Special Issue "Thallium: Mineralogy, Geochemistry and Ore Processes"

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Deposits".

Deadline for manuscript submissions: closed (31 August 2018)

Special Issue Editors

Guest Editor
Dr. Cristian Biagioni

Dipartimento di Scienze della Terra, Università di Pisa, Pisa, Italy
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Interests: crystal-chemistry; sulfosalts; new minerals; single crystal X-ray diffraction; ore mineralogy
Guest Editor
Assoc. Prof. Dr. Massimo D’Orazio

Dipartimento di Scienze della Terra, Università di Pisa, Pisa, Italy
Website | E-Mail
Interests: geochemistry; petrology of igneous rocks; geoanalysis, ore geology

Special Issue Information

Dear Colleagues,

Thallium (Z = 81) is either chalcophile or lithophile. It is widely distributed within the Earth’s continental crust and is more abundant than other well-known elements, such as Ag, Sb, and Hg. Nonetheless, its availability is limited due to its tendency to substitute alkaline metals in rock-forming minerals. Consequently, the occurrence of thallium minerals or the presence of high-thallium concentrations within rocks should be considered as exceptional.

Such occurrences are of outstanding significance for both the environment and global economy. Indeed, thallium is toxic to living organisms, being more toxic to humans than other heavy elements. Notwithstanding its toxicity, thallium is a high-valued element (7200 $·kg-1 in 2015), owing to its applications in current and future high-tech industry. Therefore, it is fascinating chemistry, its high toxicity, and its increasing economic value make the element thallium and its compounds of particular interest and of environmental concern.

This Special Issue welcomes contributions on thallium mineralogy, geochemistry, and ore geology, helping to describe the intriguing crystal-chemistry of such a compound, its variable geochemistry, and to give further insights in the ore processes related to the formation of thallium-bearing ore deposits.

Dr. Cristian Biagioni
Assoc. Prof. Dr. Massimo D’Orazio
Guest Editors

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Keywords

  • thallium
  • crystal-chemistry
  • thallium ore geology
  • thallium geochemistry

Published Papers (7 papers)

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Research

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Open AccessArticle Assessing Thallium Elemental Systematics and Isotope Ratio Variations in Porphyry Ore Systems: A Case Study of the Bingham Canyon District
Minerals 2018, 8(12), 548; https://doi.org/10.3390/min8120548
Received: 1 October 2018 / Revised: 16 November 2018 / Accepted: 19 November 2018 / Published: 26 November 2018
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Abstract
The Bingham Canyon porphyry deposit is one of the world’s largest Cu-Mo-Au resources. Elevated concentrations of thallium (Tl) compared to average continental crust have been found in some brecciated and igneous samples in this area, which likely result from mobilization of Tl by [...] Read more.
The Bingham Canyon porphyry deposit is one of the world’s largest Cu-Mo-Au resources. Elevated concentrations of thallium (Tl) compared to average continental crust have been found in some brecciated and igneous samples in this area, which likely result from mobilization of Tl by relatively low temperature hydrothermal fluids. The Tl-enrichment at Bingham Canyon therefore provides an opportunity to investigate if Tl isotope ratios reflect hydrothermal enrichment and whether there are systematic Tl isotope fractionations that could provide an exploration tool. We present a reconnaissance study of nineteen samples spanning a range of lithologies from the Bingham district which were analysed for their Tl content and Tl isotope ratios, reported as parts per ten thousand (ε205Tl) relative to the NIST SRM997 international standard. The range of ε205Tl reported in this study (−16.4 to +7.2) is the largest observed in a hydrothermal ore deposit to date. Unbrecciated samples collected relatively proximal to the Bingham Canyon porphyry system have ε205Tl of −4.2 to +0.9, similar to observations in a previous study of porphyry deposits. This relatively narrow range suggests that high-temperature (>300 °C) hydrothermal alteration does not result in significant Tl isotope fractionation. However, two samples ~3–4 km away from Bingham Canyon have higher ε205Tl values (+1.3 and +7.2), and samples from more distal (~7 km) disseminated gold deposits at Melco and Barneys Canyon display an even wider range in ε205Tl (−16.4 to +6.0). The observation of large positive and negative excursions in ε205Tl relative to the mantle value (ε205Tl = −2.0 ± 1.0) contrasts with previous investigations of hydrothermal systems. Samples displaying the most extreme positive and negative ε205Tl values also contain elevated concentrations of Tl-Sb-As. Furthermore, with the exception of one sample, all of the Tl isotopic anomalies occur in hydrothermal breccia samples. This suggests that ε205Tl excursions are most extreme during the migration of low-temperature hydrothermal fluids potentially related to sediment-hosted gold mineralization. Future investigation to determine the host phase(s) for Tl in breccias displaying both chalcophile element enrichment and ε205Tl excursions can potentially provide new information about hydrothermal fluid composition and could be used to locate sites for future porphyry exploration. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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Open AccessArticle Lead–Antimony Sulfosalts from Tuscany (Italy). XXIV. Crystal Structure of Thallium-Bearing Chovanite, TlPb26(Sb,As)31S72O, from the Monte Arsiccio Mine, Apuan Alps
Minerals 2018, 8(11), 535; https://doi.org/10.3390/min8110535
Received: 22 October 2018 / Revised: 14 November 2018 / Accepted: 16 November 2018 / Published: 18 November 2018
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Abstract
A thallium-bearing variety of the lead–antimony oxysulfosalt chovanite from the Monte Arsiccio mine (Apuan Alps, Tuscany, Italy) has been reexamined. It occurs as thin, ribbon-like crystals, black in color, up to 5 mm in length in vugs of dolomite ± baryte ± quartz [...] Read more.
A thallium-bearing variety of the lead–antimony oxysulfosalt chovanite from the Monte Arsiccio mine (Apuan Alps, Tuscany, Italy) has been reexamined. It occurs as thin, ribbon-like crystals, black in color, up to 5 mm in length in vugs of dolomite ± baryte ± quartz veins embedded in the metadolostone of the Sant’Olga level. Associated minerals are rouxelite, robinsonite, sphalerite, valentinite, baryte, dolomite, quartz, and Ba-rich K-feldspar. Chemical analysis pointed to contents of Tl up to 0.86 apfu, corresponding to the ideal chemical formula TlPb26(Sb,As)31S72O. The structural role of thallium has been investigated using single-crystal X-ray diffraction using synchrotron radiation (λ = 0.59040 Å). Thallium-rich chovanite is monoclinic, space group P21/c, with unit-cell parameters a = 34.280(3), b = 8.2430(7), c = 48.457(4) Å, β = 106.290(4)°, and V = 13143(2) Å3. The crystal structure was refined to a final R1 = 0.083 for 12,052 reflections with Fo > 4σ(Fo) and 1210 refined parameters. The general features of thallium-rich chovanite agree with those of chovanite. Thallium is present as Tl+; it is disordered among two mixed (Pb/Tl) positions, with a Tl/Pb atomic ratio below 1, that precludes this compound to be a new species. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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Open AccessArticle The Crystal Chemistry of Rathite Based on New Electron-Microprobe Data and Single-Crystal Structure Refinements: The Role of Thallium
Minerals 2018, 8(10), 466; https://doi.org/10.3390/min8100466
Received: 21 September 2018 / Revised: 4 October 2018 / Accepted: 15 October 2018 / Published: 18 October 2018
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Abstract
Crystal-structure refinements in space group P21/c were performed on five grains of rathite with different types and degrees of thallium, silver, and antimony substitutions, as well as quantitative electron-microprobe analyses of more than 800 different rathite samples. The results [...] Read more.
Crystal-structure refinements in space group P21/c were performed on five grains of rathite with different types and degrees of thallium, silver, and antimony substitutions, as well as quantitative electron-microprobe analyses of more than 800 different rathite samples. The results of these studies both enlarged and clarified the complex spectrum of cation substitutions and the crystal chemistry of rathite. The [Tl+ + As3+] ↔ 2Pb2+ scheme of substitution acts at the structural sites Pb1, Pb2, and Me6, the [Ag+ + As3+] ↔ 2Pb2+ substitution at Me5, and the Sb-for-As substitution at the Me3 site only. The homogeneity range of rathite was determined to be unusually large, ranging from very Tl-poor compositions (0.16 wt%; refined single-crystal unit-cell parameters: a = 8.471(2), b = 7.926(2), c = 25.186(5) Å, β = 100.58(3)°, V = 1662.4(6) Å3) to very Tl-rich compositions (11.78 wt%; a = 8.521(2), b = 8.005(2), c = 25.031(5) Å, β = 100.56(3)°, V = 1678.4(6) Å3). The Ag content is only slightly variable (3.1 wt%–4.1 wt%) with a mean value of 3.6 wt%. The Sb content is strongly variable (0.20 wt%–7.71 wt%) and not correlated with the Tl content. With increasing Tl content (0.16 wt%–11.78 wt%), a clear increase of the unit-cell parameters a, b, and V, and a slight decrease of c is observed, although this is somewhat masked by the randomly variable Sb content. The revised general formula of rathite may be written as AgxTlyPb16−2(x+y)As16+x+yzSbzS40 (with 1.6 < x < 2, 0 < y < 3, 0 < z < 3.5). Based on Pb–S bond lengths, polyhedral characteristics and Pb-site bond-valence sums, we conclude that the Pb1 site is more affected by Tl substitution than the Pb2 site. When Tl substitution reaches values above 13 wt% (or 3 apfu), a new phase (“SR”), belonging to the rahite group, appears as lamellar exsolution intergrowths with Tl-rich rathite (11.78 wt%). Rathite is found only in the Lengenbach and Reckibach deposits, Binntal, Canton Wallis, Switzerland. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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Open AccessArticle Tsygankoite, Mn8Tl8Hg2(Sb21Pb2Tl)Σ24S48, a New Sulfosalt from the Vorontsovskoe Gold Deposit, Northern Urals, Russia
Minerals 2018, 8(5), 218; https://doi.org/10.3390/min8050218
Received: 2 May 2018 / Revised: 18 May 2018 / Accepted: 19 May 2018 / Published: 21 May 2018
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Abstract
Tsygankoite, ideally Mn8Tl8Hg2(Sb21Pb2Tl)Σ24S48, is a new sulfosalt discovered at the Vorontsovskoe gold deposit, Northern Urals, Russia. It occurs as lath-like elongated crystals up to 0.2 mm embedded in calcite–dolomite–clinochlore [...] Read more.
Tsygankoite, ideally Mn8Tl8Hg2(Sb21Pb2Tl)Σ24S48, is a new sulfosalt discovered at the Vorontsovskoe gold deposit, Northern Urals, Russia. It occurs as lath-like elongated crystals up to 0.2 mm embedded in calcite–dolomite–clinochlore matrix. The associated minerals also include aktashite, alabandite, arsenopyrite, barite, cinnabar, fluorapatite, orpiment, pyrite, realgar, routhierite, sphalerite, tilasite, and titanite. The new mineral is non-fluorescent, black, and opaque with a metallic lustre and black streak. It is brittle with an uneven fracture and no obvious parting and cleavage. Its Vickers hardness (VHN10) is 144 kg/mm2 (range 131–167 kg/mm2) and its calculated density is 5.450 g cm. In reflected light, tsygankoite is white; between crossed polars it is dark grey to black. It is strongly anisotropic: rotation tints vary from light grey to dark grey to black. Pleochroism and internal reflections are not observed. The chemical composition of tsygankoite (wt %, electron-microprobe data) is: Mn 6.29, Hg 5.42, Tl 26.05, Pb 5.84, As 3.39, Sb 30.89, S 21.87, total 99.75. The empirical formula, calculated on the basis of 90 atoms pfu, is: Mn8.06Tl8.00Hg1.90(Sb17.87As3.19Pb1.99Tl0.97)Σ24.02S48.03. Tsygankoite is monoclinic, space group C2/m, a = 21.362(4) Å, b = 3.8579(10) Å, c = 27.135(4) Å, β = 106.944(14)°, V = 2139.19(17) Å3 and Z = 1. The five strongest diffraction peaks from X-ray powder pattern (listed as (d,Å(I)(hkl)) are: 3.587(100)(112), 3.353(70)(−114), 3.204(88)(405), 2.841(72)(−513), and 2.786(99)(−514). The crystal structure of tsygankoite was refined from single-crystal X-ray diffraction data to R = 0.0607 and consists of an alternation of two thick layer-like arrays, one based on PbS-archetype and the second on SnS-archetype. Tsygankoite has been approved by the IMA-CNMNC under the number 2017-088. It is named for Mikhail V. Tsyganko, a mineral collector from Severouralsk, Northern Urals, Russia, who collected the samples where the new mineral was discovered. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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Open AccessArticle Vorontsovite, (Hg5Cu)Σ6TlAs4S12, and Ferrovorontsovite, (Fe5Cu)Σ6TlAs4S12: The Tl- and Tl-Fe-Analogues of Galkhaite from the Vorontsovskoe Gold Deposit, Northern Urals, Russia
Minerals 2018, 8(5), 185; https://doi.org/10.3390/min8050185
Received: 11 April 2018 / Revised: 24 April 2018 / Accepted: 25 April 2018 / Published: 28 April 2018
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Abstract
Two new mineral species, vorontsovite, ideally (Hg5Cu)TlAs4S12, and ferrovorontsovite, ideally (Fe5Cu)TlAs4S12, the Tl- and Tl–Fe-analogues of galkhaite, respectively, have been discovered at the Vorontsovskoe gold deposit, Northern Urals, Russia. They occur [...] Read more.
Two new mineral species, vorontsovite, ideally (Hg5Cu)TlAs4S12, and ferrovorontsovite, ideally (Fe5Cu)TlAs4S12, the Tl- and Tl–Fe-analogues of galkhaite, respectively, have been discovered at the Vorontsovskoe gold deposit, Northern Urals, Russia. They occur as anhedral grains up to 0.5 mm (vorontsovite) and 0.2 mm (ferrovorontsovite) embedded in a calcite-dolomite matrix. The chemical composition of vorontsovite (wt %) is: Hg 35.70, Fe 5.36, Zn 1.26, Cu 3.42, Ag 0.64, Tl 11.53, Cs 0.35, Pb 0.04, As 15.98, Sb 2.35, Te 0.41, S 22.70, Se 0.02, total 99.76. The empirical formula, calculated on the basis of 23 atoms pfu, is: [(Hg3.02Fe1.63Zn0.33)Σ4.98(Cu0.91Ag0.10)Σ1.01](Tl0.96Cs0.04)Σ1.00(As3.62Sb0.33Te0.05)Σ4.00S12.01. The composition of ferrovorontsovite (wt %) is: Hg 25.13, Fe 9.89, Zn 1.16, Cu 3.95, Ag 0.45, Tl 12.93, Cs 0.44, Pb 0.04, As 17.83, Sb 2.15, Te 0.40, S 24.91, total 99.28. The empirical formula, calculated on the basis of 23 atoms pfu, is: [(Fe2.74Hg1.94Zn0.27)Σ4.95(Cu0.96Ag0.06)Σ1.02](Tl0.98Cs0.05)Σ1.03(As3.68Sb0.27Te0.05)Σ4.00S12.00. Both minerals are cubic, space group I-43m, with a = 10.2956(6) Å, V = 1091.3(1) Å3, Z = 2 (vorontsovite); and a = 10.2390(7) Å, V = 1073.43(22) Å3, Z = 2 (ferrovorontsovite). The crystal structures of both minerals were refined to R = 0.0376 (vorontsovite) and R = 0.0576 (ferrovorontsovite). Vorontsovite and ferrovorontsovite have been approved by the IMA-CNMNC under the numbers 2016-076 and 2017-007, respectively. The first one is named after the type locality, but also honors the mining engineer Vladimir Vasilyevich Vorontsov. The second is named for its chemical composition, as the Fe-analogue of the first. Both species are isostructural with galkhaite, being its Tl- and Tl–Fe analogues, respectively, and forming altogether the galkhaite group. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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Review

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Open AccessReview Modular Crystal Chemistry of Thallium Sulfosalts
Minerals 2018, 8(11), 478; https://doi.org/10.3390/min8110478
Received: 11 September 2018 / Revised: 18 October 2018 / Accepted: 19 October 2018 / Published: 24 October 2018
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Abstract
Complex sulfides of thallium with As, Sb, or Bi and with other cations (‘thallium sulfosalts’) are a large group of crystal structures with extreme variability. Incorporation of the large Tl+ cation in them is solved in several different ways: housing of Tl [...] Read more.
Complex sulfides of thallium with As, Sb, or Bi and with other cations (‘thallium sulfosalts’) are a large group of crystal structures with extreme variability. Incorporation of the large Tl+ cation in them is solved in several different ways: housing of Tl in columns of capped trigonal coordination prisms, which form separate walls in the structure (in different combinations with Pb and/or Sb), regular alternation of large Tl with small cations (As), presence of structural arrays of Tl coordination polyhedra paralleled by arrays of As coordination pyramids with a frequency ratio 1:2, omission derivatives with cavities for Tl accommodation and formation of layer structures with thallium concentrated into separate (inter)layers of different types. The first principle leads to a large family of sartorite homologues and rare lillianite homologues, as well as to the chabournéite group. The second one to the hutchinsonite family, omission derivatives form the routhierite and galkhaite groups, and the 1:2 periodicity ratio principle results in several outstanding structures from different groups. Layer structures consist of two-component and three-component layer combinations. Close cation-cation interactions are present but rare. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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Open AccessReview The Lengenbach Quarry in Switzerland: Classic Locality for Rare Thallium Sulfosalts
Minerals 2018, 8(9), 409; https://doi.org/10.3390/min8090409
Received: 11 July 2018 / Revised: 6 September 2018 / Accepted: 6 September 2018 / Published: 14 September 2018
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Abstract
The Lengenbach quarry is a world-famous mineral locality, especially known for its rare and well-crystallized Tl, Pb, Ag, and Cu bearing sulfosalts. As of June 2018, it is the type locality for 44 different mineral species, making it one of the most prolific [...] Read more.
The Lengenbach quarry is a world-famous mineral locality, especially known for its rare and well-crystallized Tl, Pb, Ag, and Cu bearing sulfosalts. As of June 2018, it is the type locality for 44 different mineral species, making it one of the most prolific localities worldwide. A total of 33 thallium mineral species have been identified, 23 of which are type minerals. A brief description of several thallium species of special interest follows a concise and general overview of the thallium mineralization. Full article
(This article belongs to the Special Issue Thallium: Mineralogy, Geochemistry and Ore Processes)
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