Lammerite-β, Cu3(AsO4)2, a new mineral from fumaroles of the Great Fissure Tolbachik eruption, Kamchatka Peninsula, Russia

Lammerite-β, Cu₃(AsO₄)₂, occurs as a product of the post-eruption fumarole activity of the second cinder cone of the North breach of the Great Fissure Tolbachik eruption in 1975–1976, Kamchatka Peninsula, Russia. Sporadic light to dark green splinter-shaped grains are no larger than 0.15 mm in size. Cleavage is not observed. The mechanical admixture of finely dispersed hematite forms condensed brownish spots that are occasionally zonal relative to the contours of the lammerite-β grains. Associated minerals are euchlorine, piypite, alumoklyuchevskite, alarsite, and lammerite. Lammerite-β is brittle and transparent and has vitreous luster. The calculated density is 5.06 g/cm³. The mineral is not pleochroic, biaxial (+), α = 1.887(5), β = 1.936(5), γ = 2.01(1), 2V(calc.) = 80.9°; dispersion is strong, r < v. The new mineral is monoclinic, the space group is P2₁/c, a = 6.306(1), b = 8.643(1), c = 11.310(1) Å, β = 92.26(1)°, V = 615.9(1) ų, and Z = 4. Characteristic reflections in the X-ray powder diffraction pattern (I-d-hkl) are 100-2.83-004, 10-5.65-002, and 10-4.32-020. The chemical composition is as follows, wt %: 51.30 CuO, 0.32 ZnO, 49.12 As₂O₃, with a total of 100.74 wt %. The empirical and idealized formulas are Cu_3.00Zn_0.02As_1.99O₈ and Cu₃(AsO₄)₂, respectively.     

Isotopic (C–O–S) geochemistry and Re–Os geochronology of the Haobugao Zn–Fe deposit in Inner Mongolia,NE China

The Haobugao Zn–Fe deposit is a typical skarn deposit located in the southern part of the Great Xing’an Range that hosts polymetallic mineralization over a large region. The main ore minerals at the deposit include sphalerite, magnetite, galena, chalcopyrite and pyrite, and the main gangue minerals include andradite, grossular garnet, hedenbergite, diopside, ilvaite, calcite and quartz. There are broadly two mineralizing periods represented by the relatively older skarn and younger quartz–sulfide veins. In detail, there are five metallogenic stages consisting of an early skarn, late skarn, oxide, early quartz–sulfide, and late quartz–sulfide–calcite stages. Electron microprobe analyses show that the garnet at the deposit varies in composition from And_97.95Gro_0.41Pyr_1.64 to And_30.69Gro_66.69Pyr_2.63, and pyroxene is compositionally in the diopside–hedenbergite range (i.e. Di_90.63Hd_8.00Jo_1.37–Hd_88.98Di_4.53Jo_6.49). Petrographic observations and electron microprobe analyses indicate that the sphalerite has three generations ([Zn_0.93Fe_0.08]S–[Zn_0.75Fe_0.24]S). The Zn associated with the first generation sphalerite replaced Cu and Fe of early xenomorphic granular chalcopyrite (i.e. [Cu_1.01Fe_1.03]S₂–[Cu_0.99Fe_0.99]S₂), and part of the first generation sphalerite is coeval with late chalcopyrite (i.e. [Cu_0.96Fe_0.99Zn_0.03]S₂–[Cu_1.00Fe_1.03Zn_0.01]S₂). Magnetite has a noticeable negative Ce anomaly (δCe = ∼0.17 to 0.54), which might be a result of the oxidized ore-fluid. Thirty δ³⁴S_V-PDB analyses of sulfides from the ore range from −2.3 to −0.1‰ in value, which are indicative of a magmatic source. The δ¹³C‰ and δ¹⁸O‰ values for calcite from the ore formed at quartz–sulfide–calcite stage vary from −9.9 to −5.5‰ and from −4.2 to 1.1‰, respectively, contrasting with δ¹³C‰ (2.9–4.8‰) and δ¹⁸O‰ (9.8–13.9‰) values for calcite from marble. It is suggested that the ore-forming fluid associated with late stage of mineralization was predominantly magmatic in origin with some input of local meteoric water.Molybdenite from the Haobugao deposit defines an isochron age of 142 ± 1 Ma, which is interpreted as the mineralization age being synchronous, within error, with the zircon U–Pb ages of 140 ± 1, 141 ± 2, and 141 ± 1 Ma for granite at the deposit. These data and characteristics of lithology and mineralization further show that the Zn–Fe mineralization is temporally and spatially related to the emplacement of granite in an extensional tectonic setting during the Mesozoic.     

Experimental Study on Surface Reactions of Heavy Metal Ions With Quartz—Aqueous Ion Concentration Dependence

Adsorption of divalent metal ions, including Cu²⁺, Pb²⁺, Zn²⁺, Cd²⁺ and Ni²⁺, on quartz surface was measured as a function of metal ion concentration at 30°C under conditions of solution pH= 6. 5 and ion strength I = 0. 1mol/L. Results of the experimental measurements can be described very well by adsorption isotherm equations of Freudlich. The correlation coefficients (r) of adsorption isotherm lines are > 0. 96. Moreover, the experimental data were interpreted on the basis of surface complexation model. The experimental results showed that the monodentate-coordinated metal ion surface complex species (SOM⁺) are predominant over the bidentate-coordinated metal ion surface complex species [(SO)₂M] formed only by the ions Cu²⁺, Zn²⁺ and Ni²⁺. And the relevant apparent surface complexation constants are lgK_M = 2.2–3.3 in order of K_Cd≥K_Pb > K_Zn > K_Ni≥K_Cu, and lgβ_M = 5.9-6.8 in order of β_Ni > β_Zn > β_Cu. Therefore, the reactive ability of the ions onto mineral surface of quartz follows the order of Cd > Pb > Zn > Ni> Cu under the above-mentioned solution conditions. The apparent surface complexation constants, influenced by the surface potential, surface species and hydrolysis of metal ions, depend mainly on the Born solvation coefficient of the metal ions. This project was financially supported by the National Natural Science Foundation of China (No. 49572091).     

Fluid Inclusion and Stable Isotope Studies at Don Sixto,a Precious Metal Low Sulfidation Deposit in Mendoza Province,Argentina

The Don Sixto mining area in Mendoza province, central‐western Argentina, contains an epithermal low sulfidation Au–Ag deposit. It is a small deposit (～4 km²), with a gold resource of 36 t. In Don Sixto, ore minerals are disseminated in the hydrothermal quartz veins and hydrothermally altered volcanic‐pyroclastic rock units of Permian–Triassic age. On the basis of the texture, ore mineral paragenesis and cross cutting relationship of gangue minerals, seven stages of mineralization were recognized and described. The first six stages are characterized by quartz veins with minor amounts of base metal minerals and the last stage is represented by fluorite veins with minimal quantities of base metal minerals; the precious metal mineralization is mainly related to the fourth stage. The hydrothermal veins exhibit mainly massive, crustiform and comb infilling textures; the presence of bladed quartz replacement textures and quartz veins with adularia crystals are indicative of boiling processes in the system. Fluid inclusion and complementary stable isotope studies were performed in quartz, fluorite, and pyrite samples from the vein systems. The microthermometric data were obtained from primary, biphasic (liquid‐vapor) fluid inclusion assemblages in quartz and fluorite. The maximum values for salinity and homogenization temperature (T_h) came from the stage IV where quartz with petrographic evidence of boiling has average values of 4.96 wt% NaCl_equiv. and 286.9°C respectively. The lower values are related to the last stage of mineralization, where the fluid inclusions in fluorite have average salinities of 1.05 wt% NaCl_equiv. and average homogenization temperatures of 173.1°C. The oxygen and sulfur isotopic fractionation was analyzed in quartz and pyrite. The calculated isotopic fractionation for oxygen in the hydrothermal fluid is in the range of δ¹⁸O_H2O = ?6.92 up to ?3.08‰, which indicates dominance of a meteoric source for the water, while sulfur reaches δ³⁴S_H2S = 1.09‰, which could be reflecting a possible magmatic, or even a mixed source.     

Polymetallic Mineralization at the Shin-Ohtoyo Deposit, Harukayama District, Hokkaido, Japan

Abstract: The Shin-Ohtoyo Cu–Au deposit is located in the Harukayama district, 20 km west of Sapporo, Hokkaido, Japan. Both acid-type disseminated and adularia–quartz–type vein Au mineralizations have been recognized within a small distance of less than 500 m in the district. Mineralogical characteristics of sulfide ores from the Shin-Ohtoyo deposit have been proved to be polymetallic. Ore minerals containing Sn, V, Bi and Te are recognized. Nine ore types are recognized in terms of characteristic mineral assemblage; (1) chalcedonic quartz veinlets in silicified zone around the deposit, (2) bismuthinite, emplectite, friedrichite and tetrahedrite, (3) an unnamed Cu–Sn–Fe–Zn sulfide, colusite-series minerals, stannoidite, emplectite and tetrahedrite, (4) bournonite, Se-bearing galena and tetrahedrite, (5) luzonite/famatinite and Ag-bearing tetrahedrite, (6) colusite-series minerals, emplectite, aikinite and tetrahedrite/goldfieldite, (7) luzonite/famatinite, colusite-series minerals, mawsonite and tetra–hedrite/goldfieldite, (8) enargite, luzonite/famatinite and tetrahedrite, and (9) colusite-series minerals and tetrahedrite. The first occurrence of friedrichite and stibiocolusite from Japan are reported. The chemical formula of the unnamed phase corresponds to Cu₆(Cu, Fe, Zn)Sn₃S₁₀. Sulfur isotopic ratios (δ³⁴S) of sulfides from the stockpile range from –0. 5% to +1. 9%, and those from drill cores recovered by Metal Mining Agency of Japan (MMAJ) vary from –2. 7% to +0. 8%. Sulfur isotopic ratio of barite in a cavity in the silicified tuff breccia collected from the stock pile yields +27. 1%, while that of barite collected from MMAJ core is +21. 7%. Sulfur isotopic thermometry applied for a pair of barite (+21. 7%) and associated pyrite (+1. 8%) indicates about 300°C. High–Te tetrahedrite composition from both the chalcedonic quartz vein in the silicified zone around the Shin-Ohtoyo deposit and the polymetallic sulfide ores from the adit of the deposit, suggests that the Au mineralization in the former is attributed to a hydrothermal system marginal to the polymetallic mineralization.     

H-O-S-Cu-Pb Isotopic Constraints on the Origin of the Nage Cu-Pb Deposit, Southeast Guizhou Province, SW China

The Nage Cu-Pb deposit,a new found ore deposit in the southeast Guizhou province,southwest China,is located on the southwestern margin of the Jiangnan Orogenic Belt.Ore bodies are hosted in slate and phyllite of Neoproterozoic Jialu and Wuye Formations,and are structurally controlled by EW-trending fault.It contains Cu and Pb metals about 0.12 million tonnes with grades of 0.2 wt% to 3.4 wt% Cu and 1.1 wt% to 9.27 wt% Pb.Massive and disseminated Cu-Pb ores from the Nage deposit occur as either veinlets or disseminations in silicified rocks.The ore minerals include chalcopyrite,galena and pyrite,and gangue minerals are quartz,sericite and chlorite.The H-O isotopic compositions of quartz,S-Cu-Pb isotopic compositions of sulfide minerals,Pb isotopic compositions of whole rocks and ores have been analyzed to trace the sources of ore-forming fluids and metals for the Nage Cu-Pb deposit.The δ65CuNBS values of chalcopyrite range from-0.09% to +0.33‰,similar to basic igneous rocks and chalcopyrite from magmatic deposits.δ65CuNBS values of chalcopyrite from the early,middle and final mineralization stages show an increasing trend due to63Cu prior migrated in gas phase when fluids exsolution from magma.δ34SCDT values of sulfide minerals range from 2.7‰ to +2.8‰,similar to mantle-derived sulfur(0±3‰).The positive correlation between δ65CuNBS and δ34SCDT values of chalcopyrite indicates that a common source of copper metal and sulfur from magma.δDH2OSMOW and δ18OH2O-SMOW values of water in fluid inclusions of quartz range from 60.7‰ to 44.4‰ and +7.9‰ to +9.0‰(T=260°C),respectively and fall in the field for magmatic and metamorphic waters,implicating that mixed sources for H2O in hydrothermal fluids.Ores and sulfide minerals have a small range of Pb isotopic compositions(208Pb/204Pb=38.152 to 38.384,207Pb/204Pb=15.656 to 17.708 and 206Pb/204Pb=17.991 to 18.049) that are close to orogenic belt and upper crust Pb evolution curve,and similar to Neoproterozoic host rocks(208Pb/204Pb=38.201 to 38.6373,207Pb/204Pb=15.648 to 15.673 and 206Pb/204Pb=17.820 to 18.258),but higher than diabase(208Pb/204Pb=37.830 to 38.012,207Pb/204Pb=15.620 to 15.635 and206Pb/204Pb=17.808 to 17.902).These results imply that the Pb metal originated mainly from host rocks.The H-O-S-Cu-Pb isotopes tegather with geology,indicating that the ore genesis of the Nage Cu-Pb deposit is post-magmatic hydrothermal type.     

四方铜金矿CuAu在我国发现

四方铜金矿产于新疆玛纳斯县清水河上游萨尔达拉含铂基性-超基性岩体中。岩体主要为暗绿色蛇纹石化斜辉辉橄岩,岩石化学成分多数为正常系列,少数为铝过饱和系列。岩体长9公里,宽140米,是一个向南倾斜的单斜岩墙。岩体侵入到泥盆系头苏泉组的黑灰色粉砂质板岩中。外接触带仅几十厘米到1米左右宽,以绿泥石化、绿帘石化、蛇纹石化为主,其次是碳酸岩化。内接触带有1米多宽,以蛇纹石化、透辉石化、透闪石化为主,个别地段有阳起石、透闪石软玉。     

Lebediny gold deposit,Central Aldan: Mineral parageneses,stages, and formation conditions

The mineral parageneses and succession of their formation are considered for the first time for the Zverevsky, Orekhovy, and Vodonosny ore lodes of the Lebediny gold deposit and the Radostny prospect in the Central Aldan ore district, which are genetically related to the epoch of Mesozoic tectonomagmatic reactivation. The orebodies, represented by two morphological varieties—ribbonlike lodes and steeply dipping veins—are hosted in lower part of the Vendian–Cambrian dolomitic sequence, which is cut through by Mesozoic subalkaline intrusive bodies. The chemistry of fahlore and rare minerals, including native gold and bismuth, altaite, aikinite, tetradymite, and sulfosalts of lillianite series, has been studied. Native gold is related to the late hydrothermal process and occurs in skarn and in quartz–tremolite–sulfide and quartz–carbonate–sulfide veins. The data on stable sulfur (δ³⁴S) isotopes of sulfides, oxygen (δ₁₈O) and carbon (δ₁₃C) isotopes of carbonates, as well as on fluid inclusions in various generations of tremolite and quartz, provide evidence for the heterogeneity of ore-bearing solutions, their relationships to magmatism, the depth of the source feeding each specific lode, and different sources of ore-forming hydrothermal solutions.     

Characteristics of Triassic epithermal Au mineralization at the Q prospect,Chatree mining area,Central Thailand

The Chatree deposit is located in the Loei‐Phetchabun‐Nakhon Nayok volcanic belt that extends from Laos in the north through central and eastern Thailand into Cambodia. Gold‐bearing quartz veins at the Q prospect of the Chatree deposit are hosted within polymictic andesitic breccia and volcanic sedimentary breccia. The orebodies of the Chatree deposit consist of veins, veinlets and stockwork. Gold‐bearing quartz veins are composed mainly of quartz, calcite and illite with small amounts of adularia, chlorite and sulfide minerals. The gold‐bearing quartz veins were divided into five stages based on the cross‐cutting relationship and mineral assemblage. Intense gold mineralization occurred in Stages I and IV. The mineral assemblage of Stages I and IV is characterized by quartz–calcite–illite–laumontite–adularia–chlorite–sulfide minerals and electrum. Quartz textures of Stages I and IV are also characterized by microcrystalline and flamboyant textures, respectively. Coexistence of laumontite, illite and chlorite in the gold‐bearing quartz vein of Stage IV suggests that the gold‐bearing quartz veins were formed at approximately 200°C. The flamboyant and brecciated textures of the gold‐bearing quartz vein of Stage IV suggest that gold precipitated with silica minerals from a hydrothermal solution that was supersaturated by boiling. The δ¹⁸O values of quartz in Stages I to V range from +10.4 to +11.6‰ except for the δ¹⁸O value of quartz in Stage IV (+15.0‰). The increase in δ¹⁸O values of quartz at Stage IV is explained by boiling. P_H2O is estimated to be 16 bars at 200°C. The f_CO2 value is estimated to be 1 bar based on the presence of calcite in the mineral assemblage of Stage IV. The total pressure of the hydrothermal solution is approximately 20 bars at 200°C, suggesting that the gold‐bearing quartz veins of the Q prospect formed about 200 m below the paleosurface.     

Genesis of the Nanyangtian scheelite deposit in southeastern Yunnan Province,China: evidence from mineral chemistry,fluid inclusions,and C–O isotopes

The Nanyangtian skarn-type scheelite deposit is an important part of the Laojunshan W–Sn polymetallic metallogenic region in southeastern Yunnan Province, China. The deposit comprises multiple scheelite ore bodies; multilayer skarn-type scheelite ore bodies are dominant, with a small amount of quartz vein-type ore bodies. Skarn minerals include diopside, hedenbergite, grossular, and epidote. Three mineralization stages exist: skarn, quartz–scheelite, and calcite. The homogenization temperatures of fluid inclusions in hydrothermal minerals that formed in different paragenetic phases were measured as follows: 221–423 °C (early skarn stage), 177–260 °C (quartz–scheelite stage), and 173–227 °C (late calcite stage). The measured salinity of fluid inclusions ranged from 0.18% to 16.34% NaCleqv (skarn stage), 0.35%–7.17% NaCleqv (quartz–scheelite stage), and 0.35%–2.24% NaCleqv (late calcite vein stage). Laser Raman spectroscopic studies on fluid inclusions in the three stages showed H₂O as the main component, with N₂ present in minor amounts. Minor amounts of CH₄ were found in the quartz–scheelite stage. It was observed that the homogenization temperature gradually reduced from the early to the late mineralization stages; moreover, δ¹³C_PDB values for ore-bearing skarn in the mineralization period ranged from ? 5.7‰ to ? 6.9‰ and the corresponding δ¹⁸O_SMOW values ranged from 5.8‰ to 9.1‰, implying that the ore-forming fluid was mainly sourced from magmatic water with a minor amount of meteoric water. Collectively, the evidence indicates that the formation of the Nanyangtian deposit is related to Laojunshan granitic magmatism.     

Minerals in the Triassic carbonaceous silicites of Sikhote Alin

Over 60 minerals, including native elements, intermetallic compounds, haloids, sulfides, sulfates, arsenides, oxides and hydroxides, silicates, borosilicates, wolframates, phosphates and REE phosphates, were established in Triassic siliceous rocks of Sikhote Alin. Allothigenic and authigenic minerals in the carbonaceous silicites were formed over a long period through several stages. Judging from morphology, chemical composition, and structural position, K-feldspar (K-Fsp), illite, kaolinite, metahalloysite, monazite, xenotime, zircon, rutile, or its polymorphs are the disintegration products of sialic rocks of continental crust. Authigenic sulfides are dominated by diagenetic pyrite (fine-crystalline, microglobular, framboidal, as well as those developed after biogenic siliceous and carbonate fragments), which has been formed prior to precipitation of siliceous cement and lithification of siliceous rocks. Most of other sulfides (sphalerite, galena, chalcopyrite, pyrrhotite, argentite, pentlandite, antimonite, ulmanite, and bravoite), arsenides and sulfoarsenides (arsenopyrite, nickeline, skutterudite, cobaltite, glaucodot, and gersdorffite), wolframates (scheelite and wolframite), intermetallides (Cu₂Zn, Cu₃Zn₂, Cu₃Zn, Cu₄Zn, CuSn, Cu₄Sn, Cu₈Sn, Cu₄Zn₂Ni, Ni₂Cu₂Zn, Ni₄Cd), and native elements (Au, Pd, Ag, Cu, Fe, W, Ni, Se) were crystallized later (during catagenesis after the lithification and brecciation of siliceous beds) from metals involved in the easily mobile fractions of bitumens. Supergene mineral formation was mainly expressed in the sulfide oxidation and replacement of diagenetic pyrite by jarosite and iron hydroxides.     

Mineral CuFe<Subscript>2</Subscript>S<Subscript>4</Subscript> from sulfide Copper–Nickel ores of the Lovnoozero deposit,Kola Peninsula

The unnamed mineral CuFe₂S₄ has been found from sulfide Cu–Ni ores of the Lovnoozero deposit in the Kola Peninsula, Russia. It occurs in norite composed of orthopyroxene (bronzite), Ca-rich plagioclase (66% An), pargasite, and phlogopite. The last two minerals are replaced by talc, chlorite and carbonates. Monoclinic pyrrhotite, pentlandite, chalcopyrite, and pyrite are associated ore minerals. Phase CuFe₂S₄ is enclosed predominantly in chalcopyrite, probably replacing it, and occurs in later carbonate veinlets together with redeposited sulfides. It is light yellow with a brownish tint and metallic luster. The Mohs hardness is 5–5.5; VHN 654 ± 86 kgs/mm². Density (calc.) = 4.524 g/cm³. The mineral is anisotropic, internal reflections are absent. Reflectance values (λ, nm R′ _g and R′ _p %) are: 440 30.3 29.5, 500 43.7 42.8, 560 50.9 49.6, 620 52.4 51.2, 640 52.6 51.4, 680 52.8 51.6, 700 52.7 51.4. CuFe₂S₄ is monoclinic, a = 6.260(4), b = 5.39(1), c = 13.19(1) Å, β = 94.88(7)°, V = 443(1) ų, Z = 4. The strongest reflections in the powder diffraction pattern are [d, Å (I) (hkl)]: 4.150 (10) (012), 3.559 (4) (\(11\bar 2\)), 3.020 (4) (\(10\bar 4\)), 2.560 (3) (\(21\bar 2\)), 2.500 (3) (\(10\bar 5\)), 2.340 (3) (\(12\bar 2\)), 1.817 (3) (215), 1.489 (3) (402). The chemical composition is as follows, wt %: 20.44 Cu, 35.85 Fe, 0.65 Ni, 0.14 Co, 43.15 S, total is 100.23. The empirical formula calculated on the basis of 7 atoms is Cu_0.969(Fe_1.934Ni_0.034Co_0.007)_1.975S_4.056. According to its mode of occurrence, the mineral was formed as a result of low temperature processes involving metamorphic hydrothermal solutions.     

FEG-EPMA mapping and Fe-Ti oxide mineral chemistry of Brahmaputra River sediments in Bangladesh: provenance and petrogenetic implications

The present research deals with the FEG-EPMA mapping and Fe-Ti oxide mineral chemistry of Brahmaputra River sediments in Bangladesh. Major heavy minerals in the sediments consist of garnet (8.5–21.3%), kyanite (5.35–11.9%), monazite (2.3–5.3%), sillimanite (1.8–4.7%), zircon (3.6–9.1%), and a considerable amount of opaques mainly Fe-Ti oxide minerals (23.1–35.4%). The detrital Fe-Ti oxide minerals carry significant clues to the parent rocks or sources. In these contexts, detrital opaques (Fe-Ti oxides) have been analyzed with an electron probe microanalyzer (EPMA). These opaques (Fe-Ti oxide) display six types of textural patterns, dominantly seriate with granular, emulsion, and acicular sandwich structures and trellis type of textural patterns. These textural patterns belong to five intergrowths of Fe-Ti oxide minerals such as (1) ilmenite-hematite, (2) magnetite-ilmenite, (3) hematite-rutile, (4) ilmenite-hematite-rutile, and (5) ilmenite-rutile, where ilmenite-hematite intergrowth is common. Alteration is seen in both exsolved and unexsolved ilmenites. Textural patterns and mineral chemistry of the studied ilmenite minerals provide lines of evidence of low-temperature magmatic inheritance, later modified by diffusional processes. The estimated temperature and oxygen fugacity from the magnetite-ilmenite exsolution range from 547.6 to 558.2 °C and from 10^?21.4 to 10^?21.7, respectively. The data are also consistent with hematite-ilmenite temperature (between 537 and 540 °C) and oxygen fugacity (10^?21.7 to 10^?21.9) measurements in Cox’s Bazar beach placers. These temperatures and oxygen fugacities specify Fe-Ti oxide assemblages equilibrated in a T-fO₂ field very near to the FMQ buffer curve suggesting a crustal source (magmatic and/or metamorphic), which is modified significantly by metamorphic processes.     

Uptake of Cu2+ by the calcium carbonates vaterite and calcite as studied by continuous wave (cw) and pulse electron paramagnetic resonance

The investigation of the Cu²⁺ uptake by the calcium carbonate minerals vaterite and calcite with continuous wave and pulse electron paramagnetic resonance (EPR) yields information on a molecular scale about the relevant complexation reactions at the mineral–water interface. The structural assignment is based on changes in the coordination geometry of the copper complexes. Magnetic interactions of the unpaired Cu²⁺ electron with nuclei of ¹³C-labeled carbonate ligands and protons from water or hydroxyl ligands in the first and second coordination spheres of the cation are detected by pulse EPR techniques. Our results show that the Cu²⁺ ions are rapidly dehydrated upon adsorption on the mineral surface. The strong surface binding is due to monodentate coordination to three or four carbonate surface ions, comparable to chelate complexation in solution. The formation of square-planar or square-pyramidal copper complexes at exposed surface sites like kinks and steps yields a convincing explanation for the inhibition of calcium carbonate growth and dissolution. Upon recrystallization the Cu²⁺ ions are integrated into the calcite lattice where they exhibit a dynamic Jahn–Teller effect. The resulting local lattice distortions are expected to destabilize the Cu_xCa_(1−x)CO₃(s) solid solution. Our results support the concept of a dynamic calcium carbonate surface, covered by a thin, structured surface layer. The detailed structural information obtained for Cu²⁺ provides a better understanding of the interaction of other metal ions with calcium carbonate minerals.     

Evidence for aqueous clusters as intermediates during zinc sulfide formation

Using zinc sulfide as an example, we demonstrate a plausible stepwise process for the formation of minerals from low temperature aqueous solutions. The process occurs with the formation of soluble complexes that aggregate into soluble rings and clusters. The final moiety in solution has a structure similar to the moiety in the first formed solid, which is a restatement of the Ostwald step rule. Titrations of aqueous Zn(II) with bisulfide indicate that sulfide clusters form at concentrations of 20 μM (or less) of metal and bisulfide. Precipitation does not occur according to voltammetric measurements using a mercury electrode and UV-VIS (ultra-violet to visible) spectroscopic data. UV-VIS data and filtration experiments indicate that the material passes through 0.1 μm Nuclepore and 1000 dalton filters. The complexes form rapidly (k_f > 10⁸ Ms⁻¹), are kinetically inert to dissociation and thermodynamically strong. Although a neutral complex of 1:1 (ZnS) empirical stoichiometry initially forms, an anionic complex with an empirical 2 Zn:3 S stoichiometry results with continued addition of sulfide. Gel electrophoresis confirms the existence of a cluster that is negatively charged with a molecular mass between 350 and 750 daltons. On the basis of known mineral and thiol complex structures for these systems, a tetrameric cluster unit of Zn₄S₆(H₂O)₄⁴⁻ is likely. Molecular mechanic calculations show that this cluster is structurally analogous to ZnS minerals (particularly sphalerite) and is a viable precursor to mineral formation and a product of mineral dissolution.The formation of Zn₄S₆(H₂O)₄⁴⁻ can occur from condensation of Zn₃S₃(H₂O)₆ rings, which are neutral molecular clusters. The Zn atoms on one Zn₃S₃(H₂O)₆ ring combine with the S atoms on another Zn₃S₃(H₂O)₆, to lead to higher order clusters with loss of water. The Zn₄S₆⁴⁻ species form by the cross-linking of two neutral Zn₃S₃ rings by added sulfide; thus a Zn–S–Zn bridge forms across the rings with subsequent rearrangement and condensation to Zn₄S₆⁴⁻; this combination results in a sphalerite-like cluster. If the rings condense without additional sulfide, a wurtzite-like structure could form. All condensations result in sulfide displacement of water from Zn to form Zn–S bonds. Water loss is an example of an entropy-driven process, which leads to a more favorable thermodynamic process. These clusters would be resistant to oxidation by O₂. Voltammetric experiments indicate neutral and anionic clusters for Zn and agree with ion chromatographic data from the sulfidic waters of the Black Sea.     

Batisivite,V<Subscript>8</Subscript>Ti<Subscript>6</Subscript>[Ba(Si<Subscript>2</Subscript>O)]O<Subscript>28</Subscript>, a new mineral species from the derbylite group

Batisivite has been found as an accessory mineral in the Cr-V-bearing quartz-diopside metamorphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. A new mineral was named after the major cations in its ideal formula (Ba, Ti, Si, V). Associated minerals are quartz, Cr-V-bearing diopside and tremolite; calcite; schreyerite; berdesinskiite; ankangite; V-bearing titanite; minerals of the chromite-coulsonite, eskolaite-karelianite, dravite-vanadiumdravite, and chernykhite-roscoelite series; uraninite; Cr-bearing goldmanite; albite; barite; zircon; and unnamed U-Ti-V-Cr phases. Batisivite occurs as anhedral grains up to 0.15–0.20 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black and opaque, with a black streak and resinous luster. Batisivite is white in reflected light. The microhardness (VHN) is 1220–1470 kg/mm² (load is 30 g), the mean value is 1330 kg/mm². The Mohs hardness is near 7. The calculated density is 4.62 g/cm³. The new mineral is weakly anisotropic and bireflected. The measured values of reflectance are as follows (λ, nm—R _max ^′ /R _min ^′ ): 440—17.5/17.0; 460—17.3/16.7; 480—17.1/16.5; 500—17.2/16.6; 520—17.3/16.7; 540—17.4/16.8; 560—17.5/16.8; 580—17.6/16.9; 600—17.7/17.1; 620—17.7/17.1; 640—17.8/17.1; 660—17.9/17.2; 680—18.0/17.3; 700—18.1/17.4. Batisivite is triclinic, space group P \(\overline 1\); the unit-cell dimensions are: a = 7.521(1) Å, b = 7.643(1) Å, c = 9.572(1) Å, α = 110.20°(1), β = 103.34°(1), γ = 98.28°(1), V = 487.14(7) ų, Z = 1. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %)(hkl)] are: 3.09(8)(12\(\overline 2\)); 2.84, 2.85(10)(021, 120); 2.64(8)(21\(\overline 3\)); 2.12(8)(31\(\overline 3\)); 1.785(8)(32\(\overline 4\)), 1.581(10)(24\(\overline 2\)); 1.432, 1.433(10)(322, 124). The chemical composition (electron microprobe, average of 237 point analyses, wt %) is: 0.26 Nb₂O₅, 6.16 SiO₂, 31.76 TiO₂, 1.81 Al₂O₃, 8.20 VO₂, 26.27 V₂O₃, 12.29 Cr₂O₃, 1.48 Fe₂O₃, 0.08 MgO, 11.42 BaO; the total is 99.73. The VO₂/V₂O₃ ratio has been calculated. The simplified empirical formula is (V _4.8 ³⁺ Cr_2.2V _0.7 ⁴⁺ Fe_0.3)_8.0(Ti_5.4V _0.6 ⁴⁺ )_6.0[Ba(Si_1.4Al_0.5O_0.9)]O₂₈. An alternative to the title formula could be a variety (with the diorthogroup Si₂O₇) V₈Ti₆[Ba(Si₂O₇)]O₂₂. Batisivite probably pertains to the V ₈ ³⁺ Ti ₆ ⁴⁺ [Ba(Si₂O)]O₂₈-Cr ₈ ³⁺ Ti ₆ ⁴⁺ [Ba(Si₂O)]O₂₈ solid solution series. The type material of batisivite has been deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

(Au,Ag)Te2 Minerals from Epithermal Gold Deposits in Japan

Chemical composition and mode of occurrences of (Au, Ag)Te₂ minerals such as calaverite (AuTe₂), sylvanite (AuAgTe₄) and krennerite ((Au, Ag)Te₂) in epithermal gold telluride ores from Suzaki, Kawazu and Teine are examined. In the ores from Suzaki, (Au, Ag)Te₂ minerals occur in microbands of tellurides and fine quartz. The minerals in telluride bands change from krennerite, via calaverite‐native tellurium, to sylvanite, in the order of crystallization. A sample from Kawazu contains sylvanite and native tellurium with stutzite, hessite and tetradymite in the coarser gray quartz part. The Teine sample also contains sylvanite and native tellurium with barite and quartz. The peak patterns of XRD of calaverite, krennerite and sylvanite from Suzaki are almost identical to that of JCPDS 43–1472, JCPDS 8–20 and JCPDS 9–477, respectively. The Te, Au, Cu, and Ag contents of calaverite from Suzaki range from 56.4 to 57.9 wt.%, from 41.6 to 42.6 wt.%, from 0.28 to 0.45 wt.% and from 0.14 to 0.31 wt.%, respectively, corresponding to the formula Au_0.97Ag_0.01Cu_0.02Te₂. The Te, Au, Ag, and Cu contents of krennerite from Suzaki range from 59.6 to 61.4 wt.%, from 31.3 to 33.6 wt.%, from 4.91 to 6.13 wt.% and from 0.66 to 0.80 wt.%, respectively, corresponding to the formula Au_0.71Ag_0.22Cu_0.05Te₂ with Au and Ag ranging from 0.68 to 0.74 and from 0.20 to 0.25, respectively. The Te, Au, Ag, and Cu contents of sylvanite from Suzaki range from 61.5 to 63.4 wt.%, from 24.1 to 27.4 wt.%, from 10.0 to 12.5 wt.% and from 0.00 to 0.12 wt.%, respectively. The Te, Au, Ag, and Cu contents of sylvanite from Kawazu range from 62.7 to 63.3 wt.%, from 23.5 to 24.1 wt.%, from 12.0 to 12.5 wt.% and from 0.09 to 0.16 wt.%, respectively. The Te, Au, Ag, Cu and Fe contents of sylvanite from Teine range from 61.8 to 63.5 wt.%, from 23.6 to 24.7 wt.%, from 11.9 to 13.3 wt.%, from 0.01 to 1.65 wt.% and from 0.00 to 0.02 wt.%, respectively. The average formulae of sylvanite from Suzaki, Kawazu, and Teine are expressed as Au_1.06Ag_0.94Cu_0.02Te₄, Au_1.00Ag_0.95Cu_0.02Te₄ and Au_1.01Ag_0.95Cu_0.06Te₄, respectively. Judging from the mineral assemblages of these ores and other localities, Au–Te mineralization in the Japanese Islands can be divided into four types: native gold–calaverite at Date and Agawa, krennerite(?native tellurium) at Osore‐zan and Mutsu, sylvanite–native tellurium–hessite at Teine, Kawazu, Kobetsuzawa, and Kato, and polyminerallic assemblages at Suzaki and Kushikino. The pH–Eh diagram of aqueous tellurium species and tellurium minerals at 250°C indicates that (Au, Ag)Te₂ minerals in epithermal gold telluride mineralization would have been formed under middle to low Eh and acidic (to intermediate) pH conditions. It is possible that dilute tellurium‐containing fluid would scavenge dilute gold.     

Anatomy of a large Ag–Pb–Zn deposit in the Great Xing'an Range,northeast China: metallogeny associated with Early Cretaceous magmatism

The Bairendaba vein-type Ag–Pb–Zn deposit, hosted in a Carboniferous quartz diorite, is one of the largest polymetallic deposits in the southern Great Xing'an Range. Reserves exceeding 8000 tonnes of Ag and 3 million tonnes of Pb?+?Zn with grades of 30 g/t and 4.5% have been estimated. We identify three distinct mineralization stages in this deposit: a barren pre-ore stage (stage 1), a main-ore stage with economic Ag–Pb–Zn mineralization (stage 2), and a post-ore stage with barren mineralization (stage 3). Stage 1 is characterized by abundant arsenopyrite?+?quartz and minor pyrite. Stage 2 is represented by abundant Fe–Zn–Pb–Ag sulphides and is further subdivided into three substages comprising the calcite–polymetallic sulphide stage (substage 1), the fluorite–polymetallic sulphide stage (substage 2), and the quartz–polymetallic sulphide stage (substage 3). Stage 3 involves an assemblage dominated by calcite with variable pyrite, galena, quartz, fluorite, illite, and chlorite. Fluid inclusion analysis and mineral thermometry indicate that the three stages of mineralization were formed at temperatures of 320–350°C, 200–340°C, and 180–240°C, respectively. Stage 1 early mineralization is characterized by low-salinity fluids (5.86–8.81 wt.% NaCl equiv.) with an isotopic signature of magmatic origin (δ¹⁸O_fluid = 10.45–10.65‰). The main ore minerals of stage 2 precipitated from aqueous–carbonic fluids (4.34–8.81 wt.% NaCl equiv.). The calculated and measured oxygen and hydrogen isotopic compositions of the ore-forming aqueous fluids (δ¹⁸O_fluid = 3.31–8.59‰, δD_fluid?=??132.00‰ to??104.00‰) indicate that they were derived from a magmatic source and mixed with meteoric water. Measured and calculated sulphur isotope compositions of hydrothermal fluids (δ³⁴S_∑S?=??1.2–3.8‰) indicate that the ore sulphur was derived mainly from a magmatic source. The calculated carbon isotope compositions of hydrothermal fluids (δ¹³C_fluid?=??26.52‰ to??25.82‰) suggest a possible contribution of carbon sourced from the basement gneisses. The stage 3 late mineralization is dominated (1.40–8.81 wt.% NaCl equiv.) by aqueous fluids. The fluids show lower δ¹⁸O_fluid (?16.06‰ to??0.70‰) and higher δD_fluid (?90.10‰ to??74.50‰) values, indicating a heated meteoric water signature. The calculated carbon isotope compositions (δ¹³C_fluid?=??12.82‰ to??6.62‰) of the hydrothermal fluids in stage 3 also suggest a possible contribution of gneiss-sourced carbon. The isotopic compositions and fluid chemistry indicate that the ore mineralization in the Bairendaba deposit was related to Early Cretaceous magmatism.     

Romanorlovite,a New Copper and Potassium Hydroxychloride from the Tolbachik Volcano,Kamchatka, Russia

A new mineral romanorlovite has been found in the upper, moderately hot zones of two fumaroles, Glavnaya Tenoritovaya (Major Tenorite) and Arsenatnaya (Arsenate), located at the second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with avdoninite in both fumaroles, and in Glavnaya Tenoritovaya, it is also associated with belloite, sylvite, carnallite, mitscherlichite, sanguite, chlorothionite, eriochalcite, chrysothallite, and mellizinkalite. Romanorlovite occurs as prismatic, equant, or tabular tetragonal crystals up to 0.1 mm in size, crystal clusters up to 0.5 mm, and crusts up to 2 × 2 mm in area. The mineral is transparent with vitreous luster. Its color varies from yellow-brown to dark brown, and tiny crystals are honey- or golden-yellow. Cleavage is not observed. Romanorlovite is brittle. The Mohs hardness is ca ~3. The calculated density varies from 2.72 to 2.79 g/cm³ depending on the content of admixed Pb. The mineral is optically uniaxial (–), ω = 1.727(3), ε = 1.694(2). The Raman spectrum has been reported. The chemical composition of the holotype sample (wt %; electron microprobe data, contents of О and H calculated by stoichiometry) is as follows: 21.52 K, 0.89 Pb, 28.79 Cu, 0.02 Zn, 44.74 Cl, 4.85 O_calc, 0.41 H_calc, total 101.22. Its empirical formula calculated based on Cl₂₅ with (ОН)₄(Н2О)₂ is K_10.90Pb_0.09Cu_8.97Zn_0.01Cl₂₅(OH)₄ · 2H₂O. The simplified formula is K₁₁Cu₉Cl₂₅(OH)₄ · 2H₂O (Z = 4). Romanorlovite is tetragonal, space group[ I4/mmm. The unit cell parameters are (1) holotype: a = 17.5804(7), c = 15.9075(6) Å, V = 4916.5(3) ų; (2) the sample enriched in Pb on which the crystal structure was refined: a = 17.5538(19), c = 15.8620(17) Å, V= 4887.7(9) ų. The strongest reflections of the powder XRD pattern (d, Å–I[hkl]) are 12.48–56[110], 11.74–36[101], 8.80–100[200], 7.97–34[002], 6.71–40[112], 3.165–32[512], 2.933–80[215, 433], 2.607–38[514]. The mineral is named in honor of Roman Yu. Orlov (1929-2005), Russian mineralogist and physicist, who worked in the Department of Mineralogy, Moscow State University.     

Lahnsteinite, Zn4(SO4)(OH)6 · 3H2O, a new mineral from the Friedrichssegen Mine, Germany

A new mineral, lahnsteinite, has been found in the dump of the Friedrichssegen Mine, Bad Ems district, Rhineland-Palatinate (Rheinland-Pfalz), Germany. Lahnsteinite, occurring as colorless tabular crystals in the cavities of goethite, is associated with pyromorphite, hydrozincite, quartz, and native copper. The Mohs’ hardness is 1.5; the cleavage is perfect parallel to (001). D _calc = 2.995 g/cm³, D _meas = 2.98(2) g/cm³. The IR spectrum is given. The new mineral is optically biaxial, negative, α = 1.568(2), β = 1.612(2), γ = 1.613(2), 2V _meas = 18(3)°, 2V _calc = 17°. The chemical composition (wt %, electron microprobe data; H₂O was determined by gas chromatography of ignition products) is as follows: 3.87 FeO, 1.68 CuO, 57.85 ZnO, 15.83 SO₃, 22.3 H₂O, total is 101.53. The empirical formula is (Zn_3.3Fe_0.27Cu_0.11)_Σ3.91(S_0.98O₄)(OH)₅ · 3H_2.10O. The crystal structure has been studied on a single crystal. Lahnsteinite is triclinic, space group P1, a = 8.3125(6), b = 14.545(1), c = 18.504(2) Å, α = 89.71(1), β = 90.05(1), γ = 90.13(1)°, V = 2237.2(3) ų, Z = 8. The strong reflections in the X-ray powder diffraction pattern [d, Å (I, %)] are: 9.30 (100), 4.175 (18), 3.476 (19), 3.290 (19), 2.723 (57), 2.624 (36), 2.503 (35), 1.574 (23). The mineral has been named after its type locality near the town of Lahnstein. The type specimen of lahnsteinite is deposited in the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration number 4252/1.