O)4⋅H2O, a new mineral species from Eastern Liguria, Italy

The complex mechanism of Ti4+ incorporation into litidionite from the Somma–Vesuvius volcano, Italy

Evolution of fumarolic anhydrous copper sulfate minerals during successive hydration/dehydration

Contact Info

Product

Resources

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Isselite, Cu₆(SO₄)(OH)₁₀(H₂O)₄⋅H₂O, a new mineral species from Eastern Liguria, Italy

Isselite, Cu₆(SO₄)(OH)₁₀(H₂O)₄⋅H₂O, a new mineral species from Eastern Liguria, Italy

The complex mechanism of Ti⁴⁺ incorporation into litidionite from the Somma–Vesuvius volcano, Italy