Polytypism of natural sphalerite and its typomorphic significance

Structural modifications of natural and synthetic sulfides of zinc and conditions of their origination are examined. Data on polytypism of sphalerites from deposits in different ore-bearing formations in eastern Zabaykal'ye are reported. Effect of isomorphous iron on polytypism of natural sphalerites is investigated. — Authors     

天然闪锌矿矿物学特征与光催化性能

本文采集了我国19个产地的天然闪锌矿进行矿物学和光催化性能研究。样品皆为立方Zn S结构,化学成分变化较大,其中Fe对闪锌矿中Zn的替代范围为0.235%~14.826%(质量分数,下同),Cd对闪锌矿中Zn的替代范围为0.133%~1.576%。闪锌矿中Fe含量由低到高,导致颜色由浅变深直至呈黑色,半导体禁带宽度由大变小,估算获得天然闪锌矿的禁带宽度范围为3.18~2.28 e V,明显低于纯Zn S禁带宽度3.68 e V,光催化响应均在可见光范围。验证光催化实验结果表明含Fe较低、含Cd较高的天然闪锌矿可见光催化还原降解甲基橙的效果较佳,如可见光下1 g/L闪锌矿样品(含铁4.262%,含镉1.576%)对30 mg/L甲基橙催化反应4 h后的脱色降解率达到82.11%。天然闪锌矿中Fe含量影响着禁带宽度和光响应范围,Cd含量影响着光催化性能,为高附加值开发利用贱金属资源天然闪锌矿提供了科学依据。     

Phase differences between bed configuration and flow in natural environments, and their geological relevance

In nature where unsteady flows prevail, the characters of bed configurations lag, or differ in phase from, the flow conditions. This is demonstrated from quantitative data for dune beds in the Fraser River (Canada) and the Gironde Estuary (France), where the flow conditions change ahead of the bed form by as much as 1/4 period. Qualitative evidence for lag abounds, for instance, substantially unmodified dunes exposed during low water. The existence of lag appears to confuse attempts to establish from field data the relationships between bed-form properties and flow conditions and, at the same time, makes difficult the confident application to field situations of formulae based on steady-state experiments or theories. Unfamiliar types of field study and experiments are needed to increase understanding of the degree and precise significance of lag.     

Nuclear field shift in natural environments

The nuclear field shift (NFS) is an isotope shift in atomic energy levels caused by a combination of differences in nuclear size and shape and electron densities at the nucleus. The effect of NFS in isotope fractionation was theoretically established by Bigeleisen in 1996 [Bigeleisen J. (1996) J. Am. Chem. Soc. 118:3676–3680] and has been analytically measured in laboratory chemical exchange reactions. More recently, some isotopic variations of heavy elements (Hg, Tl, U) measured in natural systems as well as isotopic anomalies measured for lower-mass elements in meteorites have been attributed to the NFS effect. These isotopic variations open up new and exciting fields of investigations in Earth sciences. In this paper, we review the different natural systems in which NFS has been proposed to be the origin of isotopic variations.     

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.     

表生环境下闪锌矿氧化反应模拟实验

采用混合流反应器装置,进行了表生环境条件下闪锌矿氧化动力学模拟实验研究,选择Fe³⁺和O₂为氧化剂,实验条件为:温度20～55℃,pH=1.0～7.8、氧化剂Fe³⁺浓度1.0×10^-5～1.0×10^-2 mol/L,氧气流量0.5 L/min。实验结果表明,在Fe³⁺为氧化剂时,闪锌矿氧化速率随着Fe³⁺浓度的增加、温度升高、pH值降低而增加,且氧化过程中Zn和Cd的释放速率大致相同,其反应的活化能分别为Ea(Zn) 41.75 kJ/mol或Ea(Cd) 42.51 kJ/mol,表明闪锌矿氧化速率主要受矿物表面反应控制;而以氧气作为氧化剂时,随着pH值的变化闪锌矿的氧化机理发生变化,在pH值小于5.95范围内,闪锌矿氧化速率随着pH值的增加而降低,进入碱性范围后,随着pH值增加,闪锌矿氧化速率反而增加。对实验数据进行双对数处理并建立了闪锌矿的氧化速率公式。     

Reductive kinetics of the reaction between a natural ilmenite and carbon

The reductive degree and rate of Bama ilmenite concentrate by graphite under argon atmosphere were measured by using thermogravimetric analysis system at the temperatures from 850 °C to 1400 °C. The reduction degree of the ilmenite increased with temperature rise, the case similar to reaction rate. The higher the temperature was, the faster the reaction rate was. The phases before and after reduction and the morphology of reduced samples were identified by using X-ray diffraction and optical microscopy analysis, respectively. The reduction degree of the ilmenite decreased due to the presence of impurities. Manganese and magnesium oxide-rich zones formed which prevented complete reduction of Fe²⁺. In general, the reaction products were iron, Ti₃O₅, reduced rutiles and pseudobrookite solid solution. The kinetics was also discussed and it was found that the rate-controlling steps were different in the different temperature ranges.     

Arsenic fixation on iron-hydroxide-rich and plant litter-containing sediments in natural environments

Iron-hydroxide-rich and plant litter-containing sediments from natural sites contaminated with uranium mine tailing leachates were examined for their ability to adsorb arsenic. The samples with high contents of iron hydroxides (Fe_total concentration, >300 g kg⁻¹) exhibited remarkable fixation of arsenic (up to 40 g As kg⁻¹). This value corresponded approximately to the supersaturation point for natural iron hydroxides under the present conditions, and it was significantly lower than the value found for synthetic iron hydroxides. There was a strong correlation (R=0.8999) between the concentration of iron and that of arsenic at low arsenic contents, indicating adsorption on strong binding sites. Although all the samples had noticeable contents of organic carbon (plant litter), calcium, and manganese, no obvious effect of these elements on arsenic fixation could be detected. The amount of iron hydroxides was found the only fixation-controlling parameter immediately below a leaching water source.     

Minor elements in sphalerite and galena from Binnatal

The trace element contents of 23 sphalerites and galenas from Binnatal, Switzerland, have been determined. Most of these samples have been previously studied in respect to lead and sulphur isotope abundances. Coloration of sphalerites — varying from yellow to black for nearly identical iron contents — seems to be strongly influenced by the manganese content. A linear relationship between sulphur isotope composition and copper content in sphalerites was found. Trace elements in galenas show a significant inverse relationship between silver and copper. With the determination of the bismuth content, it is possible to distinguish several galena types; a similar grouping has been found by lead isotope determinations. The results of the trace analyses are discussed in connection with the occurrence of a large number of very rare and special Pb-As-sulphosalt minerals in the Binnatal dolomites.     

Partition of cadmium and manganese between coexisting sphalerite and galena from some Japanese epithermal deposits

Sphalerites from Japanese epithermal Pb-Zn vein-type deposits, namely, Yatani, Oizumi and Hosokura, contain 2900–3400 ppm cadmium and 760–2100 ppm manganese. And galenas from the same deposits contain cadmium and manganese 19.2–26.9 ppm and 7.8–218.3 ppm, respectively. The temperatures, evaluated from the partition of cadmium between coexisting sphalerite and galena, are consistent within a total range of 150°C at maximum within an individual deposit. No systematic change with depth can be observed at the Shoko-hi vein, Hosokura mine and Hompi vein, Yatani mine. In several samples, the temperatures obtained from the partition of cadmium have been compared with those obtained from sulfur isotope fractionations. Iron content in sphalerite coexisting with pyrite indicates that the deposition of ore minerals at these deposits may have taken place from ore-forming solutions in which H₂S or HS^– was the predominant dissolved sulfur species, and the solutions may have been free from in situ oxidation or reduction.     

Organic species of lanthanum in natural environments: Implications to mobility of rare earth elements in low temperature environments

Naturally occurring organic ligands, such as acetate, citrate, malonate, oxalate, and succinate, play important roles in mobility and accumulation of La and other rare earth elements in low temperature systems under Earth surface conditions. However, a comprehensive and consistent thermodynamic database covering the complexes of rare earth elements with those naturally occurring organic ligands is lacking. In this study, thermodynamic data of organic species of rare earth elements (REE) represented by La, with an emphasis on their aqueous complexes with organic ligands, are critically reviewed. The organic ligands covered by this study include acetate, citrate, malonate, oxalate and succinate. In this critical review, the Specific Interaction Theory (SIT) model is adopted for extrapolation to infinite dilution. This model is a reliable activity coefficient model valid for a wide range of ionic strengths. These critically reviewed data, including complex formation constants, SIT interaction coefficients and solubility product constants, would enable accurate modeling of the speciation and solubility of REE in various environments including high ionic strength environments, providing insight into mobility and enrichment of REE in various environments.     

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

闪锌矿的Cd含量与颜色关系

过去人们普遍认为黑色闪锌矿贫镉,浅色闪锌矿富镉。笔者统计了国内外74个矿床,385个Cd含量数据。其中33个矿床有不同颜色闪锌矿的Cd含量数据37组。闪锌矿从黑色到浅色,Cd含量依次降低的有15矿床,17组数据,占统计矿床的44.1%,数据组的48.6%;Cd含量逐渐增加有14个矿床,14组数据,分别占统计矿床的45.5%,数据组的38.9%;Cd含量先降后升,黑色闪锌矿含量最高的有2个矿床,2组数据,分别占统计矿床的6.1%,数据组的5.7%;Cd含量先减后增,浅色闪锌矿含量最高和先升后降,褐色闪锌矿含量最高的各有一个矿床,一组数据,分别各占统计矿床的3.0%,占数据组的2.9%。由此看来,黑色闪锌矿与浅色闪锌矿的Cd含量无明显差异,说明闪锌矿的Cd含量与其颜色无明显关系。     

激光剥蚀电感耦合等离子体质谱-电子探针分析白山堂铜矿中的黄铁矿成分

硫化物矿物中元素含量及其分布可示踪硫化物成矿过程、辨别金属来源和沉积过程的物理化学条件,在地质学、矿床学等领域具有重要的应用价值。激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）已成功应用于硫化物矿物元素微区分析研究,但激光与物质作用产生的热效应严重制约分析结果的可靠性。本文建立了一种高精密度、高准确度的低温剥蚀LA-ICP-MS测定硫化物矿物多元素方法。采用自行研制的Peltier低温剥蚀池可有效抑制硫化物矿物LA-ICP-MS分析中的热效应,提高分析结果的精密度和准确度。扫描电子显微镜（SEM）表明：在低温（−30℃）条件下可在一定程度地抑制激光剥蚀引起的热效应,减少样品熔化和气溶胶气相再沉积;而通过气溶胶颗粒分析发现低温剥蚀可以减小样品气溶胶颗粒的平均尺寸,得到的颗粒粒径分布范围也较小。不同元素信号强度的精密度（RSD）从常温下的20.1%～34.4%改善到11.5%～15.8%,元素的检出限为0.054～0.077μg/g。将该低温LA-ICP-MS系统应用于实验室内部标样黄铜矿Ccp-1分析,测定值与参考值之间的标准偏差在7%以内。

     

Trace and minor elements in sphalerite from metamorphosed sulphide deposits

Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.     

Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

Geothermometry based on fractionation of Mn and Cd between coexisting sphalerite and galena from some carbonate-hosted sulfide deposits in India

Geothermometry based on the fractionation of Mn and Cd between coexisting sphalerite and galena from concordantly banded, strata-bound ores and younger vein ores of Rajpura-Dariba, Zawar, and Bandalamottu has been attempted. Different fractionation trends for the banded and vein ores in the same deposit at Rajpura-Dariba indicate different thermal regimes of final equilibration for the two varieties of ores. In contrast, a single trend incorporating both types of ores is suggestive of isothermal conditions of final equilibration for the banded and vein ores at Zawar. Unrealistically high temperatures obtained for the vein ores of Bandalamottu suggest equilibrium in the sphalerite-galena aggregates of this deposit was not attained. Thermometric data from Mn and Cd fractionation are compared with other independent geothermometric determinations obtained from fluid inclusion homogenization studies and based on phase equilibria. It has been found that, in general, the Cd-fractionation temperature (T_Cd) is a more reliable geothermometer than the Mn-fractionation temperature (T_Mn). This presumably may be due to the susceptibility of aqueous Mn species to subtle changes in in the ore fluid and consequent heterogeneity in Mn concentration in sphalerite, thus affecting the distribution coefficient. The investigation also suggests that T_Cd becomes increasingly more dependable when the ores are metamorphosed and reequilibrated at higher grades of metamorphism.     

Oxidation state and electronic configuration determination of copper in tetrahedrite group minerals by L-edge X-ray absorption spectroscopy

L-edge X-ray absorption spectroscopy employing a synchrotron radiation source has been used to study the electronic structure and valency of Cu in the chemically and structurally complex tetrahedrite group of minerals. Mechanical mixtures of Cu²⁺O and Cu⁺FeS₂ were used to estimate the relative cross sections of Cu²⁺ and Cu⁺; the absorption of Cu²⁺ at 931 eV is 25 times greater than that of Cu⁺ at 945 eV. Using this calibration, Cu²⁺/Cu ratios were found to vary from 0.00 to 0.054 in the tetrahedrite samples studied; the highest proportion of Cu²⁺ occurs in synthetic tetrahedrites with a composition close to Cu₁₂Sb₄S₁₃. This study reveals the utility of the technique for determining the valence state of copper in complex minerals, allowing the crystal chemistry to be more fully characterised.