Electrochemical studies of sulphides,I. The electrocatalytic activity of galena,pyrite and cobalt sulphide for oxygen reduction in relation to xanthate adsorption and flotation

The electrocatalytic activity of galena, pyrite and Co₃S₄ for oxygen reduction has been studied by potentiostatic methods. Open circuit potentials of the sulphide electrodes have also been measured as a function of pH in nitrogen, air and oxygen atmospheres and also in the presence of H₂O₂ and ethyl xanthate. The adsorption of xanthate on sulphides was followed by observing bubble attachment to the electrodes.The catalytic activity for oxygen (or H₂O₂) reduction (the cathodic currents), the electrode potentials and the xanthate adsorption as shown by bubble attachment within certain pH limits, all varied as $\text{Co}{}_3\text{S}{}_4\text{> pyrite (≈ PbS in H}{}_2\text{O}{}_2\text{) ? PbS}$ indicating considerable dependence of the redox processes in flotation on the d - electron character of the sulphides.In the absence of oxygen, xanthate is probably bonded to the water structure of the surface through hydrogen-bonding, thus keeping the surface hydrophilic. Such adsorption reduces the electrode potential and inhibits oxygen reduction.     

Thermodynamic calculations on sulfide flotation systems, II. Comparisons with electrochemical experiments on the galena-ethyl xanthate system

Extensive thermodynamic calculations have been carried out to study the oxidation of galena and its flotation by potassium ethyl xanthate (KEX). In order to include some kinetic effects, three cases have been considered by assuming that sulfur oxidation can proceed as far as the formation of sulfate, thiosulfate and elemental sulfur.The results of these calculations have been compared with those of linear sweep voltammetry and intermittent galvanostatic polarization experiments conducted on galena at pH 9.2. Analysis of the experimental data indicates that in xanthate-free solutions, galena is oxidized primarily to PbO and S⁰ and, to a lesser extent, S₂O₃²⁻, rather than to the thermodynamically most favored PbOH⁺ and SO₄²⁻. Tests carried out in the presence of collector confirm the previous finding (Woods, 1971) that the interaction of xanthate with the mineral begins with chemisorption by a one-electron reaction. This cannot, of course, be predicted by calculations based on bulk thermodynamics.     

A quantum chemical investigation of the oxidation and dissolution mechanisms of Galena

The oxidation and dissolution mechanisms of galena (PbS) remain uncertain with a wide variety of possible mechanisms having been proposed in the literature. In this study, the thermodynamic viability of some possible mechanisms has been tested using semi-empirical quantum chemical calculations applied to a perfect (001) galena surface.The adsorption of O₂ and H₂O has been examined in both the gaseous and aqueous environments. In agreement with previous ab initio quantum chemical calculations, the surface induced dissociation of H₂O in either environment was found to be energetically unfavourable. However, the dissociative adsorption of O₂ was found to be possible and resulted in two O atoms bonded to diagonally adjacent S atoms with the O atoms oriented along the diagonal.The adsorption of H⁺ and possible subsequent dissolution mechanisms have been examined in the aqueous environment. An anaerobic mechanism leading to the dissolution of hydroxylated Pb²⁺ was identified. The mechanism involves the protonation of 3 surface S atoms surrounding a central surface Pb atom followed by substitution of this Pb by a further H⁺. The activation energy of this mechanism was estimated to be ≈100 kJ mol⁻¹. Pb²⁺ dissolution could only occur with vacancy stabilisation by a H⁺. The analogous mechanisms for systems comprising H⁺ adsorbed on either 2 or 4 of the S atoms surrounding a central surface Pb were not found to be energetically viable. Subsequent dissolution of one of the protonated S atoms to form H₂S_(g) was not found to be possible thus indicating the likely formation of a Pb-deficient S-rich surface under acidic anaerobic conditions.Acidic aerobic dissolution has also been examined. Congruent dissolution to form H₂SO₄ and Pb²⁺•6H₂O is energetically viable. The dissolution of one of the protonated S atoms neighbouring the Pb²⁺ vacancy, resulting from the anaerobic dissolution, to form H₂SO₄, is also possible.     

Flotation of galena. Influence of grain size,of pulp deoxygenation,and of cleaning with ammonium acetate

The flotation of < 10, 10–20, and 20–40 μm galena fractions was studied. For uncleaned galena a given collector coverage produced better floatability with increasing grain size. Nitrogen had a detrimental effect only for the < 10 μm fraction, producing at a given collector coverage a recovery smaller than that obtained with air.Galena cleaned with 400 g/l ammonium acetate had very poor floatability, although xanthate abstraction was fairly high; this confirms that strong xanthate adsorption is necessary for flotation. Formation of monothiocarbonate was small in all cases, which points to a very minor influence, if any, of this compound in the flotation process.In blank flotation tests, or for very low residual xanthate concentrations, a peak at 208 nm and a shoulder at 255 nm were observed. The former was assigned to the uncomplexed Pb²⁺ ion, and the latter was tentatively attributed to the PbOH⁺ ion.Lead in solution results from dissolution of the oxidation products of galena, as galena itself has an exceedingly low solubility. The curve for total lead in solution vs. initial xanthate concentration, had a minimum for an initial xanthate concentration of 10^?5M, the further increase in dissolved lead is attributed to formation of complexes such as PbX⁺ (X = xanthate). Dissolved lead concentrations were nearly as high for cleaned as for uncleaned galena, which indicates a high oxidation rate of the mineral.     

Interaction of finely ground galena and potassium amylxanthate in relation to flotation, 3. Influence of acid and neutral grinding

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Hallimond tube flotation and microelectrophoresis have been utilized to investigate the reactions in the adsorption-abstraction of K-amylxanthate on finely ground galena. The mineral was ground in a laboratory stainless steel rod mill under controlled conditions (pH 4.0 and 7.0) using HCl as a pH regulator. X-ray photoelectron spectroscopic (XPS) studies have been carried out in order to characterize the surface oxidation products after grinding (weak amounts of S_n and PbS₂O₃). The two-stage adsorption process discovered in previous studies was confirmed. For low concentrations or submonolayer capacity, the layer is formed with 1:1 monocoordinated lead xanthate and dixanthogen. For higher values of surface coverage, it is composed of lead xanthate (stoichiometric at pH 7 and non-stoichiometric at pH 4), amyldixanthogen and amylcarbonate disulphide. In the second stage mainly dixanthogen is formed. This stage corresponds to complete flotation and to a sharp decrease in zeta potentials.     

Decomposition of alkyl dixanthogens in aqueous solutions

Alkyl dixanthogens, (ROCSS)₂, decompose in aqueous solution in the presence of nucleophiles in many ways.It is proposed here that in alkaline solution the principal methods of decomposition of ethyl dixanthogen are by simultaneous attack of OH^? ions on the sulphur-sulphur bond to give products which include xanthate ion (ROCSS^?) and peroxide (H₂O₂) and on the carbon-sulphur bond to give products which include monothiocarbonate ion (ROSCO^?), sulphide ion (S^2?), and sulphur (S⁰). Above pH 12 reaction is complete in a few minutes, and more monothiocarbonate than xanthate is formed. At pH 9 the reaction takes over 20 h and more xanthate than monothiocarbonate is formed.The primary products react further to give various ions which depend in part on the pH of the system. In alkaline solution some of the xanthate and peroxide react to give perxanthate (ROCSSO^?). In acid solution both xanthate and monothiocarbonate decompose rapidly; CS₂ is formed from xanthate and OCS from monothiocarbonate.In the presence of other nucleophiles at pH 9.2, dissolved dixanthogen decomposes much more quickly than with OH^? alone, and other reactions occur. With thiosulphate a higher proportion of xanthate is formed together with some xanthyl thiosulphate and monothiocarbonate but no perxanthate. With sulphite (in the absence of oxygen) or cyanide the products include xanthate and monothiocarbonate but no perxanthate. With sulphite in the presence of oxygen, perxanthate is also formed.Suspensions of dixanthogens react slowly but in a similar fashion to dissolved dixanthogens.Longer-chain dixanthogens are much less soluble than ethyl dixanthogen but, in general, react in a similar way. Higher temperatures increase the rate of decomposition by OH^?.This work has various implications in operating plants.     

Observation of the oxidation of galena using Raman spectroscopy

Oxidation of galena (PbS) to oxysulfates, (PbO·PbSO₄, 3PbO·PbSO₄ and 4PbO·PbSO₄)_, has been observed using Raman spectroscopy. Peaks associated with the oxidation products have been assigned. The reaction appears to be a high temperature oxidation induced by the high laser (25 mW at 514.5 nm) power density at freshly cleaved galena surfaces. Damage to the galena surface was observed visually under the microscope. Moderate laser powers (5 mW at 514.5 nm) did not result in any damage. No Raman bands were observed or expected for freshly cleaved galena because it has the rock salt structure. Laser-induced production of these oxysulfates is dramatically different from high temperature methods previously employed. This procedure will permit easy identification of galena in complex mineral ore samples. Spontaneous air oxidation of freshly cleaved galena to oxides or polysulfides was not detected.     

The aqueous oxidation of complex sulfide concentrates in hydrochloric acid

Complex sulfides containing sphalerite, galena, chalcopyrite, and small amounts of silver in a matrix of pyrite can be decomposed at 120°C and oxygen pressure of 1000 kPa in 1–2 N HCl for 90 min to yield > 97% of the zinc and > 95% of the copper in solution while about 83% of the lead remains in the residue as PbCl₂ and PbSO₄ and 85% of the silver, together with most of the pyrite. The recovery of elemental sulfur is nearly 100% with respect to ZnS, PbS, and CuFeS₂. Leaching in HCl is faster than in H₂SO₄ at the same acid normality, and the process is diffusion-controlled (strongly dependant on agitation speed and having an activation energy of 3.6 kcal/mole). Lead jarosite, Pb_0.5Fe₃ (SO₄)₂?(OH)₆, is mainly formed when H₂SO₄ is used as a leaching agent.     

Galvanic interactions between galena–sphalerite and their reactivity

The galvanic effect between the main associated mineralogical phases in a mineral sphalerite concentrate was evaluated using an alternative methodology. Comparative voltammetric studies were performed between high purity galena mineral (94.65%) and sphalerite concentrate (content of 78.11% sphalerite, ZnS; 13.64% galena, PbS; 0.57% chalcopyrite, CuFeS₂; 0.41% cadmium sulfide, CdS; and 0.11% arsenopyrite, FeAsS) using carbon paste electrodes (CPE) in order to identify galvanic interactions that affect their reactivity. The electrolyte was an aqueous solution of 0.1 M NaNO₃ (pH 6.5). The results showed that, in sphalerite concentrate, the electrochemical reactivity of the galena was diminished and displaced to more positive potentials with respect to the high purity galena mineral response. This behavior can be attributed to the galvanic protection offered by the sphalerite on the galena, thereby avoiding its free oxidation. On the other hand, sphalerite oxidation was diminished by the formation of a passive products film that is dissolved to more positive potentials which provokes oxidation of other minerals like CuFeS₂, (Zn,Cd)S and FeAsS present in a minor proportion in the sphalerite concentrate.     

Geological Characteristics and Genesis of the Jiamoshan MVT Pb–Zn Deposit in the Sanjiang belt, Tibetan Plateau

The carbonate-hosted Pb–Zn deposits in the Sanjiang metallogenic belt on the Tibetan Plateau are typical of MVT Pb–Zn deposits that form in thrust-fold belts. The Jiamoshan Pb–Zn deposit is located in the Changdu area in the middle part of the Sanjiang belt, and it represents a new style of MVT deposit that was controlled by karst structures in a thrust–fold system. Such a karst-controlled MVT Pb–Zn deposit in thrust settings has not previously been described in detail, and we therefore mapped the geology of the deposit and undertook a detailed study of its genesis. The karst structures that host the Jiamoshan deposit were formed in Triassic limestones along secondary reverse faults, and the orebodies have irregular tubular shapes. The main sulfide minerals are galena, sphalerite, and pyrite that occur in massive and lamellar form. The ore-forming fluids belonged to a Mg2+–Na+–K+–SO2-4–Cl-–F-–NO-3–H2 O system at low temperatures(120–130°C) but with high salinities(19–22% NaCl eq.). We have recognized basinal brine as the source of the ore-forming fluids on the basis of their H–O isotopic compositions(-145‰ to-93‰ for δDV-SMOW and-2.22‰ to 13.00‰ for δ18 Ofluid), the ratios of Cl/Br(14–1196) and Na/Br(16–586) in the hydrothermal fluids, and the C–O isotopic compositions of calcite(-5.0‰ to 3.7‰ for δ13 CV-PDB and 15.1‰ to 22.3‰ for δ18 OV-SMOW). These fluids may have been derived from evaporated seawater trapped in marine strata at depth or from Paleogene–Neogene basins on the surface. The δ34 S values are low in the galena(-3.2‰ to 0.6‰) but high in the barite(27.1‰), indicating that the reduced sulfur came from gypsum in the regional Cenozoic basins and from sulfates in trapped paleo-seawater by bacterial sulfate reduction. The Pb isotopic compositions of the galena samples(18.3270–18.3482 for 206 Pb/204 Pb, 15.6345–15.6390 for 207 Pb/204 Pb, and 38.5503–38.5582 for 208 Pb/204 Pb) are similar to those of the regional Triassic volcanic-arc rocks that formed during the closure of the Paleo-Tethys, indicating these arc rocks were the source of the metals in the deposit. Taking into account our new observations and data, as well as regional Pb–Zn metallogenic processes, we present here a new model for MVT deposits controlled by karst structures in thrust–fold systems.     

Formation and recognition of alkyl xanthyl thiosulphates in sulphide ore flotation liquors

Alkyl xanthyl thiosulphates (R.OCSS.S₂O₃^?) (RXT^?) are formed in solution by mild oxidation (e.g. by I₂) of solutions containing both xanthate and thiosulphate. They can also be formed by reaction of Cu²⁺ with xanthate and thiosulphate, reaction of dixanthogen with thiosulphate, and by reaction of xanthate with tetrathionate; these last three reactions can occur in flotation pulps in slightly acid or alkaline solutions (pH 5–10).Alkyl xanthyl thiosulphates are stable in acid and neutral solution; the solutions have a UV absorption maximum at 289 nm. In strongly alkaline solution (pH 12) RXT^? decomposes within a few minutes to yield a xanthate (mostly) plus a little perxanthate. At pH 10 this decomposition to xanthate takes about 48 h. At pH 7–9 RXT^? is relatively stable. RXT^? is not extracted from aqueous solution with common solvents (chloroform, iso-octane, cyclohexane, or ether). It forms a water-insoluble adduct with cetyltrimethyl-ammonium bromide (CTAB); this adduct can be extracted into chloroform, and the extract has a UV absorption maximum at 296 nm.RXT^? was found in solutions from the gangue-sulphide flotation section at Renison Ltd, the zinc flotation circuit and the copper flotation circuit at Mount Isa Mines Ltd, and the lead flotation section of The Zinc Corporation Ltd. The presence of RXT^? in operating flotation plants has various practical and theoretical implications.     

P-T-X parameters of metamorphogene and hydrothermal fluids,isotopy and age of the Bogunai gold deposit,southern Yenisei Ridge (Russia)

Fluid inclusions in quartz, sulfides from quartz veins, and quartz, garnet, plagioclase, and orthoclase from granulites of the Bogunai gold deposit located in the granulites of the Angara-Kan block of the Yenisei Ridge were studied by thermobarometry, gas chromatography, chromato-mass-spectrometry, Raman spectroscopy, and mass spectrometry with inductively coupled plasma. The formation temperatures (850-950 °C) and pressures (8.5-9.0 kbar) of minerals of the granulite metamorphic facies are much higher than the crystallization temperatures (220-420 °C) and pressures (0.1-1.6 kbar) of gold-quartz veins of the Bogunai deposit. These veins formed with the participation of H₂O-CO₂-hydrocarbon fluids with a salt (predominantly MgCl₂) concentration of 2-19 wt.% NaCl equiv. The gas phase of fluid inclusions from quartz, pyrite, chalcopyrite, galena, and sphalerite contains not only H₂O, CO₂, CH₄, and N₂ but also the first found compounds of sulfur (CS₂, O₂S, COS, C₂H6S₂) and nitrogen (C3H₇N, C3H₇NO, C₄H8N₂O) and numerous hydrocarbons of different classes (paraffins, arenes, naphthenes, alcohols, aldehydes, ketones, carbonic acids, and furans). The age of the Krasnoyarsk mineralized zone, one of the sites of the Bogunai deposit, is 466 ± 3.2-461.6 ± 3.1 Ma, which is almost 1400 Ma younger than the age of granulite metamorphism and 255 Ma younger than the age of diaphthoresis but is close to the age of the Lower Kan granitoid pluton (455.7 ± 3.4 Ma). The sulfur isotope ratios (5³⁴S) of sulfides (pyrite, chalcopyrite, sphalerite, and galena) are close to the mantle values, 0.8 to 3.5%c, and are in the range of the granitoid values, which indicates the crustal source of the fluid sulfur. Gold of the Bogunai deposit accumulated with the participation of H₂O-CO₂-hydrocarbon fluids generated both in deep-fault zones and in granitoid intrusions.     

Arsenite adsorption on galena (PbS) and sphalerite (ZnS)

Arsenite, As(III), sorption on galena (PbS) and sphalerite (ZnS) was investigated as a function of solution composition and characterized using X-ray absorption spectroscopy (XAS). Adsorption conformed to a Langmuir isotherm except at the highest surface loadings, and it was not strongly affected by changes in ionic strength. Arsenite sorbed appreciably only at pH > ∼5 for PbS and pH ∼4.5 for ZnS, behavior distinct from its adsorption on other substrates. Arsenite adsorption on PbS and ZnS resulted in the conversion from As-O to As-S coordination. Arsenite does not adsorb through ligand-exchange of surface hydroxyl or sulfhydryl groups. Rather, it forms a polynuclear arsenic sulfide complex on ZnS and PbS consistent with the As₃S₃(SH)₃ trimer postulated by Helz et al. (1995) for sulfidic solutions. This complex was unstable in the presence of oxidizing agents and synchrotron light—it quickly converted to As(V), which was largely retained by the surface. These data illustrate the complexity of As(III) adsorption to even simple sulfide minerals.     

Fluid inclusion,rare earth element geochemistry,and isotopic characteristics of the eastern ore zone of the Baiyangping polymetallic Ore district,northwestern Yunnan Province,China

The Baiyangping Cu–Ag polymetallic ore district is located in the northern part of the Lanping–Simao foreland fold belt, which lies between the Jinshajiang–Ailaoshan and Lancangjiang faults in western Yunnan Province, China. The source of ore-forming fluids and materials within the eastern ore zone were investigated using fluid inclusion, rare earth element (REE), and isotopic (C, O, and S) analyses undertaken on sulfides, gangue minerals, wall rocks, and ores formed during the hydrothermal stage of mineralization. These analyses indicate: (1) The presence of five types of fluid inclusion, which contain various combinations of liquid (l) and vapor (v) phases at room temperature: (a) H₂O (l), (b) H₂O (l) + H₂O (v), (c) H₂O (v), (d) C_mH_n (v), and (e) H₂O (l) + CO₂ (l), sometimes with CO₂ (v). These inclusions have salinities of 1.4–19.9 wt.% NaCl equivalents, with two modes at approximately 5–10 and 16–21 wt.% NaCl equivalent, and homogenization temperatures between 101 °C and 295 °C. Five components were identified in fluid inclusions using Raman microspectrometry: H₂O, dolomite, calcite, CH₄, and N₂. (2) Calcite, dolomitized limestone, and dolomite contain total REE concentrations of 3.10–38.93 ppm, whereas wall rocks and ores contain REE concentrations of 1.21–196 ppm. Dolomitized limestone, dolomite, wall rock, and ore samples have similar chondrite-normalized REE patterns, with ores in the Huachangshan, Xiaquwu, and Dongzhiyan ore blocks having large negative δCe and δEu anomalies, which may be indicative of a change in redox conditions during fluid ascent, migration, and/or cooling. (3) δ³⁴S values for sphalerite, galena, pyrite, and tetrahedrite sulfide samples range from −7.3‰ to 2.1‰, a wide range that indicates multiple sulfur sources. The basin contains numerous sources of S, and deriving S from a mixture of these sources could have yielded these near-zero values, either by mixing of S from different sources, or by changes in the geological conditions of seawater sulfate reduction to sulfur. (4) The C–O isotopic analyses yield δ¹³C values from ca. zero to −10‰, and a wider range of δ¹⁸O values from ca. +6 to +24‰, suggestive of mixing between mantle-derived magma and marine carbonate sources during the evolution of ore-forming fluids, although potential contributions from organic carbon and basinal brine sources should also be considered. These data indicate that ore-forming fluids were derived from a mixture of organism, basinal brine, and mantle-derived magma sources, and as such, the eastern ore zone of the Baiyangping polymetallic ore deposit should be classified as a “Lanping-type” ore deposit.     

Sulfur and carbon isotope compositions in the stratiform Zn-Pb-Cu sulfide deposits of the Rajpura-Dariba belt,Rajasthan, NW India: A model of ore genesis

The sulfur isotope composition of 86 sulfide minerals from the Middle Proterozoic, metamorphosed, stratiform, sediment-hosted Zn-Pb-CU sulfide deposits of Dariba and Sindeswar Kalan located within the Rajpura-Dariba belt in Rajasthan, NW India, have been determined. In addition, 16 carbonaceous and 2 carbonate rock samples from the ore zone have been analyzed for their C_tot and C_org contents and carbon isotope compositions. The sulfur isotope compositions range from 9.1 to –6.7 (mean value of 1.9). Increasing ³⁴S values stratigraphically upward are observed, particularly for pyrite and pyrrhotite suggesting a syngenetic origin for the sulfur. No marked lateral isotopic variations or isotopic variation in minerals from successive laminae in banded ore samples occur. Fractionation of sulfur isotopes between coexisting sulfides suggests that the original isotopic pattern was basically preserved during the amphibolite-facies metamorphism suffered by the deposits. C_org in carbonaceous rocks ranges 0.5–9.3 wt%, with ¹³C values between –21 and –31 (mean of –25.4) in keeping with the biogenic derivation of the carbon. Recrystallized dolostones have ¹³C values close to –14.4Geological evidence and isotopic features are consistant with the following genetic scheme: (a) base-metal ores along the belt formed from geothermal emanations carrying H₂S, produced by the chemical reduction of seawater sulfates and leaching of mafic volcanics, in a semiclosed (with respect to SO₄), shallow-water, rift-related basin with high biological activity; (b) pyrite and pyrrhotite formed diagenetically by bacterial reduction of sulfate in pore seawater in a system open to H₂S, thus bringing about the gradual enrichment of ³⁴S in these minerals stratigraphically upward; and (c) northward in the belt, at Sindeswar Kalan, the basin of ore deposition was relatively more open.     

Kinetics and thermochemistry of amyl xanthate adsorption by pyrite and marcasite

The kinetics and thermochemistry of the xanthate adsorption reaction on pyrite and marcasite were evaluated with respect to the existing theory. The rate of xanthate adsorption was studied in a stirred reactor and the xanthate concentration was determined by UV spectrophotometry as a function of time. The heat of the adsorption reaction was measured with a microcalorimeter. The results from both experiments indicate that xanthate adsorption by pyrite or marcasite involves the formation of dixanthogen by an electrochemical reaction at the solid surface which supports the conclusions of other investigators:

$\text{1}\text{2}\text{O}{}_2\text{(aq) =}\text{1}\text{2}\text{O}{}_2\text{(ad) 2X + 2H}{}^{\mathrm{+}}\text{+}\text{1}\text{2}\text{O}{}_2\text{→ X}{}_2\text{(ad) + H}{}_2\text{O}$

The rate of the adsorption reaction was found to be approximately one-half order with respect to the xanthate concentration and to have an activation energy of 7.5 kcal/mole. Additionally, the rate was found to have a slight dependence on pH under certain conditions. In view of these results, it appears that the adsorption reaction is controlled by electrochemical discharge at the pyrite surface. Analysis of the data in terms of an electrochemical kinetic model successfully explained the observed rate phenomena.The measured heat of the adsorption reaction at low pH was found to be between ?63 and ?56 kcal/mole of adsorbed dixanthogen and independent of surface coverage. These experimental heats of adsorption agree with the value of ?57 kcal/mole of dixanthogen calculated for the oxidation of xanthate by oxygen from thermodynamic data reported in the literature.     

Experimental study of a low-alkali tholeiite at 1–5 kbar: optimal condition for the crystallization of high-An plagioclase in hydrous arc tholeiite

We conducted melting experiments on a low-alkali tholeiite (SiO₂ ~52 wt%, MgO ~6.5 wt%, CaO/Na₂O~4.4, Al₂O₃/SiO₂ ~0.33) under both H₂O-undersaturated and H₂O-saturated conditions to investigate the effect of H₂O on the Ca–Na partitioning between plagioclase and melt. Experiments were performed in the temperature and pressure ranges of 1,000–1,300°C and 1–5 kbar, respectively, with varying H₂O contents of 0–12wt%. Redox condition was 0–2 log unit above NNO (nickel–nickel oxide) buffer. Temperature-bulk H₂O diagrams for the low-alkali tholeiite are constructed at 1, 2, and 5 kbar, and compositions of near-liquidus plagioclase and coexisting melt are determined. To exclude the effect of melt composition (CaO/Na₂O and Al₂O₃/SiO₂ ratios) on plagioclase composition and to reveal the effect of H₂O on An (=100×Ca/(Ca+Na)) content and (=(Ca/Na)_pl/(Ca/Na)_melt), we focused on the composition of near-liquidus plagioclases which crystallized from melts with nearly constant CaO/Na₂O and Al₂O₃/SiO₂ ratios. Our experimental results show that, at each experimental pressure, An content of the near-liquidus plagioclase and the K_D^Ca-Na almost linearly increases as H₂O content in melt increases. Each of the An content and the variations in a low-alkali tholeiitic system (CaO/Na₂O~4.0–4.5, Al₂O₃/SiO₂ ~0.27–0.33) can be described by one equation using temperature, pressure, and melt H₂O content as parameters. An content and of liquidus plagioclase increases with increasing melt H₂O and with decreasing pressure, elucidating that nearly H₂O-saturated conditions of 2–3 kbar is optimal for the crystallization of the most An-rich plagioclase (>An₈₈). We suggest this pressure condition of 2–3 kbar, corresponding to depth of 7–11 km, plays an important role for the origin of An-rich plagioclase in H₂O-rich low-alkali tholeiite. At pressures more than ca. 4 kbar, crystallization of liquidus Ca-rich clinopyroxene decreases the CaO/Na₂O ratio of liquid, thus prohibiting the crystallization of high-An plagioclase from hydrous tholeiite.     

The crystal structure of sonoraite,Fe3+Te4+O3(OH)·H2O

Summary Sonoraite, FeTeO₃(OH)·H₂O, is monoclinic,P 2₁/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm³; the observed value is 3.95(1) g/cm³. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H₂O are involved in the chains. The Te⁴⁺ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.

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Die Kristallstruktur von Sonorait, Fe³⁺Te⁴⁺O₃(OH).H₂O

Zusammenfassung Sonorait, FeTeO₃(OH)·H₂O, ist monoklin, P 2₁/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm³; die gemessene Dichte beträgt 3,95(1) g/cm³. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H₂O-Molekül ist nicht Teil einer Kette. Die Te⁴⁺-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

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With 3 Figures     

Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control

Rare earth element (REE) abundances were measured by neutron activation analysis in anhydrite (CaSO₄), barite (BaSO₄), siderite (FeCO₃) and galena (PbS). A simple crystal-chemical model qualitatively describes the relative affinities for REE substitution in anhydrite, barite, and siderite. When normalized to ‘crustal’ abundances (as an approximation to the hydrothermal fluid REE pattern), log REE abundance is a surprisingly linear function of (ionic radius of major cation—ionic radius of REE)² for the three hydrothermal minerals, individually and collectively. An important exception, however, is Eu, which is anomalously enriched in barite and depleted in siderite relative to REE of neighboring atomic number and trivalent ionic radius. In principle, REE analyses of suitable pairs of co-existing hydrothermal minerals, combined with appropriate experimental data, could yield both the REE content and the temperature of the parental hydrothermal fluid.The REE have only very weak chalcophilic tendencies, and this is reflected by the very low abundances in galena—La, 0.6 ppb; Sm, 0.06 ppb; the remainder are below detection limits.     

Genetic Environment of the Intrusion-related Yuryang Au-Te Deposit in the Cheonan Metallogenic Province, Korea

Abstract. The Yuryang gold deposit, comprising a Te‐bearing Au‐Ag vein mineralization, is located in the Cheonan area of the Republic of Korea. The deposit is hosted in Precambrian gneiss and closely related to pegmatite. The mineralized veins display massive quartz textures, with weak alteration adjacent to the veins. The ore mineralization is simple, with a low Ag/Au ratio of 1.5:1, due to the paucity of Ag‐phases. Ore mineralization took place in two different mineral assemblages with paragenetic time; early Fe‐sulfide mineralization and late Fe‐sulfide and Au‐Te mineralization. The early Fe‐sulfide mineralization (pyrite + sphalerite) occurred typically along the vein margins, and the subsequent Au‐Te mineralization is characterized by fracture fillings of galena, sphalerite, pyrrhotite, Te‐bearing minerals (petzite, altaite, hessite and Bi‐Te mineral) and electrum. Fluid inclusions characteristically contain CO₂ and can be classified into four types (Ia, Ib, IIa and IIb) according to the phase behavior. The pressure corrected temperatures (≥500d?C) indicate that the deposit was formed at a distinctively high temperature from fluids with moderate to low salinity (<12 wt% equiv. NaCl) and CH₄ (1?22 mole %). The sphalerite geo‐barometry yield an estimated pressure about 3.5 ?2.1 kbar. The dominant ore‐deposition mechanisms were CO₂ effervescence and concomitant H₂S volatilization, which triggered sulfidation and gold mineralization. The measured and calculated isotopic compositions of fluids (δ¹⁸O_H2^O = 10.3 to 12.4 %o; δD_H2^O = ‐52 to ‐77 %o) may indicate that the gold deposition originated from S‐type magmatic waters. The physicochemical conditions observed in the Yuryang gold deposit indicate that the Jurassic gold deposits in the Cheonan area, including the Yuryang gold deposit are compatible with deposition of the intrusion‐related Au‐Te veins from deeply sourced fluids generated by the late Jurassic Daebo magmatism.