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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With 5 Figures

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Deceased     

Low-temperature crystal structures of stibnite implying orbital overlap of Sb 5s2 inert pair electrons

The crystal structure of stibnite [Sb₂S₃, Pnma, a=11.314(2), b=3.837(2), c=11.234(3) Å, V= 487.7(3) ų at 293 K] was refined in situ at 230, 173, and 128 K. It is a major characteristic of the structure that the Sb–S secondary bonds enclosing Sb 5s² inert lone-pair electrons at 293 K are significantly shorter than the corresponding sum of the Sb and S van der Waals radii. Concerning the temperature dependence, although both the polyhedral volume and the cation eccentricity of the two SbS₇ polyhedra exhibit continuous contractions with decreasing temperature, the sphericity values remain constant, indicating isotropic shrinkage. Consequently, the geometries of Sb 5s² inert lone-pair electrons and ligand atoms remain unchanged at low temperatures. This is because the crystal structure of stibnite at low temperature induces contraction with attractive interactions, which is called the orbital overlap between Sb 5s² inert lone-pair electrons and ligand orbitals to maintain the coordination environment. In this case, Sb 5s² lone-pair electrons are not inert, but active. Such orbital overlaps of inert lone-electron pairs can provide a reasonable explanation for shorter secondary bonds and lower band gap energy of the binary compounds containing heavy elements such as Sb, Te, Pb, and Bi, which are key factors in tracing the origins of color, luster, and semiconductivity of their minerals or compounds.     

A study of speciation of Sb in bisulfide solutions by X-ray absorption spectroscopy.

Direct evidence of the structure of thioantimonide species in alkaline aqueous solutions is provided by X-ray absorption spectroscopy. Twenty solutions containing thioantimonide species were prepared by dissolving stibnite (Sb₂S₃) in deoxygenated aqueous NaHS solutions; the solution pH range was 8–14, the [Sb_tot] 1–100 mM and the [HS⁻] 0.009–2.5 M. The structural environment of the dissolved Sb was determined by EXAFS analysis of the Sb K-edge over the temperature range 80–473 K.Many of the solutions contain a species with Sb bonded to four S atoms at 2.34 Å, consistent with the presence of a [Sb(V)S₄³⁻] species, demonstrating that oxidation of Sb(III) to Sb(V) has occurred on dissolution. There is evidence that the complementary reduced phase is H₂. In three solutions, the Sb has three nearest neighbor S atoms and two of these solutions have an additional S shell of two atoms at 2.9Å, with one showing evidence of an Sb shell at 4.15 Å. This provides evidence of the presence of multimeric Sb(V) thioantimonide species. Analysis of several solutions reveals the presence of a species with three Sb–S interactions of 2.41–2.42 Å, supporting the presence of a Sb(III) species such as Sb₂S₂(SH)₂. Six solutions have S coordination numbers from 2.7–4 Å and Sb–S distances of 2.37–2.39 Å, and are likely to contain mixtures of at least two species in concentrations such that each make a significant contribution to the EXAFS. There was no clear relationship between either [Sb_tot] or [HS⁻] and the type of species present, but Sb(III) species were only present in the solutions with high pH. The effect of temperature was most significant in one solution, where at 423 K partial hydrolysis occurred and the presence of a species such as Sb₂S₂(OH)₂, with an Sb–O distance of 1.91 Å, is indicated.The study provides new information on the coordination environment of thioantimonide species, complementary to previous studies and provides a basis for a better understanding of Sb speciation in aqueous solutions found in hydrothermal systems, anoxic basins and man-made, high pH environments. In particular it demonstrates the need for Sb(V) to be considered in theoretical and experimental studies of such systems. However, more definitive interpretation of some of the data is inhibited by the presence of mixtures of species and the lack of information on the outer coordination shells that would confirm the presence of multimeric species.     

Thallium-rich murunskite from the Lovozero pluton,Kola Peninsula,and partitioning of alkali metals and thallium between sulfide minerals

A new thallium-rich variety of murunskite has been found in the Palitra peralkaline pegmatite at Mount Kedykverpakhk, the Lovozero alkaline pluton, Kola Peninsula, Russia. This mineral occurs as a flattened dark bronze segregation (0.3 × 0.8 × 0.8 mm) overgrowing ussingite in a cavity. The chemical composition is as follows, wt %: 8.35 K, 24.31 Tl, 29.01 Cu, 14.58 Fe, 23.26 S, total is 99.51. The empirical formula is (K_1.18Tl_0.66)_1.84(Cu_2.53Fe_1.45)_3.98S_4.02. According to X-ray powder diffraction data, the dimensions of the tetragonal unit cell are: a = 3.869 (1), c = 13.206 (6) Å, V = 197.7 (2) ų. This variety is the closest to the intermediate member of the murunskite-thalcusite series. The youngest mineral complex of the Palitra Pegmatite includes four sulfides belonging to three different structure types. These sulfides also may be regarded as three topological types distinguished by the arrangement of alkali metal atoms in their structures: (1) bartonite and chlorbartonite belonging to the zero-dimensional topological type with K atoms in isolated cells, (2) pautovite pertaining to the one-dimensional type with Cs (+Rb, K, Tl) atoms making up chains in ample tunnels, and (3) murunskite belonging to the two-dimensional type with K (+Tl) atoms forming sheets. There is pronounced partitioning of K (Cs + Rb) and Tl between these sulfides: bartonite and chlorbartonite contain 9.5–9.7 wt % K and 0.2 wt % Tl; pautovite, 36.1 wt % Cs, 1.3 wt % Rb, 0.5 wt % Tl, and 0.2 wt % K; and murunskite, 8.35 wt % K and 24.31 wt % Tl.     

Strukturverfeinerung des Freibergits

Zusammenfassung Aus 3-dimensionalen Filmdaten wurde die Kristallstruktur eines Freibergits mit 13 Gew% Ag für 130F _hkl aufR=0,035 verfeinert. Es wird abgeleitet, daß das Silber von den beiden zur Verfügung stehenden Punktlagen die 3-koordinierte bevorzugt; somit ergibt sich die kristallchemische Formel (Cu_3,8Ag_2,2)[3S]Cu₆[4S][SbS₃]₄Sk. Eine Aufspaltung der partiell von Ag besetzten Punktlage ist wahrscheinlich.

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Refinement of the crystal structure of Freibergite

Summary The crystal structure of a silver-tetrahedrite with 13 weight% Ag was refined toR=0.035 for 130F _hkl using 3-dimensional photographic data. It is shown that, of the two possible positions, silver is preferentially 3-coordinated. So the formula reads (Cu_3.8Ag_2.2)[3S]Cu₆[4S][SbS₃]₄Sk. Probably the position partially occupied by silver is split.

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Mit 1 Abbildung     

“Mysterite” : a late condensate from the solar nebula

We have attempted to clarify the nature of “mysterite”, a material that had been postulated to explain the overabundance of Tl, Bi and Ag in certain chondrites. Four dark clasts and a vein sample from the H6 chondrite Supuhee were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Os, Rb, Re, Sb, Se, Te, Tl and Zn. One of the clasts is enriched in all volatile elements, while the other 4 samples are enriched only in the siderophile volatiles Ag, Bi and Tl. The enrichments range up to 100 times typical H6 chondrite abundances. The proportions of Ag, Bi, Tl suggest the presence of at least two, Tl-rich and Tl-poor, varieties of mysterite ($\text{Tl}\text{Bi}\text{= 7.2}$ and <0.1). The former seems to dominate in Supuhee and Krymka, and the latter in Mezö-Madaras. Apparently mysterite is a late condensate from the solar nebula that collected volatiles left behind by earlier generations of chondrites. It was incorporated in Supuhee and perhaps in other chondrites (mainly of low petrologic types) during brecciation events.     

A note on the bonding,optical spectrum and composition of tetrahedrite

Tetrahedrites of composition (Cu, Ag)₁₀(Cu₂, Fe, Zn)₂(Sb, As)₄S₁₃ or Cu₁₂Sb_14/3S₁₃ have 208 valence electrons per unit cell and are expected to be semiconductors. The bands are full in these cases, whereas compositions towards the classical formula Cu₁₂Sb₄S₁₃ (204 valence electrons per unit cell) have only partially filled bands and are therefore expected to be metallic. These predictions are supported by new optical absorption spectra of tetrahedrites with 205 and 208 valence electrons per unit cell. The gap between valence and conduction bands of the semiconductor is about 1.7 (±0.2) eV. A further prediction based on a nearly-free electron model is that 208 valence electrons per unit cell represent a compositional limit for tetrahedrites, and that the stability increases as compositions approach this limit. Existing data indicate an exponential increase in the number of occurrences as the limit is approached.     

Geochemical evolution of Sb migration species in carbonate and thermal waters in relation to Sb hydrogenic mineralization

Based on the synthesis of hydrogeochemical materials on Sb occurrence in carbonate and thermal waters and thermodynamic simulations, genetic analysis was conducted of the transformations of probable Sb migration species (particularly oxygen-bearing and sulfide ones), and their transformations were calculated depending on the main parameters of hydrogeochemical systems (\(P_{CO_2 } \), T, R/W, Eh, and pH). The oxygen 2HSbO ₂ ⁰ + 3H₂S = Sb₂S₃ + 4H₂O (2SbO ₂ ^? + 3HS^? + 5H⁺ = Sb₂S₃ + 4H₂O) and sulfide HSb₂S ₄ ^? + H⁺ = Sb₂S₃ cr + H₂S (Sb₂S ₄ ^2? + 2H⁺ = Sb₂S₃cr + H₂S) models for the genesis of hydrogenic Sb₂S₃(cr) were simulated. Information on occurrences of carbonate and thermal waters in various regions worldwide was generalized, and the reasons were identified for the geochemical separation of As and Sb in carbonate and thermal waters. The causes and conditions of an increase in Sb concentrations in thermal waters were revealed, and Sb migration species in carbonate and thermal waters were identified for various parameters of hydrogeochemical systems. Variations in Sb speciation were demonstrated for hydrogeochemical systems depending on their boundary conditions (\(P_{CO_2 } \), T, and R/W). Models were outlined responsible for the precipitation of Sb₂S₃(cr) from carbonate and thermal waters.     

Calculation of the visible-UV absorption spectra of hydrogen sulfide,bisulfide, polysulfides,and As and Sb sulfides,in aqueous solution

Recently we showed that visible-UV spectra in aqueous solution can be accurately calculated for arsenic (III) bisulfides, such as As(SH)₃, As(SH)₂S^- and their oligomers. The calculated lowest energy transitions for these species were diagnostic of their protonation and oligomerization state. We here extend these studies to As and Sb oxidation state III and v sulfides and to polysulfides S _n ^2- , n = 2–6, the bisulfide anion, SH^-, hydrogen sulfide, H₂S and the sulfanes, S _n H₂, n = 2–5. Many of these calculations are more difficult than those performed for the As(iii) bisulfides, since the As and Sb(v) species are more acidic and therefore exist as highly charged anions in neutral and basic solutions. In general, small and/or highly charged anions are more difficult to describe computationally than larger, monovalent anions or neutral molecules. We have used both Hartree-Fock based (CI Singles and Time-Dependent HF) and density functional based (TD B3LYP) techniques for the calculations of absorption energy and intensity and have used both explicit water molecules and a polarizable continuum to describe the effects of hydration. We correctly reproduce the general trends observed experimentally, with absorption energies increasing from polysulfides to As, Sb sulfides to SH^- to H₂S. As and Sb(v) species, both monomers and dimers, also absorb at characteristically higher energies than do the analogous As and Sb(III)species. There is also a small reduction in absorption energy from monomeric to dimeric species, for both As and Sb III and v. The polysufides, on the other hand, show no simple systematic changes in UV spectra with chain length, n, or with protonation state. Our results indicate that for the As and Sb sulfides, the oxidation state, degree of protonation and degree of oligomerization can all be determined from the visible-UV absorption spectrum. We have also calculated the aqueous phase energetics for the reaction of S₈ with SH^- to produce the polysulfides, S _n H^-, n = 2–6. Our results are in excellent agreement with available experimental data, and support the existence of a S₆ species.     

Migration paths and precipitation mechanisms of ore-forming fluids at the Shuiyindong Carlin-type gold deposit,Guizhou, China

Shuiyindong is one of the largest and highest grade stratabound Carlin-type gold deposits in China. This paper reports on the results of petrographic studies, electron microprobe analyses (EMPA) of arsenian pyrite, and the mass transfer during mineralization and alteration, and it presents the deposit-scale distributions of Au, As, Sb, Hg, Tl, and trace elements in a representative cross section across the Shuiyindong Carlin-type gold deposit, Guizhou Province. The main objectives were to identify the precipitation mechanisms of minerals, or elements from fluids, and the migration paths of ore-forming fluids.Petrographic and EMPA studies indicate that gold in the primary ores is mainly hosted by arsenian pyrite. Mass transfer associated with alteration and mineralization shows that Au, As, Sb, Hg, Tl, and S were significantly added to all mineralized rocks, Fe₂O₃ and SiO₂ were immobile in the main orebodies that are hosted in bioclastic limestone, and CaO, Na₂O, Sr, and Li were removed from country rocks. The relations between Fe and S indicate that the sedimentary rocks at the Shuiyindong deposit contain more iron than is needed to combine with all of their contained sulfur to form pyrite. This suggests that sulfidation and decarbonation were the principal mechanism of gold precipitation at the Shuiyindong deposit. Hg, Sb, and As commonly formed sulfide minerals, such as stibnite, realgar, and orpiment, in late-stage quartz–calcite veins, or absorbed by organic matter in argillite. Fluid cooling presumably led to depositions of stibnite, realgar, and orpiment in late-stage quartz–calcite veins. Organic matter likely served as a reductant in argillite for the ore fluids, causing the precipitation of As, Sb, Hg, and S, as well as Au.Deposit-scale distributions of gold and other relevant elements reflect the passage of fluids through the rocks. Rock strata and structures allowed the ore-forming fluids to migrate horizontally along the unconformity surface of the Middle–Upper Permian, converge on the high position of an anticline, and then ascend into the overlying strata along the anticlinal axis. The distributions of the major and trace elements show that elements that accompanied the ore-forming fluids include Au, As, Sb, Hg, Tl, and S, and that Na₂O and Li were exhausted in the Longtan Formation at the anticlinal core during gold mineralization. The enrichment of Co, Cr, and Ni in the Longtan Formation at the anticlinal core might be associated with deformation that formed the anticline, or with gold mineralization. Different host rocks were preferentially mineralized by different elements. The bioclastic limestone is commonly enriched in Au, whereas the argillite is preferentially enriched in As, Hg, Sb, and Tl. The zonation of ore-forming elements in the deposit appears to be Sb–Tl–As–Hg–Au–Hg–As (from bottom to top). Enrichment of Au, As, Sb, Hg, and Tl provides useful guidance for the exploration for Carlin-type gold deposits in Guizhou. Anomalies of As and Hg in soil or stream sediment might be an important clue and these elements can be used as indicator elements. Ore-forming fluids migrated along the unconformity surface of the Middle–Upper Permian and the anticlinal axis, so these are favorable sites for exploration for Carlin-type gold deposits in Guizhou.     

Equilibrium thallium isotope fractionation and its constraint on Earth’s late veneer

Equilibrium isotope fractionation of thallium (Tl) includes the traditional mass-dependent isotope fractionation effect and the nuclear volume effect (NVE). The NVE dominates the overall isotope fractionation, especially at high temperatures. Heavy Tl isotopes tend to be enriched in oxidized Tl³⁺-bearing species. Our NVE fractionation results of oxidizing Tl⁺ to Tl³⁺ can explain the positive enrichments observed in ferromanganese sediments. Experimental results indicate that there could be 0.2–0.3 ε-unit fractionation between sulfides and silicates at 1650 °C. It is consistent with our calculation results, which are in the range of 0.17–0.38 ε-unit. Importantly, Tl’s concentration in the bulk silicate Earth (BSE) can be used to constrain the amount of materials delivered to Earth during the late veneer accretion stage. Because the Tl concentration in BSE is very low and its Tl isotope composition is similar with that of chondrites, suggesting either no Tl isotope fractionation occurred during numerous evaporation events, or the Tl in current BSE was totally delivered by late veneer. If it is the latter, the Tl-content-based estimation could challenge the magnitude of late veneer which had been constrained by the amount of highly siderophile elements in BSE. Our results show that the late-accreted mass is at least five-times larger than the previously suggested magnitude, i.e., 0.5 wt% of current Earth’s mass. The slightly lighter ²⁰⁵Tl composition of BSE relative to chondrites is probable a sign of occurrence of Tl-bearing sulfides, which probably were removed from the mantle in the last accretion stage of the Earth.

     

Calculation of the energetics for the oxidation of Sb(III) sulfides by elemental S and polysulfides in aqueous solution

Recent experimental studies have reported the existence of two new Sb sulfide species, Sb₂S₅²⁻ and Sb₂S₆²⁻, in alkaline sulfidic solutions in equilibrium with stibnite, Sb₂S₃, and orthorhombic S. These species contain Sb(V), which has also recently been identified in similar solutions using EXAFS by other researchers. This represents a significant change from the consensus a decade ago that sulfidic solutions of Sb contained only Sb(III) species. I have calculated from first principles of quantum mechanics the energetics for the oxidation of the Sb(III) sulfide dimer Sb₂S₄²⁻ to the mixed Sb(III,V) dimer Sb₂S₅²⁻ and then to the all Sb(V) dimer, Sb₂S₆²⁻. Gas-phase reaction energies have been evaluated using polarized valence double zeta effective core potential basis sets and Moller-Plesset second order treatments of electron correlation. All translational, rotational and vibrational contributions to the gas-phase reaction free energy have been calculated. Hydration energies have been obtained using the COSMO version of the self-consistent reaction field polarizable continuum method. Negative free energy changes are calculated for the oxidation of the dianion of the III,III dimer to the III,V dimer by both small polysulfides, like S₄H⁻, and elemental S, modeled as S₈. For the further oxidation of the III,V dimer to the V,V dimer the reaction free energies are calculated to be close to zero. The partially protonated Sb III,III dimer monoanion HSb₂S₄⁻ can also be oxidized, but the reaction is not so favorable as for the dianion. Comparison of the calculated aqueous deprotonation energies of H₂Sb₂S₄, H₂Sb₂S₅ and H₂Sb₂S₆ and their dianions with values calculated for various oxyacids indicates that the III,V and V,V dimers will have pK_a2 values <5, so that their dianions will be the dominant species in alkaline solutions. These results are thus consistent with the recent identification of Sb₂S₅²⁻ and Sb₂S₆²⁻ species. I have also calculated the Raman spectra of Sb₂S₅²⁻ and Sb₂S₆²⁻ to assist in their identification. The calculated vibrational frequencies of the III,V and V,V dimers are characteristically higher than those of the III,III dimer I previously studied. The III,V dimer may contribute shoulders to the Raman spectrum.     

Role of nuclear volume in driving equilibrium stable isotope fractionation of mercury, thallium, and other very heavy elements

Equilibrium stable isotope fractionations of mercury and thallium are estimated for molecules, atoms and ions using first-principles vibrational frequency and electronic structure calculations. These calculations suggest that isotopic variation in nuclear volume is the dominant cause of equilibrium fractionation, driving ²⁰⁵Tl/²⁰³Tl and ²⁰²Hg/¹⁹⁸Hg fractionations of up to 3‰ at room temperature. Mass-dependent fractionations are smaller, ca. 0.5-1‰ for the same isotopes. Both fractionation mechanisms tend to enrich the neutron-rich isotopes in oxidized mercury- and thallium-bearing phases (Tl³⁺ and Hg²⁺) relative to reduced phases (Tl⁺ and Hg⁰). Among Hg²⁺-bearing species, inorganic molecules and complexes like HgCl₂, and will have higher ²⁰²Hg/¹⁹⁸Hg than coexisting methylmercury species, suggesting a possible application of Hg-isotope measurements to understanding mercury methylation and increasing methylmercury concentrations at the top of the food chain. Estimated ²⁰⁵Tl/²⁰³Tl fractionation between and is in reasonable agreement with the fractionations previously observed between seawater and Fe-Mn crusts, supporting an equilibrium-like reduction/oxidation fractionation mechanism.More generally, nuclear-volume isotope fractionation will concentrate larger (heavier) nuclei in species where the electron density at the nucleus is small—due to lack of s-electrons (e.g., Hg²⁺—[Xe]4f¹⁴5d¹⁰6s⁰ vs. Hg⁰—[Xe]4f¹⁴5d¹⁰6s²) or enhanced s-electron screening by extra p, d, or f electrons (e.g., Tl⁰—[Xe]4f¹⁴5d¹⁰6s²6p¹ vs. Tl⁺—[Xe]4f¹⁴5d¹⁰6s²6p⁰). Nuclear-volume fractionations become much smaller for lighter elements, declining from ∼1‰/amu for thallium and mercury to ∼0.2‰/amu for ruthenium and ∼0.02‰/amu for sulfur.     

Minerals and calculated low-temperature phase equilibria in the pseudoternary system Tl2S-As2S3-Sb2S3

Summary The experimental determination of phase relations in the pseudoternary system Tl₂ S-As₂S₃-Sb₂S₃ below 200°C is practically impossible, especially so under dry condensed conditions. As thallium sulfosalts are naturally formed at low temperatures equilibrium phase assemblages at 100 and 200°C were calculated by application of thermochemical approximations for the free enthalpies of formation of the sulfosalts. A comparison of the calculated conode configurations with the results of syntheses under dry condensed conditions at 200°C yielded good agreement between experiment and calculations.

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Minerale und Phasenbeziehungen im pseudoternären System Tl₂S-As₂S₃-Sb₂S₃ bei tiefen Temperaturen

Zusammenfassung Die Ableitung der Phasenbeziehungen im pseudoternären System Tl₂S-As₂S₃-Sb₂S₃ für Temperaturen unterhalb 200°C, insbesondere unter trockenen Bedingungen, ist auf experimentellem Weg praktisch nicht möglich. Da die Thalliumsulfosalze als tieftemperierte Mineralbildungen anzusehen sind, wurden die stabilen Gleichgewichtsassoziationen bei 100 und 200°C unter Verwendung thermodynamischer Näherungen für die freie Bildungsenthalpie der Sulfosalze berechnet. Ein Vergleich der berechneten Konodenverläufe mit den Ergebnissen von Versuchen unter trocken kondensierten Bedingungen bei 200°C ergab gute Übereinstimmung zwischen Experiment und Berechnung.

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Partitioning of Se, As, Sb, Te and Bi between monosulfide solid solution and sulfide melt - Application to magmatic sulfide deposits

The chalcogenes (S, Se, Te), semimetals (As, Sb) and the metal Bi are important ligands for noble metals and form a wide range of compositionally diverse minerals with the platinum-group elements (PGE). With the exception of S, few experimental data exist to quantify the behavior of these elements in magmatic sulfide systems. Here we report experimental partition coefficients for Se, Te, As, Sb, and Bi between monosulfide solid solution (mss) and sulfide melt, determined at 950 °C at a range of sulfur fugacities (fS2) bracketed by the Fe-FeS (metal-troilite) and the Fe_1−×S-S_x (mss-sulfur) equilibria. Selenium is shown to partition in mss-saturated sulfide melt as an anion replacing S²⁻. Arsenic changes its oxidation state with fS₂ from predominantly anionic speciation at low fS₂, to cationic speciation at high fS₂. The elements Sb, Te, and Bi are so highly incompatible with mss that they can only be present in sulfide melt as cations and/or as neutral metallic species. The partition coefficients derived fall with increasing atomic radius of the element. They also reflect the positions of the respective elements in the Periodic Table: within a group (e.g., As, Sb, Bi) the partition coefficients fall with increasing atomic radius, and within a period the elements of the 15th group are more incompatible with mss than the neighboring elements of the 16th group.     

Fahlore thermochemistry: Gaps inside the (Cu,Ag)<Subscript>10</Subscript>(Fe,Zn)<Subscript>2</Subscript>(Sb,As)<Subscript>4</Subscript>S<Subscript>13</Subscript> cube

Possible topologies of miscibility gaps in arsenian (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores are examined. These topologies are based on a thermodynamic model for fahlores whose calibration has been verified for (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ fahlores, and conform with experimental constraints on the incompatibility between As and Ag in (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores, and with experimental and natural constraints on the incompatibility between As and Zn and the nonideality of the As for Sb substitution in Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores. It is inferred that miscibility gaps in (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores have critical temperatures several °C below those established for their Sb counterparts (170 to 185°C). Depending on the structural role of Ag in arsenian fahlores, critical temperatures for (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores may vary from comparable to those inferred for (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores, if the As for Sb substitution stabilizes Ag in tetrahedral metal sites, to temperatures approaching 370°C, if the As for Sb substitution results in an increase in the site preference of Ag for trigonal-planar metal sites. The latter topology is more likely based on comparison of calculated miscibility gaps with compositions of fahlores from nature exhibiting the greatest departure from the Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ and (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ planes of the (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlore cube.     

Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study

Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (Sb_T) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg⁻¹; in the Upper Floridan aquifer, Sb_T concentrations range from 8.1 to 1,462 pmol kg⁻¹; and for the Aquia aquifer, Sb_T concentrations range between 23 and 512 pmol kg⁻¹. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO₄ reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)₃⁰ species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)₆⁻ species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb₂S₄ ⁻ and Sb₂S₄ ²⁻, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO₄, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO₄ couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.     

The two polymorphs of TlPbSbS3 and the structural relations of phases in the system TlSbS2-PbS

Summary The synthetic TlPbSbS₃ represents a rare example of a sulphosalt with statistical distribution of Tl, Pb and Sb in the structure. Within the TlSbS₂-PbS system, TlPbSbS₃ is the end member of the solid solution series with TlSbS₂, but no solubility with PbS is detected. The high temperature-TlPbSbS₃ is orthorhombic and inverts at about 620 K to the low-temperature phase. The low-temperature modification of TlPbSbS₃ was structurally investigated by X-ray powder diffraction and by the Rietveld analysis of the data. The structure is monoclinic, with a = 4.1707(4) Å, b = 4.2856(4) Å, c = 12.157(1) Å, = 105.49(1)°, space group P2₁/c. Like in the high-temperature form, there is a cation disorder over the equivalent positions in the structure. The interatomic distances of (Tl, Ph, Sb) to S are 2.71, 2.72, 2.88, 3.15, 3.29, 3.51 (Å). There is a close similarity between the TlPbSbS₃ polymorphs and the and forms of SnS, as regards the atomic coordinations and the general structure types and the same type of phase transformation is supposed for both cases. The small differences in the structure type and symmetry, between the low temperature forms of SnS and TlPbSbS₃, result probably from stronger metal-metal interactions in the latter. A substitution-derivative relation to SnS type is established owing to the strong structural effect of the lone electron pairs of Tl and Sb. The substitution of Ag for Tl and Bi for Sb in ABCS₃ type compounds diminishes this effect and PbS type structures are produced.

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Die zwei Polymorphen von TlPbSbS₃ und die Strukturellen Beziehungen von Phasen in System TlSbS₂-PbS

Zusammenfassung Die synthetische Phase TlPbSbS₃ ist ein seltenes Beispiel von einem Sulfosalz mit der statistischen Verteilung von TI, Pb und Sb in der Struktur. In der TlSbS2-PbS Phasensystem, ist TlPbSbS₃ das Endmitglied der Mischkristallreihe, die sich im Richtung TlSbS₂ ausstreckt. Weitere Ausdehnung der Mischkristallreihe in der Richtung SbS konnte nicht bewiesen werden. Die Hochtemperatur-TlPbSbS₃ ist rhombisch und wird beim 620 K in die Tieftemperatur Modifikation umgewandelt. Die Tieftemperaturphase ist mit der Röntgenpulverdiffraktion und Rietveld Methode strukturell untersucht worden. Die ist monoklin, mit den Gitterkonstanten: a = 4.1707(4) Å, b = 4.2856(4) Å, c = 12.157(1) Å, = 105.49(1)°, Raumgruppe P2₁/c. Die statistische Verteilung von Kationen ist auch hier vorhanden. Die zwischenatomare Abstande (Tl, Pb, Sb)-S sind: 2.71, 2.72, 2.88, 3.14, 3.28, 3.51 (Å). Es besteht eine enge Verwandschaft zwischen den polymorphen Modifikationen von TlPbSbS₃ und den und Polymorphen von SnS, was die atomare Koordinationen und den generellen Strukturtypus betrifft, wobei ein ähnlicher Mechanismus der Phasenumwandlung für die beiden Fälle vermutet werden könnte. Die Differenzen in der Struktur und Symmetrie zwischen der Tieftemperaturmodifikationen von SnS und TlPbSbS₃ sind wahrscheinlich durch die bedeutende Metall-Metall Wirkungen in der zweiten verursacht. Die Phase TlPbSbS₃ ist ein substitution-derivative von der SnS Struktur, was durch die starke lone-electron-pair Aktivität von Kationen zu erklären ist. Die Ersetzung von Tl durch Ag und Sb durch Bi vermindert diese Aktivität und die entstandenen Strukturen sind in dem Fall dem PbS-Typus verwandt.

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With 3 Figures     

The system Ag-Sb-S from 600°C to 200°C

The system Ag-Sb-S was studied between 600°C and 200°C in evacuated silica glass tubes. Results from lower temperature runs require shifts in the stable tie-line configuration found by Barstad at 400°C. It is proposed that the configuration changes near 300°C, and that at 200°C the equilibrium assemblages correspond to those usually reported for minerals in ores. Most of the minerals of the system were synthesized. In addition, the synthetic phase Ag₇SbS₆ (antimony analogue of the arsenic mineral billingsleyite) is characterized, and the ease of its synthesis in the composition area bounded by argentite-pyrargyrite-sulfur suggests the probable existence of a mineral of this composition. The relatively common mineral stephanite (Ag₅SbS₄) was not formed as a synthetic product in the temperature range of this study. Combined DTA and X-ray data show that at 197±5°C stephanite decomposes in the absence of sulfur to form pyrargyrite plus argentite, whereas with excess sulfur the products are Sb-billingsleyite plus pyrargyrite. Pyrostilpnite (Ag₃SbS₃), the low temperature dimorph of pyrargyrite, is unstable above 192±5°C.

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Das ternäre System Silber-Antimon-Schwefel wurde zwischen 600° und 200°C untersucht und versucht, die Gleichgewichtszustände aller stabilen Phasen zu analogen natürlichen Mineralien in Beziehung zu setzen. Neben den Elementen wurden an binären Phasen Allargentum, Dyskrasit, Antimonit, Argentit bzw. Akanthit gefunden oder bestätigt. Auf dem pseudo-binären Schnitt Ag₂S-Sb₂S₃ liegen Pyrargyrit und Miargyrit, während eine als Mineral unbekannte ternäre Phase Ag₇SbS₆ (entsprechend dem natürlichen As-Analogon Billingsleyit) nur bei höherem Schwefelangebot beständig ist. Hier nicht synthetisch dargestellte Silber-Antimon-Sulfosalze liegen vermutlich unterhalb der 200°C-Grenze. So ließ sich mittels Differential-Thermo-Analyse und röntgenographischer Bestimmungsmethoden der inkongruente Zerfall von Stephanit in Argentit und Pyrargyrit bei 197±5°C bestimmen. Pyrostilpnit (Ag₃SbS₃) ist nur unterhalb 192±5°C beständig.