Phase relations in the systems Cu2S-PbS-Bi2S3 and Ag2S-PbS-Bi2S3 and their mineral assemblages

The phase diagrams of the systems Cu₂S-PbS-Bi₂S₃ and Ag₂S-PbS-Bi₂S₃ have been investigated in the present study. The paper is concerned with the complete solid solution between bismuthtite and aikinite above 300°C in the system Cu₂S-PbS-Bi₂S₃. The synthetic phases CuBi₃S₅ and Cu₃Bi₅S₉ have their solid solution ranges in the ternary system with 9 and 26 mole% PbS at maximum, respectively. A complete solid solution between PbS and AgBiS₂ divides the phase diagram of the system Ag₂S-PbS-Bi₂S₃ into two parts: Bi-rich and Ag-rich. All sulfosalt minerals and solid solutions, including pavonite ss, lillianite ss, heyovskyite and benjaminite are on the Bi-rich side. And divarant relations were found between pavonite ss -lillianite ss, benjaminite and bismuthtite as well as between lillianite ss -bismuthtite and galenobismutite. Synthetic experiments using LiCl-KCl flux technique show that when a minor amount of copper (less lwt.%) is added in, many of Ag-and Pb-bismuth sulfosalt minerals, for example, vikingite (Ag₅Pb₈Bi₁₃S₃₀), are synthesized successively, particularly at 400°C. So is heyrovskyite, which has a solid solution range with 3.7 mole% Cu₂S at maximum in the system Cu₂S-PbS-Bi₂S₃.     

Two Se-bearing Ag–Bi Sulphosalts, Benjaminite and Matildite from the Ikuno Deposits, Hyogo Prefecture, Japan –Au–Ag Mineralization in Polymetallic Zone

Abstract: Se-bearing benjaminite and matildite are described from the polymetallic zone of the Ikuno deposits, Japan. The former is the first occurrence in Japan, and is from two separate veins, the Nanten and Daimaru, while the locality of the latter could not be specified. The empirical formulae of two benjaminites based on 22 atoms are (Ag_{2. 74}Cu_{0. 24})_{Σ2. 98}(Bi_{7. 00}Sb_{0. 01})_{Σ7. 01}(S_{10. 89}Se_{1. 12})_{Σ12. 01} (Nanten) and (Ag_{2. 90}Cu_{0. 10})_{Σ3. 00}(Bi_{6. 74}Pb_{0. 18}Sb_{0. 07})_{Σ6. 99}(S_{11. 68}Se_{0.33)Σ12. 01} (Daimaru), leading to the validation of the formula Ag₃Bi₇S₁₂ as the ideal one for benjaminite, and that of matildite based on 4 atoms is Ag_{1. 00}Bi_{1. 00}(S_{1. 78}Se_{0. 22})Σ_{2. 00}. These designate the substitution of Se for S in all of them, where Se is preferentially incorporated into these Ag-Bi sulphosalts. The unit-cell parameters of them and matildite are: a 13. 272, b 4. 037, c 20. 185 Å, and β 103. 16° (Daimaru), a 13. 270, b 4. 040, c 20. 273 Å, and β103. 17° (Nanten); and a 4. 0670, c 18. 996 Å, respectively. The products of Au-Ag mineralization in the Ikuno polymetallic vein-type deposits also occur as such Ag-Bi sulfosalts as benjaminite and matildite, in addition to pavonite, “treasurite derivative” and “electrum” with cassiterite in the polymetallic zone, and also do as “electrum”, acanthite, and pyrargyrite-proustite in the Au-Ag zone. The significant quantity of the Ag-Bi sulfosalts does not violate the zoning occupying the outermost part of the zonal distribution of ores in the deposits.     

Bismuthoan Galena—A New Variety of Galena

Bismuthoan galena is a variety of galena, resulting from the replacement of Bi for some Pb in galena.This mineral occurs in the No.11 orebody of the Lamo skarn-type Zn-Cu deposit in the Dachang ore field ,but only the No,11 orebody of the Lamo deposit is developed such bismuthoan galena.This is closely related to such a geochemical background that the No.11 orebody contains high Bi and Bi-sulfosalt minerals are well developed there.Eight electron microprobe analyses of five samples give 60.17-70.20%Pb(66.94% on average),10.00-16.06%Bi (12.47%),4.83-8.97%Ag(6.39%)and 13.25-13.98% S(13.65%).Its molecular formula is Pb0.76,Bi0.14,Ag0.13,1.03S.No galena so high in Bi has been reported in the literature and this is the first report in China.     

Phase relations and mineral assemblages in the Ag-Bi-Pb-S system

Phase relations within the Ag-Bi-S, Bi-Pb-S, and Ag-Pb-S systems have been determined in evacuated silica tube experiments. Integration of experimental data from these systems has permitted examination and extrapolation of phase relations within the Ag-Bi-Pb-S quaternary system. — In the Ag-Bi-S system liquid immiscibility fields exist in the metal-rich portion above 597±3°C and in the sulfur-rich portion above 563±3°C. Ternary phases present correspond to matildite (AgBiS₂) and pavonite (AgBi₃S₅). Throughout the temperature range 802±2°C to 343±2°C the assemblage argentite (Ag₂S) + bismuth-rich liquid is stable; below 343°C this assemblage is replaced by the assemblage silver + matildite. — Five ternary phases are stable on the PbS-Bi₂S₃ join above 400°C — phase II (18 mol-% Bi₂S₃), phase III (27 mol-% Bi₂S₃), cosalite (33.3 mol-% Bi₂S₃), phase IV (51 mol-% Bi₂S₃), and phase V (65 mol-% Bi₂S₃). Phase IV corresponds to the mineral galenobismutite and is stable below 750±3°C. Phases II, III, and V do not occur as minerals, but typical lamellar and myrmekitic textures commonly observed among the Pb-Bi sulfosalts and galena evidence their previous existence in ores. Phase II and III are stable from 829±6°C and 816±6°C, respectively, to below 200°C; Phase V, stable only between 730±5°C and 680±5°C in the pure Bi-Pb-S system is stabilized to 625±5°C by the presence of 2% Ag₂S. Experiments conducted with natural cosalites suggest that this phase is stable only below 425±25°C in the presence of vapor. — In the Ag-Pb-S system the silver-galena assemblage is stable below 784±2°C, whereas the argentite + galena mineral pair is stable below 605±5°C. — Solid solution between matildite and galena is complete above 215±15°C; below this temperature characteristic Widmanstätten structure-like textures are formed through exsolution. Schematic phase relations within the quaternary system are presented at 1050°C, at 400°C, and at low temperature.

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Zusammenfassung Die Phasenbeziehungen in den Systemen Ag-Bi-S, Bi-Pb-S und Ag-Pb-S wurden durch Versuche in evakuierten Quarzglasröhrchen bestimmt. Die Auswertung aller experimentellen Daten gestattete eine Extrapolation der Phasenbeziehungen im quaternären System Ag-Bi-Pb-S. — Im System Ag-Bi-S besteht ein Zwei-Schemlzenfeld im metallreichen Teil über 597±3°C und im schwefelreichen Teil über 563±3°C. Die ternären Phasen entsprechen den Mineralien Schapbachit (AgBiS₂) und Pavonit (AgBi₃S₅). Zwischen 802±2°C und 343±2°C ist die Paragenese Silberglanz (Ag₂S) + Bi-reiche Schmelze stabil; unterhalb 343°C wird sie jedoch ersetzt durch die Paragenese Silber + Schapbachit. — Fünf ternäre Phasen sind stabil im Schnitt PbS-Bi₂S₃ oberhalb von 400°C: Phase II (18 Mol-% Bi₂S₃), Phase III (27 Mol-% Bi₂S₃), Cosalite (33.3 Mol-% Bi₂S₃), Phase IV (51 Mol-% Bi₂S₃) und Phase V (65 Mol-% Bi₂S₃). Phase IV entspricht dem Mineral Galenobismutit und ist stabil unterhalb 750±3°C. Die Phasen II, III und V kommen zwar nicht in der Natur vor, jedoch weisen typische myrmekitische und lamellare Gefüge, die man häufig in Pb-Bi-Sulfosalzen und deren Verwachsungen mit Bleiglanz beobachtet, auf die ehemalige Existenz solcher Phasen in diesen Erzen hin. Die Phasen II und III sind stabil von 829±6°C bzw. 816±6°C bis unter 200°C. Die Phase V, die im reinen System Bi-Pb-S zwischen 730±5°C und 680±5°C auftritt, wird in Gegenwart von 2% Ag₂S stabilisiert bis herab zu 625±5°C. Versuche mit natürlichen Cosaliten lassen darauf schließen, daß diese Phase nur unterhalb 425±25°C in Gegenwart einer Gasphase stabil ist. — Im System Ag-Pb-S ist die Paragenese Silber-Bleiglanz unterhalb von 784±2°C stabil, die Paragenese Silberglanz-Bleiglanz dagegen unterhalb 605±5°C. — Die Mischkristallreihe von Schapbachit und Bleiglanz ist vollständig oberhalb 215±15°C; unterhalb dieser Temperatur entstehen charakteristische Entmischungsgefüge ähnlich den Widmannstättenschen Figuren. Für das quaternäre System werden schematische Phasenbeziehungen für 1050°C, 400°C und eine noch tiefere Temperatur gegeben.

     

The role of iron in tetrahedrite and tennantite determined by Rietveld refinement of neutron powder diffraction data

Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12?xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12?xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I $ \ifmmode\expandafter\bar\else\expandafter\=\fi{4} Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12−xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12−xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I 3 m). The refinement results also confirm that M2 is a split (24g), flat-pyramidal site situated statistically on both sides of the S1−S1–S2 triangle. In tetrahedrite, this split is about 0.6 ?, in tennantite about 0.7 ?. Trends in bond lengths and magnitude of the M2 split were evaluated by means of linear regression with Fe concentration as the independent variable.     

Ag2(S,Se) solid solutions in the ores of the Rogovik gold-silver deposit (northeastern Russia)

The relationships and chemical compositions of silver sulfoselenides in the ores of the Rogovik gold-silver deposit (northeastern Russia) were studied to refine the low-temperature region of the Ag₂S-Ag₂Se phase diagram and identify contradictions between natural and experimental data. Two types of relationships between the phases of the system Ag₂S-Ag₂Se have been recognized using optical and scanning electron microscopy: (1) Se-acanthite and S-naumannite occur as monomineral microinclusions or fill cracks in the grains or the interstices of other minerals, and acanthite (free of impurities) forms rims on Fe-sphalerite; (2) Se-acanthite forms rims on S-naumannite. Electron probe microanalysis of silver sulfoselenides from the Rogovik ores revealed 0–7.9 wt.% Se in acanthite and 0–3.2 wt.% S in naumannite, which corresponds to the acanthite series Ag₂S-Ag₂S₀.₇₄Se₀.₂₆ and naumannite series Ag₂S₀.₂₈Se₀.₇₂-Ag₂Se. The composition ranges of the studied acanthite and naumannite series are wider than those of natural silver sulfoselenides from the Guanajuato (Mexico), Silver City (USA), Salida (Indonesia), and other deposits (Ag₂S-Ag₂S0.85Se0.₁5 and Ag₂S0.₁₂Se0.88-Ag₂Se, respectively) but are significantly narrower than the composition ranges of synthetic samples: Ag₂S-Ag₂S0.₄Se0.6 and Ag₂S0.3Se0.₇-Ag₂Se. The presence of intergrowths of two phases of the Ag₂S-Ag₂Se series in the form of Se-acanthite rims on S-naumannite in the Rogovik ores and the absence of three-phase intergrowths of silver sulfoselenides Ag₂S_1 -xSe_x from this and other deposits do not confirm the assumption on the existence of the third solid solution. The results of earlier studies of natural Ag₂(S,Se) solid solutions show the existence of two solid solutions (of the acanthite and naumannite series) in the Ag₂S-Ag₂Se system and confirm the experimental data. It is necessary to carry out a detailed examination of natural silver sulfoselenides falling in the interval from Ag2S0.4Se0.6 to Ag2S0.3Se0.7 in order to identify the limits of two-phase immiscibility.     

57Fe-Moessbauer spectra,electronic and crystal structure of members of the CuS2-FeS2 solid solution series

Members of the (Cu, Fe)S₂ solid solution crystallize in the pyrite structure type, space group Pa 3, Cu and Fe being statistically distributed on the metal sites. Within this series, a semiconductor to metal transition can be detected between 25 and 38 mole% CuS₂. Compositional dependent ⁵⁷Fe-Moessbauer spectra reveal Fe²⁺ in low-spin configuration. A minimum of the quadrupole splitting and the slope in the ⁵⁷Fe-isomer shift in the intermediate part of the system, near 30 mole% CuS₂, can be correlated with the onset of metallic conductivity, whereas the structural parameters are not influenced by this transition. The analysis of the compositional dependency of the quadrupole splitting, in comparison to the isotypic system (Co, Fe)S₂, leads to the conclusion that Cu in solid (Cu, Fe)S₂ compounds is Cu⁺ with an Ar -3 d¹⁰ electronic configuration.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

A microscopic study of synthetic PbS-Rich homologues nPbS-mBi2S3

The PbS-Bi₂S₃ join was studied up to 25 mole percent Bi₂S₃ by electron microscopy and diffraction. It was found that Bi₂S₃ can be incorporated into the PbS matrix by tropochemical twinning, forming isolated {113}_PbS microtwins, or after clustering of these defects, lamellar twinned regions. Only two known mineral members of the homologous series (lillianite Pb₃Bi₂S₆ and heyrowskyite Pb₆Bi₂S₉) were found to be stable in this part of the PbS-Bi₂S₃ join, while irregularly spaced twin bands within these two structures were observed where deviations in the PbS/Bi₂S₃ ratio from 6/1 and 3/1, respectively, took place. No ordered intergrowth members were found between heyrowskyite and lillianite. The difference between the PbS-Bi₂S₃ join and the analogous MnS-Y₂S₃ one was attributed to the lone pair of nonbonded electrons from the Bi³⁺ ions, which tends to concentrate these ions in the vicinity of the twin planes.     

Ore mineralogy of the Waschgang gold-copper deposit,upper carinthia,Austria

Summary The gold-copper deposit at Waschgang (Southern Goldberg mountains, Upper Carinthia) belongs to a type of stratiform, dominantly pyritic deposit, which is hosted by greenschists (Alpine Kieslager;Friedrich, 1936). The ores occur as impregnations (ore type 1) and as massive ores (ore type 2) in prasinitic rocks of the Obere Schieferhülle of the Penninic unit. A N–S trending fault zone cuts the ore deposit to the W (Lettenkluft); the position of the displaced part is unknown.The mineralogical composition of type 1 ores is rather monotonous. Pyrite is the most important ore, minor components are chalcopyrite, bornite, sphalerite and magnetite. No visible native gold has been observed in this type of ore. Type 2 ores are dominated by chalcopyrite and are characterized by large amounts of visible native gold. The majority of these ores occur in the vicinity of the Lettenkluft.Type 2 ores carry a great variety of cogenetic mineral inclusions, of which several have been studied with the electron microprobe and investigated by X-ray methods. These include: tetradymite, Bi₂Te_1.81Se_0.13S; hessite, Ag₂Te; matildite, AgBiS₂; gladite, Cu_1.09Pb_1.14Bi_5.28S₉; krupkaite, CuPbBiS₆; pekoite, Cu_1.09Pb_0.97Bi_12.56S₁₈; (?) benjaminite, (Ag_2.72Cu_0.42)_3.14 (Bi_6.88Pb_0.12)₇(S_11.08Se_0.92)₁₂; pavonite, (Ag_0.74Cu_0.45)_1.19(Bi_2.86Pb_0.27)_3.13 (S_4.96Se_0.04)₅; (?) cupropavonite, (Cu_0.73Ag_0.4)_1.13(Bi_2.59Pb_0.83)_3.42S₅; and siegenite, (Ni_1.07Co_1.76Cu_0.19)_3.02S₄. Other components have been determined by qualitative and quantitative microscopy and include: bornite, idaite, mawsonite, sphalerite, millerite, magnetite, hematite, ilmenite, rutile and a variety of silicates.While the layered ore impregnations (type 1 ores) can be considered as being syngenetic with the associated volcanics of Jurassic age, a syn- to postkinematic (Alpidic) crystallization can be postulated for the type 2 ores. These ores are considered as remobilized and reconcentrated parts of the type 1 ores formed in tectonic stress zones. The crystallization of chalcopyrite and included ore minerals occurred during the cooling history of Alpidic metamorphism, for which in this region a maximum temperature of 500°C and pressures between 4–6 kb have been deduced from the mineral assemblage of the surrounding prasinites, consisting of albite with rims of oligoclase, epidote, chlorite, sphene and amphibole (Höck, 1980). Based onSpringer's limit of 300°C as approximately representing the maximum temperature at which natural members of the bismuthinite-aikinite mineral series have been formed, krupkaite and gladite with the intergrown pavonite type phases might have been deposited directly from solutions at or below 300°C. Unmixing of pekoite from gladite probably occurred at or below the same temperature.

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Zur Erzmineralogie der Gold-Kupfer-Lagerstätte Waschgang, Oberkärnten, Österreich

Zusammenfassung Die Gold-Kupfer-Lagerstätte Waschgang (südliche Goldberggruppe, Oberkärnten) ist dem Typus der stratiformen Kiesvererzungen in Grüngesteinen (Alpine Kieslager;Friedrich, 1936) zuzurechnen. Die Erzmineralisationen treten als stoffkonkordante Imprägnationen (Vererzungstypus 1) und als Derberze (Vererzungstypus 2) in Prasiniten der Oberen Schieferhülle des Penninikums auf. Das Erzlager wird im W an einer N–S streichenden Störung abgeschnitten; die Position des verworfenen W-Flügels ist nicht bekannt.Die Imprägnationserze sind in ihrer mineralogischen Zusammensetzung monoton; Pyrit als Haupterz überwiegt bei weitem die sporadischen Begleiter Kupferkies, Bornit, Sphalerit und Magnetit. Dieser Typus führt kein Freigold.Die von Kupferkies dominierten und an Freigold reichen Derberze treten vor allem im Bereich der Lettenkluft auf. Sie sind durch eine Vielfalt zum Teil komplex zusammengesetzter Einschlußminerale gekennzeichnet, von denen einige mittels Mikrosonde und röntgenographischer Methoden untersucht wurden: Tetradymit, Bi₂Te_1,81Se_0,13S; Hessit, Ag₂Te; Matildit, AgBiS₂; Gladit, Cu_1,09Pb_1,14Bi_5,28S₉; Krupkait, CuPbBiS₆; Pekoit, Cu_1,09Pb_0,97Bi_12,56S₁₈; (?) Benjaminit (Ag_2,72Cu_0,42)_3,14(Bi_6,88Pb_0,12)₇(S_11,08Se_0,92)₁₂; Pavonit, (Ag_0,74Cu_0,45)_1,19(Bi_2,86Pb_0,27)_3,13 (S_4,96Se_0,04)₅; (?) Cupropavonit, (Cu_0,73Ag_0,4)_1,13(Bi_2,59Pb_0,83)_3,42S₅; Siegenit, (Ni_1,07Co_1,76 Cu_0,19)_3,02S₄. Andere Mineralphasen wurden mittels qualitativer und quantitativer Mikroskopie bestimmt: Bornit, Idait, Mawsonit, Sphalerit, Millerit, Magnetit, Hämatit, Ilmenit, Rutil und Silikate.Während die stoffkonkordaten Imprägnationserze syngenetisch mit den assoziierten jurassischen Vulkaniten anzusehen sind, wird für die Derberze eine syn- bis postkinematische Kristallisation angenommen. Sie sind als remobilisierte und rekonzentrierte Teile der Imprägnationserze in tektonisch besonders beanspruchten Lagerstättenteilen anzusehen. Die Kristallisation des Kupferkieses und seiner Einschlußminerale erfolgte während der Abkühlungsphase der alpidischen Metamorphose, für die im betrachteten Gebiet eine Maximaltemperatur von ca. 500°C und Drucke zwischen 4–6 kb aufgrund der Petrologie der erzführenden Prasinite angenommen werden können. Die dafür maßgebende Paragenese besteht aus Albit mit Oligoklasrändern, Epidot, Chlorit, Sphen und Amphibol (Höck, 1980). Zieht man die vonSpringer (1971) ermittelte Stabilitätsgrenze von ±300°C für natürliche Mischkristalle der Bismuthinit-Aikinit-Reihe in Betracht, können für Krupkait und Gladit und den damit verwachsenen Pavonit-Phasen Bildungstemperaturen um oder unterhalb 300°C angenommen werden. Die Kristallisation dieser Minerale dürfte dabei direkt aus Lösungen erfolgt sein. Die als Entmischungsstrukturen interpretierten Gladit-Pekoit-Verwachsungen legen den Schluß einer primären Bildung beider Minerale als feste Lösung nahe, deren Zerfall vermutlich unterhalb von 300°C erfolgte.

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With 13 Figures

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Herrn em. Univ.-Prof. Dr.-Ing. O. M. Friedrich zum 80. Geburtstag in Dankbarkeit gewidmet

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This investigation forms part 2 of a major study on Genetic Types of Gold Deposits of the Alps.     

A cervelleite-like mineral and other Ag-Cu-Te-S minerals [Ag2CuTeS and (Ag,Cu)2TeS] in gold-bearing veins in metamorphic rocks of the Cycladic Blueschist Unit, Kallianou, Evia Island, Greece

A cervelleite-like mineral, two unnamed silver sulfotellurides in the system Ag-Cu-Te-S [Ag₂CuTeS, (Ag,Cu)₂TeS], Te-rich polybasite and cadmian tetrahedrite occur in gold-bearing quartz veins in metapelites and faults within brecciated marbles of the Cycladic Blueschist Unit in the Kallianou area (southern Evia Island, Greece). The quartz veins and faults are discordant to syn-metamorphic structures and formed during ductile to brittle deformation in the final stages of exhumation of the Styra Nappe extrusion wedge (~21?Ma). Te-rich polybasite (up to 7.4 wt. % Te), cadmian tetrahedrite (up to 12.4 wt. % Cd), together with electrum (23?C54 wt. % Ag) and the sulfotellurides, are the main silver carriers in the mineralization. The two unnamed sulfotellurides, Ag₂CuTeS and (Ag,Cu)₂TeS are believed to be new quaternary minerals in the system Ag-Cu-Te-S. These minerals and the cervelleite-like phase could have exsolved from galena during cooling (below 200°C). Initial temperatures for the formation of the sulfotellurides, in the form of hessite-intermediate solid solution, at Kallianou may be up to 300°C under logfS₂ values between?~ ?11.5 to ?8.3, and logfTe₂ from?~ ?14.8 to ?7.8. The values of logfTe₂ and logfS₂ during re-equilibration (at ~200°C) were constrained to ?19.5 to ?15.2 and to ?15.8 to ?11.5 respectively.     

The Hiendelaencina mining district (Guadalajara,Spain)

The Hiendelaencina mining district (Guadalajara, Spain), includes the ore deposits of the Hiendelaencina, La Bodera and Congostrina areas. In this paper a general overview of this district is given, with special emphasis on the parageneses, mineralizing stages and chemical characteristics of the sulphides and sulphosalts. These deposits contain silver in Sb-rich sulphosalts such as freibergite, pyrargyrite, polybasite, stephanite, freieslebenite and the Bi-rich sulphosalt, aramayoite. Three mineralizing stages have been detected in Hiendelaencina and Congostrina: (1) As-Fe; (2) Cu-Zn-Fe-Sb-Ag; and (3) Pb-Sb-Ag (±Bi) but only two in La Bodera (stages 2 and 3). The average sulphosalt formulas are: freibergite (Cu_0.5 Ag_5.9) (Fe_1.42 Zn_0.66) (Sb_4.49 As_0.02) S₁₃; pyrargyrite Ag_3.38 Sb_1.0 S₃; polybasite (Ag_16.3Cu_0.15) (Sb_2.8 As_0.15) S₁₁; stephanite Ag_6.7 Sb_1.38 S₄; freieslebenite Ag_1.1 Sb_0.83 Pb_1.05 S₃ and aramayoite Ag_1.06 Bi_{0. 35} Sb_0.7 Pb_0.03 S₂. The compositional patterns of these sulphosalts (mainly based on the Sb/(Sb + Ag), Ag/ (Ag + Cu), Sb(Ag + As) and Ag/(Ag + Cu) ratios) are outlined, pointing broadly to similar tendencies in their chemistry and genetic conditions.     

Heyrovskýite, 6(Pb0.86Bi0.08(Ag,Cu)0.04)S . Bi2S3 from Hůrky,Czechoslovakia, a new mineral of genetic interest

Heyrovskýite has a composition range from 6(Pb_0.83Bi_0.10(Ag, Cu)_0.07) S . Bi₂S₃ to 6(Pb_0.92Bi_0.05(Ag, Cu)_0.03) S . Bi₂S₃. It is orthorhombic. Crystal forms {100}, {010}, {120}, {140}, {250}, and {321} (?) were observed; {010} and {140} are dominant. Elongated c, flattened (010). a:b:c _morph=0.432:1:0.128. Cell parameters a=13.705±0.013 Å, b=31.194±0.033, c=4.121±0.003, a:b:c _X-ray=0.439:1:0.132. The diffraction symbol is Bb, compatible with Bbmm, Bb2₁ m, Bbm2. Morphology corresponds to point groups mmm or mm2, reducing the possible space groups to Bbmm and Bbm2. Density at 20 °C is 7.17 g/cm³, calculated, 7.18; Z=4. Micro-indentation hardness (VHN) (50 g load) is 166 to 234 kp/mm². Strongly anisotropic; reflectance strongly variable, roughly the same as of galena. Etch tests: HNO₃ (1:1) and HCl (1:1) positive, FeCl₃ 20%, HgCl₂ 5%, KCN 20%, and KOH 40% all negative. Powder data are identical with those for phase II of Otto and Strunz (1968). Heyrovskýite is associated with galena and cosalite at H?rky, Czechoslovakia.     

Sulfur–selenium isomorphous substitution and morphotropic transition in the Ag3Au(Se,S)2 series

Gold–silver sulfoselenides of the series Ag3AuSexS2–x (x = 0.25; 0.5; 0.75; 1; 1.5) were synthesized from melts on heating stoichiometric mixtures of elementary substances in evacuated quartz ampoules. According to X-ray single-crystal analysis, compound Ag₃Au₁Se_0.5S_1.5 has the structure of gold–silver sulfide Ag3AuS2 (uytenbogaardtite) with space group R3c. The volume of this compound is 1.5% larger than that of the sulfide analog. According to powder X-ray diffraction, compounds Ag₃AuSe_0.25S_1.75 and Ag₃AuSe_0.75S_1.25 also show trigonal symmetry. Compounds Ag₃AuSeS and Ag₃AuSe_1.5S_0.5 are structurally similar to the low-temperature modification of gold–silver selenide Ag₃AuSe₂ (fischesserite) with space group I4132. These data suggest the existence of two solid solutions: petzite-type cubic Ag₃AuSe₂–Ag₃AuSeS (space group I4132) and trigonal Ag₃AuSe_0.75S_1.25–Ag₃AuS₂ (space group R3c).It was found that fischesserite from the Rodnikovoe deposit (southern Kamchatka) contains 3.5–4 wt.% S. At the Kupol deposit (Chukchi Peninsula), fischesserite contains up to 2.5 wt.% S and uytenbogaardtite contains up to 5.3 wt.% Se. At the Ol’cha and Svetloe (Okhotskoe) deposits (Magadan Region), uytenbogaardtite contains up to 0.5 and 1.8 wt.% Se, respectively. Literature data on the compositions of silver–gold selenides and sulfides from different deposits were summarized and analyzed. Analysis of available data on the S and Se contents of natural fischesserite and uytenbogaardtite confirms the miscibility gap near composition Ag3AuSeS.     

Pb−Bi−(Cu)-sulfosalts in Paleozoic gneisses and schists from Oberpinzgau,Salzgurg province,Austria

Summary Pb–Bi–(Cu)-sulfosalts occur as minor minerals widely distributed in rocks of the Penninic unit (gneisses, schists, metavolcanics, etc.), Oberpinzgau, Salzburg. The sulfosalts have been investigated by ore microscopy, X-ray diffraction and electron microprobe analysis. The phases identified are: heyrovskyite, cosalite (Moaralm, Sedl, and Wiesbachrinne in the Habach Valley), lillianite (Moaralm, Sedl; Modereck near the Fuscher Valley), galenobismutite (Bärenbad in the Hollersbach Valley) and Bi-bearing galena. Heyrovskyite (Moaralm) has a composition close to Pb₆Bi₂S₉, with Ag contents between 0.2 (Sedl) and 0.6 (Moaralm) wt.%. Lillianite has the composition Pb_2.86–2.91 Bi_2.08–2.17Ag_0.04–0.08 S₆, and cosalite, Pb_1.81–2.04 Bi_1.92–2.02 Ag_0.02–0.06 Cu_0.11–0.18S₅. The average chemical composition of galenobismutite is Pb_1.25Bi_1.6Sb_0.1Cu_0.1Ag_0.02Fe_0.1S₄. Needle-like inclusions of a joseite-type mineral, joseite-A (Bi,Pb)_4.01 Te_0.9S_2.08, and irregular to needle-like grains of native bismuth usually occur along the elongation direction of the lath-like galenobismutite crystals.The occurrences can be divided into two types: 1) stratiform Pb–Bi sulfosalts which occur only in the quartzite intercalations of the Paleozoic Habach unit (Frasl, 1958), and 2) alpidic vein type Pb–Bi sulfosalts which occur in quartz veins intersecting gneisses and are considered to be the remobilization products of the first type. Temperature of formation for heyrovskyite in this region is estimated at between 400±25°C and 500°C. Most probably, the assemblage heyrovskyite-lillianite-galena (Moaralm) was formed at or below 473°C.

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Pb–Bi–(Cu)-Sulfosalze in paläozoischen Gesteinen des Oberpinzgau, Salzburg, Österreich

Zusammenfassung Pb–Bi-Sulfosalze verschiedener Vorkommen des Oberpinzgau, Salzburg, wurden mittels Erzmikroskopie, röntgenographischer Methoden und Mikrosonde untersucht. Folgende Phasen wurden identifiziert: Heyrovskyit, Cosalit (Moaralm, Sedl und Wiesbachrinne; alle Habachtal), Lillianit (Moaralm, Sedl; Modereck nahe des Fuschertales), Galenobismutit (Bärenbad, Hollersbachtal) und Bi-hältiger Bleiglanz. Heyrovskyit (Moaralm) ist nahezu Pb₆Bi₂S₉, mit Ag-Gehalten zwischen 0,2 (Sedl) und 0.6 (Moaralm) Gew.%, Lillianit Pb_2,86–2,91Bi_2,08–2,17Ag_0,04–0,08S₆, und Cosalit Pb_1,81–2,04Bi_1,92–2,02Ag_0,02–0,06 Cu_0,11–0,18S₅. Galenobismutit ist Pb_1,25Bi_1,6Sb_0,1Cu_0,1Ag_0,02Fe_0,1S₄. Nadelige Einschlüsse von Joseit-A, (Bi, Pb)_4,01Te_0,9S_2,08, und unregelmäßige bis nadelige Körner von ged. Wismut treten entlang der Längsrichtung der Galenobismutit-Kristalle auf. Die Mineralisationen sind an stratiforme, sulfidreiche Quarzlagen (Typus 1, z. B. Bärenbad) oder an diskordante Quarzgänge (Typus 2; alle anderen Vorkommen) gebunden. Typus 1 tritt innerhalb der altpaläzozischen Habachserie (Frasl, 1958), Typus 2 in Randbereichen dieser zu den Gneismassen der Habachzunge (z. T. auch in letzteren) auf. Die dem Typus 2 zugerechneten Vererzungen werden als Remobilisationsprodukte der altpaläozoischen Mineralisationen (Typus 1) angesehen.Die Bildungstemperatur des Heyrovskyit dürfte im betrachteten Bereich zwischen 400±25°C und 500°C gelegen haben; eine Bildungstemperatur von 473°C oder wening darunter wird für die Assoziation Heyrovskyit-Lillianit-Bleiglanz in Anlehnung an experimentelle Untersuchungen vonSalanci undMoh (1969) angenommen.

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This investigation forms part of a wider study Genetic types of gold deposits in the Alps.     

Mineralogy and textural relationships among sulphosalts and related minerals in the Bleikvassli Zn-Pb-(Cu) deposit, Nordland, Norway

Several distinct assemblages of Pb-Sb, Pb-As, Cu-Pb-Sb and Cu-Fe-Zn-Sn sulphosalts are identified in sulphide samples from Bleikvassli mine, Norway. Detailed optical microscopy and electron probe microanalysis have permitted investigation of textural relationships between minerals and compositional variations between different ore types. Tetrahedrite, typically containing 10–16?wt.% Ag (rare freibergite containing 25–30?wt.% Ag has also been identified in two samples), stannite (Cu₂(Fe>Zn)SnS₄), and meneghinite, CuPb₁₃Sb₇S₂₄, are widely distributed as trace constituents throughout massive pyritic and galena-rich ores. Native antimony and pyrargyrite occur in trace amounts in all ore types, as the breakdown products of earlier sulphosalts. Several distinct types of wall-rock mineralisation are present at Bleikvassli. Of considerable mineralogical interest are the coarse-grained sulphide mobilisates within the wall rock which contain a distinct?and characteristic suite of Pb-As sulphosalts:?tennantite?+?jordanite (Pb₁₄As₆S₂₃)?+?seligmannite (CuPbAsS₃) ± dufrenoysite (Pb₂As₂S₅). Bournonite (CuPbSbS₃) is the only Sb-bearing sulphosalt recognised in significant amounts within the mobilisates, meneghinite and tetrahedrite being conspicuously absent. These mobilisates display considerable Au enrichment; electrum can be confirmed, intimately associated with jordanite and tennantite. Appreciable Sb (up to 3?wt.%) is contained within galena in the mobilisates, in contrast to galena from massive ores which contains only negligible Sb. Contents of Ag and Bi in galena vary considerably in all ore types, but confirm earlier suggestions that galena is a major Ag-carrier at Bleikvassli. Boulangerite (Pb₅Sb₄S₁₁), jamesonite (FePb₄Sb₆S₁₄) and gudmundite (FeSbS) occur in trace amounts. Sn-sulphosalts are represented by kësterite, (Cu₂(Zn> Fe)SnS₄), but commonly zoned with respect to Zn/Fe ratio, in the mobilisates, rather than by stannite. A rare type of mobilisate, also in the wall rock, in which chalcocite and bornite are the main minerals, contains native Ag, stromeyerite (AgCuS), mckinstryite ((Ag,Cu)₂?S), Ag-free tetrahedrite, an unnamed Cu-Ag-Fe sulphide (Cu₃Ag₂FeS₄) and native Bi, myrmekitically intergrown with chalcocite. Although a comprehensive genetic model for the wall-rock mineralisation at Bleikvassli is largely impossible given the limitations in the present state of knowledge regarding mechanisms involved in remobilisation processes, a multi-stage model of remobilisation during regional metamorphism is considered to best explain the observations. An interplay of different solid- and liquid-state remobilisation mechanisms, in various combinations, is required to account for the macro- and microscopic observations. Remobilisation probably began during the earlier stages of metamorphism, with crystallisation and further remobilisation taking place during the entire metamorphic cycle, giving rise to the extensive chemical and mineralogical diversity observed today. Preserved mineral assemblages and their textural relationships reflect a complex sequence of replacement and decomposition reactions taking place during the latest phase of late-metamorphic crystallisation and subsequent cooling.     

Experimental investigation of the Ag-TI-Bi-Sb-S system

Summary Polymetallic ore deposits of low temperature origin often contain thallium as a minor element. By means of modern analytical methods numerous new T1 minerals are described, but their coexistence and equilibria are not investigated yet.The equilibria at 200°C of the quasi-quaternary system Ag₂S-Tl₂S-Sb₂-Sb₂S₃-Bi₂S₃ and the corresponding subsystems were studied. The system Ag₂S-Tl₂S-Sb₂S₃-Bi₂S₃ contains only one quasiquaternary phase, AgTlSbBiS₄, which is connected by tie-lines with all quasiternary phases in the system (Ag₄Sb₃BiS₈ and Ag₃Tl₃Sb₂S₆) and with most quasibinary phases: SbBiS₃, weissbergite (TlSbS₂), (TlBiS₂, pyrargyrite (Ag₃SbS₃), miargyrite (AgSbS₂) and matildite (AgBiS₂). This phase diagram makes it possible to investigate all important naturally occurring parageneses of Ag and Tl sulphosalts containing Sb and Bi.

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Die experimentelle Untersuchung des Ag-TI-Sb-Bi-S Systems

Zusammenfassung In polymetallischen Sulfiderzen niedriger Bildungstemperaturen sind Spuren von Thallium fast immer nachweisbar. In jüngster Zeit wurde mittels moderner Analysentechniken eine Reihe neuer Thalliumminerale entdeckt, charakteristische Paragenesen sind bisher und Phasengleichgewichte jedoch unerforscht.In einer experimentellen Studie wurde das quasi-quaternäre System Argentit (Ag₂S)-Carlinit (Tl₂S)-Antimonglanz (Sb₂S₃)-Wismutglanz (Bi₂S₃) bei 200 °C untersucht. Es enthält nur eine quasi-quaternäre Phase AgTlSbBiS₄, welche durch Konoden mit den quasi-ternären Phasen Ag₄Sb₃BiS₈ und Ag₃Tl₃Sb₂S₆, sowie mit den quasi-binären Phasen Pyrargyrit (Ag₃SbS₃), Miargyrit (AgSbS₂), Schapbachit (Matildit, AgBiS₂), Weissbergit (TlSbS₂), TlBiS₂ und SbBiS₃ verknüpft ist. Das vorliegende Phasendiagramm ermöglichtes die Phasenbeziehungen natürlich vorkommender Ag- und Tl-Sulfosalze, die Sb und Bi enthallen, darzustellen.

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Phase Relations in the System Pb—Sn—Fe—Sb—S

Phase relations in the system Pb-Sn-Fe-Sb-S were investigated through the diagrams of projecting plane 8x(PbS-SnS-SnS2)from the vertrex point Fe0.96Sb2.04S4.12by vacuum silica tube technique.Experimental results have shown that franckeite has a wide solid solution with substitution of Pb^2 by Sn^2 ,In franckeite s.s.the content of Sn^2 varies from 0 to 4.8 atoms (total metal atoms are 11 atoms per formula) at 500℃ and 0-4.0 atoms at 400℃,respectively,Meanwhile,the content of Sn^4 ranges from 1.3to 2.0 atoms at 500℃ and 1.5-2.1 atoms at 400℃ in franckeite s.s.These results are consistent well with analytic data on natural franckeite.The cylindrite solid solutiopn has a relatively small range with Sn^2 -1.8atoms and Sm^4 =3.2-4.2 atoms per formula at 500℃ and ,Sn^2 =0.5-1.7 atoms and Sm^4 =3.3-4.2 atoms at 400℃ which are comparable with natural cylindrite.The phases coexisting in equilibrium with franckeite s.s. are galena,boulangerite,robinsonite.teallite,SnS,cylindrite.s.s.and synthetic phase Ⅲ ss or I ss.The cylindrite s.s.coexists with SnS2 and the above mentioned phases,but not with galena.teallite and SnS,and probably not with boulangerite in this projecting plane.     

Native bismuth,tsumoite, and Pb-bearing tsumoite from the Tarn’er copper-zinc massive sulfide deposit,northern Urals

Bismuth mineralization, including native bismuth, tsumoite (Bi_1.99–2.03Te_2.00), and Pb-bearing tsumoite (Bi_1.56–1.88Pb_0.45–0.14)_2.00–2.03Te_2.00, was identified in the Au-enriched disseminated ore at the Tarn’er massive sulfide deposit formed under the effect of a large diorite intrusion. Native bismuth associated with hessite forms idiomorphic inclusions in chalcopyrite. The assemblage of Pb-bearing tsumoite, hessite, and altaite occurs as angular allotriomorphic-granular inclusions in silicates or at the contact between silicate and sulfide aggregates. Tsumoite in allotriomorphic-granular aggregates with galena, hessite, and sphalerite is devoid of lead. Gold (Au_0.65Ag_0.35) was identified along with bismuth tellurides. The temperature of contact methamorphism (500–800°C) was estimated from the stability of andalusite, sillimanite, and cordierite. The morphology of the bismuth telluride aggregates in silicates and graphic intergrowth of tsumoite with galena suggest possible crystallization from anatectic melt. The positive correlation between Bi, Te, and Au confirms their probable joint transportation in the melt.