Dissolution kinetics of galena in acid NaCl solutions at 25—75 °C

Experiments on dissolution kinetics of galena were performed in 1 mol l⁻¹ NaCl solutions at pH 0.43–2.45 and 25–75 °C. When the dissolution reaction is far from equilibrium, a linear relation exits between the dissolution rate, r, and the H⁺ ion activity, [H⁺]. The rate law for galena dissolution is given by the following equation: r=k[H⁺]. With respect to H⁺, the dissolution reaction is in the first order. The apparent rate constant, k, has values of 2.34×10⁻⁷ mol m⁻² s⁻¹ at 25 °C, 1.38×10⁻⁶ mol m⁻² s⁻¹ at 50 °C, and 7.08×10⁻⁶ mol m⁻² s⁻¹ at 75 °C. The activation energy of dissolution reaction is 43.54 kJ mol⁻¹. The mechanism of dissolution is suggested to be surface chemical reaction, and the rate determining step is the dissociation of the Pb–S bond of the surface complex, which releases Pb²⁺ into the solution.     

Loss of metals from pelites during regional metamorphism

In aluminous metapelites the ratio H₂O⁺/K₂O decreases with increasing metamorphic grade and degree of reaction. This ratio is a very practical indicator for the progress of the mineral reconstitution during progressive metamorphism. With decreasing values of the ratio H₂O⁺/ K₂O the Cu concentration and the following element ratios also decrease either continuously or in stepwise fashion: Tl/K₂O, Ba/K₂O, Pb/K₂O, Bi/K₂O, Hg/K₂O, Sr/Na₂O, Zn/(Fe²⁺+Mg), Cd/(Fe²⁺+Mg); Rb/K₂O remains approximately constant. In the aluminous metapelites of the Damara Orogen in Namibia the following losses occur between the biotite isograd and anatexis: 61% Cu, 20% Tl, 34% Ba, 59% Pb, 86% Bi, 46% Hg, 30% Sr, 25% Zn, 31% Cd. Thus the potential of regional metamorphism to form hydrothermal deposits in the low grade environment should not be neglected.     

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.     

Constraints of C–O–S–Pb isotope compositions and Rb–Sr isotopic age on the origin of the Tianqiao carbonate-hosted Pb–Zn deposit,SW China

The Tianqiao Pb–Zn deposit in the western Yangtze Block, southwest China, is part of the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province. Ore bodies are hosted in Devonian and Carboniferous carbonate rocks, structurally controlled by a thrust fault and anticline, and carried about 0.38 million tons Pb and Zn metals grading > 15% Pb + Zn. Both massive and disseminated Pb–Zn ores occur either as veinlets or disseminations in dolomitic rocks. They are composed of ore minerals, pyrite, sphalerite and galena, and gangue minerals, calcite and dolomite. δ³⁴S values of sulfide minerals range from + 8.4 to + 14.4‰ and display a decreasing trend from pyrite, sphalerite to galena (δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena). We interpret that reduced sulfur derived from sedimentary sulfate (gypsum and barite) of the host Devonian to Carboniferous carbonate rocks by thermal–chemical sulfate reduction (TSR). δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite range from –5.3 to –3.4‰ and + 14.9 to + 19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid was a mixture origin of mantle, marine carbonate rocks and sedimentary organic matter. Sulfide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.378 to 18.601, ²⁰⁷Pb/²⁰⁴Pb = 15.519 to 15.811 and ²⁰⁸Pb/²⁰⁴Pb = 38.666 to 39.571) that are plotted in the upper crust Pb evolution curve and overlap with that of Devonian to Carboniferous carbonate rocks and Proterozoic basement rocks in the SYG province. Pb isotope compositions suggest derivation of Pb metal from mixed sources. Sulfide minerals have ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7125 to 0.7167, higher than Sinian to Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than basement rocks. Again, Sr isotope compositions are supportive of a mixture origin of Sr. They have an Rb–Sr isotopic age of 191.9 ± 6.9Ma, possibly reflecting the timing of Pb–Zn mineralization. C–O–S–Pb–Sr isotope compositions of the Tianqiao Pb–Zn deposit indicate a mixed origin of ore-forming fluids, which have Pb–Sr isotope homogenized before the mineralization. The Permian flood basalts acted as an impermeable layer for the Pb–Zn mineralization hosted in the Devonian–Carboniferous carbonate rocks.     

Lead enrichment, adsorption and speciation in urban garden soils under long-term wastewater irrigation in northern Nigeria

Unsafe lead (Pb) concentrations in leafy vegetables raised in urban and peri-urban agricultural production systems have been reported across cities in Northern Nigeria, even though Pb concentrations in soils are within regulatory safe levels. This study examined the soil enrichment, adsorption and chemical species of Pb in urban garden fields irrigated with untreated wastewater at three industrial locations in Kano, northern Nigeria. Total Pb in the soil profiles ranged from 9 to 91 mg kg^?1 and decreased rapidly from the surface to the subsurface layer, but attaining nearly constant concentration at depth ≥1.2 m in the profiles. The potentially labile Pb maintained fairly constant concentration with depth up to 0.9 m, but decreased fairly rapidly with depth thereafter. There was a significant Pb enrichment of the soils, extending up to 30–60 cm depth in the soil profiles. The adsorption of Pb by the soils increased drastically with pH, and attained maximum adsorption at pH ≥ 7.0 in the surface layer, and at pH ≥ 6 in the subsurface layer. The surface soils adsorbed between 85 and 97 % of added Pb at pH ≤ 5. Free Pb²⁺ activities in soil solution accounted for between 46 and 87 % at pH 5–7 of total dissolved Pb (Pb_T). The quantifiable chemical species of Pb in solution consisted mainly of PbOH⁺, PbSO ₄ ^· , PbCl⁺ and PbOH ₂ ^· which accounted for between 0.9 and 26 % of Pb_T in soil solution at pH ≥ 5.0, but declining to between 0.1 and 2.1 % at pH ≥ 7.5. There was no apparent equilibrium between Pb²⁺ activities and known Pb-compounds in the soils. It was concluded from the data that reports of excess Pb concentrations in leafy vegetables raised in these soils are consistent with high free Pb²⁺ activities maintained in soil solution by these predominantly sandy-textured soils.     

Dissolution of arsenopyrite (FeAsS) and galena (PbS) in the presence of desferrioxamine-B at pH 5

Microorganisms and higher plants produce biogenic ligands, such as siderophores, to mobilize Fe that otherwise would be unavailable. In this paper, we study the stability of arsenopyrite (FeAsS), one of the most important natural sources of arsenic on Earth, in the presence of desferrioxamine (DFO-B), a common siderophore ligand, at pH 5. Arsenopyrite specimens from mines in Panasqueira, Portugal (100-149 μm) that contained incrustations of Pb, corresponding to elemental Pb as determined by scanning electron microscopy-electron diffraction spectroscopy (SEM-EDX), were used for this study. Batch dissolution experiments of arsenopyrite (1 g L⁻¹) in the presence of 200 μM DFO-B at initial pH (pH₀) 5 were conducted for 110 h. In the presence of DFO-B, release of Fe, As, and Pb showed positive trends with time; less dependency was observed for the release of Fe, As, and Pb in the presence of only water under similar experimental conditions. Detected concentrations of soluble Fe, As, and Pb in suspensions containing only water were found to be ca. 0.09 ± 0.004, 0.15 ± 0.003, and 0.01 ± 0.01 ppm, respectively. In contrast, concentrations of soluble Fe, As, and Pb in suspensions containing DFO-B were found to be 0.4 ± 0.006, 0.27 ± 0.009, and 0.14 ± 0.005 ppm, respectively. Notably, the effectiveness of DFO-B for releasing Pb was ca. 10 times higher than that for releasing Fe. These results cannot be accounted for by thermodynamic considerations, namely, by size-to-charge ratio considerations of metal complexation by DFO-B. As determined by SEM-EDX, elemental sample enrichment analysis supports the idea that the Fe-S subunit bond energy is limiting for Fe release. Likely, the mechanism(s) of dissolution for Pb incrustations is independent and occurs concurrently to that for Fe and As. Our results show that dissolution of arsenopyrite leads to precipitation of elemental sulfur, and is consistent with a non-enzymatic mineral dissolution pathway. Finally, speciation analyses for As indicate variability in the As(III)/As(V) ratio with time, regardless of the presence of DFO-B or water. At reaction times <30 h, As(V) concentrations were found to be 50-70%, regardless of the presence of DFO-B. These results are interpreted to indicate that transformations of As are not imposed by ligand-mediated mechanisms. Experiments were also conducted to study the dissolution behavior of galena (PbS) in the presence of 200 μM at pH₀ 5. Results show that, unlike arsenopyrite, the dissolution behavior of galena shows coupled increases in pH with decreases in metal solubility at t > 80 h. Oxidative dissolution mechanisms conveying sulfur oxidation bring about the production of {H⁺}. However, dissolution data trends for arsenopyrite and galena indicate {H⁺} consumption. It is plausible that the formation of Pb species is dependent on {H⁺} and {OH⁻}, namely, stable surface hydroxyl complexes of the form (pH₅₀ 5.8) and for pH values 5.8 or above.     

Petrogenetic and Metallogenetic Background of the Dajing Cu–Sn–Ag–Pb–Zn Ore Deposit, Inner Mongolia, and Characteristics of the Mineralizing Fluid

Abstract: The Dajing Cu–Sn–Ag–Pb–Zn ore deposit, Inner Mongolia of China, is a fissure‐filling hydrothermal ore deposit that occurs within the Upper Permian Linxi group. No magmatic pluton and volcanic rocks outcrop on the surface of the deposit. Most of ore veins show clear‐cut boundary with country rocks. Wallrock alterations that include silicification, carbonation, chlori–tization, and sericitization are generally weak and occur in the close vicinity of ore veins. Mineralization is divided into three stages: (1) cassiterite–arsenopyrite–quartz stage, (2) sulfide stage, and (3) Pb–Zn–Ag–carbonate stage. These mineralization stages have distinct ranges of homogenization temperatures, 290–350C for Stage 1, 260–320C for Stage 2, and 150–250C for Stage 3. However, salinities for Stages 1, 2, and 3 overlap and range between 2.2 and 10.4 wt % NaCl equivalent. The dD values relative to V‐SMOW of inclusion water from quartz are lower than –88% and centered at –100 to –130%. The δ³⁴S values relative to CDT of sulfide ore minerals and δ¹³C values relative to PDB of carbonate gangue minerals, vary from –0.3 to +2.6%, and from –7.0 to –2.9%, respectively. Integrated isotopic data point to two major contributions to the mineralizing fluid that include a dominant meteoric‐derived water and the other from hypogene magma for sulfur and carbon species. Analyses of inclusion gas and liquid compositions are performed. The H₂O and CO₂ are the two most abundant gaseous components, whereas SO₄^2‐ and Cl^‐, and Na⁺, Ca²⁺, and K⁺ are the major anions and cations, respectively. A linear trend is shown on the gaseous H₂O versus CO₂ plot. Phase separation is excluded as cause for the trend on the basis of isotope data and fluid inclusion microthermometry. In addition, a weak wallrock alteration does not support fluid‐rock interaction as an efficient mechanism. Hence, the linear H₂O–CO₂ trend is interpreted in terms of absorption or dilution of CO₂–dominant magmatic vapor by meteoric‐derived water. Cooling effects resulting from dilution may have caused precipitation of ore minerals. Major and trace element compositions of regional granites show a high‐K calc–alkaline characteristics and an arc–affinity. Lead isotopic compositions of galena samples from the Dajing deposit exhibit elevated U/Pb and Th/Pb ratios. These characteristics indicate a common source of supra subduction zone mantle wedge for regional granites and metals from the Dajing deposit.     

Structure of heavy metal sorbed birnessite. Part III: Results from powder and polarized extended X-ray absorption fine structure spectroscopy

The local structures of divalent Zn, Cu, and Pb sorbed on the phyllomanganate birnessite (Bi) have been studied by powder and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy. Metal-sorbed birnessites (MeBi) were prepared at different surface coverages by equilibrating at pH 4 a Na-exchanged buserite (NaBu) suspension with the desired aqueous metal. Me/Mn atomic ratios were varied from 0.2% to 12.8% in ZnBi and 0.1 to 5.8% in PbBi. The ratio was equal to 15.6% in CuBi. All cations sorbed in interlayers on well-defined crystallographic sites, without evidence for sorption on layer edges or surface precipitation. Zn sorbed on the face of vacant layer octahedral sites (□), and shared three layer oxygens (O_layer) with three-layer Mn atoms (Mn_layer), thereby forming a tridentate corner-sharing (TC) interlayer complex (Zn-3O_layer-□-3Mn_layer). ^TCZn complexes replace interlayer Mn²⁺ (Mn_inter²⁺) and protons. ^TCZn and ^TCMn_inter³⁺ together balance the layer charge deficit originating from Mn_layer⁴⁺ vacancies, which amounts to 0.67 charge per total Mn according to the structural formula of hexagonal birnessite (HBi) at pH 4. At low surface coverage, zinc is tetrahedrally coordinated to three O_layer and one water molecule (^[IV]TC complex: (H₂O)-^[IV]Zn-3O_layer). At high loading, zinc is predominantly octahedrally coordinated to three O_layer and to three interlayer water molecules (^[VI]TC complex: 3(H₂O)-^[VI]Zn-3O_layer), as in chalcophanite (^[VI]ZnMn₃⁴⁺O₇·3H₂O). Sorbed Zn induces the translation of octahedral layers from −a/3 to +a/3, and this new stacking mode allows strong H bonds to form between the ^[IV]Zn complex on one side of the interlayer and oxygen atoms of the next Mn layer (O_next): O_next…(H₂O)-^[IV]Zn-3O_layer. Empirical bond valence calculations show that O_layer and O_next are strongly undersaturated, and that ^[IV]Zn provides better local charge compensation than ^[VI]Zn. The strong undersaturation of O_layer and O_next results not only from Mn_layer⁴⁺ vacancies, but also from Mn³⁺ for Mn⁴⁺ layer substitutions amounting to 0.11 charge per total Mn in HBi. As a consequence, ^[IV]Zn,Mn_layer³⁺, and Mn_next³⁺ form three-dimensional (3D) domains, which coexist with chalcophanite-like particles detected by electron diffraction. Cu²⁺ forms a Jahn-Teller distorted ^[VI]TC interlayer complex formed of two oxygen atoms and two water molecules in the equatorial plane, and one oxygen and one water molecule in the axial direction. Sorbed Pb²⁺ is not oxidized to Pb⁴⁺ and forms predominantly ^[VI]TC interlayer complexes. EXAFS spectroscopy is also consistent with the formation of tridentate edge-sharing (^[VI]TE) interlayer complexes (Pb-3O_layer-3Mn), as in quenselite (Pb²⁺Mn³⁺O₂OH). Although metal cations mainly sorb to vacant sites in birnessite, similar to Zn in chalcophanite, EXAFS spectra of MeBi systematically have a noticeably reduced amplitude. This higher short-range structural disorder of interlayer Me species primarily originates from the presence of Mn_layer³⁺, which is responsible for the formation of less abundant interlayer complexes, such as ^[IV]Zn TC in ZnBi and ^[VI]Pb TE in PbBi.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

The solubility of FeS

The solubility of FeS_m, synthetic nanoparticulate mackinawite, in aqueous solution was measured at 23 °C from pH 3-10 using an in situ precipitation and dissolution procedure and the solution species was investigated voltammetrically. The solubility is described by a pH-dependent reaction and a pH-independent reaction. The pH-dependent dissolution reaction can be described by

FeS_m+2H⁺→Fe²⁺+H₂S     

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H₂O)₅[(UO₂)(SiO₃(OH)]₂, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb²⁺-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl₂-HCl solution of pH 2. They are part of an aged silica coating of composition Si₂O₂(OH)₄(H₂O)_n. An amorphous layer forms on the surface of uranophane in a MgCl₂-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO₃)₂-HCl and BaCl₂-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO₃)₂-HCl < BaCl₂-HCl < CaCl₂-HCl < HCl < SrCl₂-HCl < MgCl₂-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl⁺).     

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

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

A quantum-mechanical study of the (110) surface of sphalerite (ZnS) and its interaction with Pb<Superscript>2+</Superscript> species

 The structure of the (110) surface of sphalerite has been studied using mainly quantum-mechanical (QM) methods. The experimentally observed puckering of the surface is well reproduced by periodic plane wave density functional calculations. Water adsorption on this surface is modelled using this QM approach and is used to judge the accuracy of less computationally demanding cluster methods. A cluster model, thus validated, is used to study the possible modes of interaction of Pb²⁺ ions with the (110) surface. It is found that adsorption of hydrated PbO and PbOH⁺ is energetically feasible and leads to Pb–O distances compatible with REFLEXAFS data. Received: 22 April 2002 / Accepted: 23 October 2002 Acknowledgements We thank EPSRC for support of this research.     

A theoretical study of the absorption spectra of Pb+ and Pb3+ in site K+ of microcline: application to the color of amazonite

The blue-green color of amazonite has been assigned by various authors to ions Pb⁺ (6 s)² (6 p) and/or Pb³⁺ (6 s) in site of K⁺ of microcline. Owing to the complex which forms between the ion Pb³⁺ and the lone pairs of the oxygen atoms surrounding it, the peripheral electron of Pb³⁺ passes on the levels (6 p) of the latter, which results in a great similarity of the spectra of Pb⁺ and Pb³⁺ in amazonite (the transition energies are multiplied by a factor greater than 1), whereas, in the isolated state, these spectra are completely different from one another. An analytical development of the crystal field around a site K⁺ is established. Under the effect of the crystal field, the transition ² P _1/2→² P _3/2 (6 p) is split into two double transitions. The lower transition only falls in the visible domain (1.6–1.8 eV for Pb⁺), the second in U−V. The green color would arise from the ion Pb⁺, whereas the blue one would be attributed to the ion Pb³⁺. Received: 23 January 1997 / Revised, accepted: 10 September 1997     

Microbial dissolution of calcite at T = 28 °C and ambient pCO2

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species (Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO₂ over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH₄⁺ as an N source, and H₂PO₄⁻ as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H₂O-CO₂-CaCO₃ system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH₄⁺ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H₂CO₃ generated by dissolution of atmospheric CO₂ (H₂CO₃ + CaCO₃ → Ca²⁺ + 2HCO₃⁻) and H⁺ released during NH₄⁺ uptake (H⁺ + CaCO₃ → Ca²⁺ + HCO₃⁻). Reaction with H₂CO₃ and H⁺ supplied ∼45% and 55% of the total Ca²⁺ and ∼60% and 40% of the total HCO₃⁻, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH₄⁺ was ∼2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H₂CO₃. In lactate bearing reactors, most H⁺ generated by NH₄⁺ uptake reacted with HCO₃⁻ produced by lactate oxidation to yield CO₂ and H₂O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H₂CO₃ at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH₄⁺ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.     

Crystal chemistry of natural and synthetic lead oxohalides: II. Crystal structure of Pb7O4(OH)4Br2

Crystals of lead oxobromide Pb₇O₄(OH)₄Br₂ have been synthesized by hydrothermal method. The structure of the new compound has been studied with X-ray single-crystal diffraction analysis. The compound is monoclinic, space group C112₁; unit-cell dimensions are a = 5.852(4), b = 13.452(7), c = 19.673(9) Å, γ = 90.04°, V = 1548.7(15) ų. The structure has been solved by direct methods and refined to R ₁ = 0.1138 for 1847 observed Pb₇O₄(OH)₄Br₂ unique reflections. The structure contains seven symmetrically independent bivalent Pb atoms. The coordination polyhedrons of Pb are strongly distorted due to stereochemical activity of unshared electron pair 6s ². Oxygen atoms are tetrahedrally coordinated by four Pb²⁺ cations with the formation of oxocentered tetrahedrons OPb₄. The compound is based on [O₂Pb₃]²⁺ double chains formed by OPb₄ tetrahedrons. (OH)Pb₂ dimers combine the [O₂Pb₃]²⁺ chains into 3D framework. Channels in the framework are parallel to [100] and are occupied by Br anions.     

EPR study of coordination of Ag and Pb cations in BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals and barium borate glasses

It is shown the possibility to determine the coordination of paramagnetic ions in disordered solid structures, e.g., in barium borate glasses. For this purpose the electron paramagnetic resonance (EPR) method was used to study α-and β-BaB₂O₄ crystals and glasses of 45·BaO × 55·B₂O₃ and 40·BaO × 60·B₂O₃ (mol%) composition activated by Ag⁺ and Pb²⁺ ions. After the samples were exposed to X-rays at 77 K, different EPR centers were observed in them. In α-and β-BaB₂O₄ crystals and glasses the EPR centers Ag²⁺, Ag⁰, Pb⁺, Pb³⁺, and hole centers of O⁻ type were studied. The EPR parameters of these centers and their arrangement in crystal structure were determined. It is shown that Pb³⁺ ions in β-BaB₂O₄ crystals occupy Ba²⁺ position in an irregular polyhedron from the eight oxygen, whereas in α-BaB₂O₄ crystals they occupy Bа₂ position in a sixfold coordination. Pb⁺ ions in α-BaB₂O₄ crystals occupy Bа₁ position in a ninefold coordination from oxygen. In barium borate glasses, Pb³⁺ ions were studied in coordination polyhedron from six oxygen atoms and in a polyhedron from nine to ten oxygen atoms. It is assumed that the established difference in the structural position of Pb³⁺ ions in glasses is due to their previous incorporation in associative cation–anion complexes (AC) and “free” structure-forming cations (FC). Computer simulations have been performed to analyze the stability of specific associative complexes and to compare their bond lengths with experimental data.     

Fracture induced emission of alkali atoms from feldspar

Emission of neutral atoms (K and Na) and molecules (H₂O and KOH) observed during fracture of K-feldspar have been accounted for by two independent mechanisms. H₂O and KOH emissions are attributed to the venting of fluid-filled inclusions, while emission of atomic K is due to surface effects accompanying cleavage of crystalline feldspar. The intensity of emitted potassium, at least 6 × 10¹⁴ atoms/cm² of surface area, is sufficient to affect K activities in solution during microbrecciation in the presence of rock-dominated fluids.     

In situ Pb and bulk Sr isotope analysis of the Yinchanggou Pb-Zn deposit in Sichuan Province (SW China): Constraints on the origin and evolution of hydrothermal fluids

The Yinchanggou Pb-Zn deposit, located in southwestern Sichuan Province, western Yangtze Block, is stratigraphically controlled by late Ediacaran Dengying Formation and contains >0.3 Mt of metal reserves with 11 wt% Pb + Zn. A principal feature is that this deposit is structurally controlled by normal faults, whereas other typical deposits nearby (e.g. Maozu) are controlled by reverse faults. The origin of the Yinchanggou deposit is still controversial. Ore genetic models, based on conventional whole-rock isotope tracers, favor either sedimentary basin brine, magmatic water or metamorphic fluid sources. Here we use in situ Pb and bulk Sr isotope features of sulfide minerals to constrain the origin and evolution of hydrothermal fluids. The Pb isotope compositions of galena determined by femtosecond LA-MC-ICPMS are as follows: ²⁰⁶Pb/²⁰⁴Pb = 18.17–18.24, ²⁰⁷Pb/²⁰⁴Pb = 15.69–15.71, ²⁰⁸Pb/²⁰⁴Pb = 38.51–38.63. These in situ Pb isotope data overlap with bulk-chemistry Pb isotope compositions of sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.11–18.40, ²⁰⁷Pb/²⁰⁴Pb = 15.66–15.76, ²⁰⁸Pb/²⁰⁴Pb = 38.25–38.88), and both sets of data plotting above the Pb evolution curve of average upper continental crust. Such Pb isotope signatures suggest an upper crustal source of Pb. In addition, the coarse-grained galena in massive ore collected from the deep part has higher ²⁰⁶Pb/²⁰⁴Pb ratios (18.18–18.24) than the fine-grained galena in stockwork ore sampled from the shallow part (²⁰⁶Pb/²⁰⁴Pb = 18.17–18.19), whereas the latter has higher ²⁰⁸Pb/²⁰⁴Pb ratios (38.59–38.63) than the former (²⁰⁸Pb/²⁰⁴Pb = 38.51–38.59). However, both types of galena have the same ²⁰⁷Pb/²⁰⁴Pb ratios (15.69–15.71). This implies two independent Pb sources, and the metal Pb derived from the basement metamorphic rocks was dominant during the early phase of ore formation in the deep part, whereas the ore-hosting sedimentary rocks supplied the majority of metal Pb at the late phase in the shallow part. In addition, sphalerite separated from different levels has initial ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7101 to 0.7130, which are higher than the ore formation age-corrected ⁸⁷Sr/⁸⁶Sr ratios of country sedimentary rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7083–0.7096), but are significantly lower than those of the ore formation age-corrected basement rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7243–0.7288). Again, such Sr isotope signatures suggest that the above two Pb sources were involved in ore formation. Hence, the gradually mixing process of mineralizing elements and associated fluids plays a key role in the precipitation of sulfide minerals at the Yinchanggou ore district. Integrating all the evidence, we interpret the Yinchanggou deposit as a strata-bound, normal fault-controlled epigenetic deposit that formed during the late Indosinian. We also propose that the massive ore is formed earlier than the stockwork ore, and the temporal-spatial variations of Pb and Sr isotopes suggest a certain potential of ore prospecting in the deep mining area.     

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.