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.     

Trace elements in galena and sphalerite and their geochemical significance in distinguishing the genetic types of Pb-Zn ore deposits

This paper deals with the trace elements Ag, Sb, Bi in galens and Fe, Mn, Cd, Se, Te, Ga and In in sphalerite from 60 Pb-Zn deposits in China and other countries. The contents of the selected trace elements and their ratios show regular variations from one type of Pb-Zn deposits to another. These elements or their ratios are plotted onto Pb-lnAg, lnSb-lnBi, lnGa-lnIn, Fe-Cd, Fe-Cd-Mn and Zn/Cd-Se/Te-Ga/In diagrams. On the basis of these diagrams, the deposits associated with magmatism(type I), those associated with volcanism(type II), the sedimentary-reformed deposits (type III) and sedimentary-metamorphic deposits(type IV) can be well distinguished. Types I and III have the definite fields in all the diagrams. Types II and IV also have their own fields in lnGa-lnIn and Zn/Cd-Se/Te-Ga/In diagrams. The author considers that these diagrams are applicable to distinguishing the genetic types of Pb-Zn deposits.     

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.     

Determination of rhenium and osmium by ICP-MS for galena and sphalerite

Digestion with aqua regia in a Carius tube and separation of Re with anion exchange resin is commonly employed for Re–Os dating of molybdenite and pyrite. However, the recovery of Re is extremely low when this routine anion exchange method is applied to galena, causing difficulty in Re–Os dating of galena. In this study, we investigated the mechanism of Re loss during sample preparation and tested a revised procedure for Re–Os dating of galena and sphalerite.     

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.     

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

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

The selective flotation of galena from sphalerite with special reference to the effects of particle size

The selectivity of galena flotation from a synthetic mixture with sphalerite and quartz and from a typical Broken Hill ore has been determined. It was found that the selectivity was limited by the relative flotabilities of coarse galena and sphalerite of intermediate sizes. The use of split conditioning in the preparation for flotation resulted in significant improvements in lead-zinc selectivity for both samples. By contrast the use of conventional zinc depressants in the flotation of the ore resulted in only slight changes in the behaviour of the minerals and had no discernible effect on the selectivity.     

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.     

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.     

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。

     

Minor and trace elements in HF-soluble zircons

Electron probe analysis of a group of HF-soluble zircons from porphyroids of the Thuringian Forest, Germany, established yttrium, phosphorus, and iron to be the significant minor constituents. It is believed that these elements render the zircon structure HF-soluble. The Y content varies from about 6500–48000 ppm=0.83–6.10% Y₂O₃; the P concentrations range from a low of about 790 to a maximum of 4000 ppm=0.18–0.92% P₂O₅; the Fe content varies from about 400–15000 ppm=0.06–2.10% Fe₂O₃. Although both Y and P are distributed throughout each given grain, they are sometimes mutually enriched in growth zones. These zones are also resolved in reflected light micrographs and the electron images.     

Origin of galena and sphalerite mineralization in the Koru Volcanics,Biga Peninsula,Turkey: insights from MELTS modelling and SUPCRT calculations

Seismic and gravity data have disclosed correlations between the structure of the major folded belts with the surface of the basaltic layer and the Moho. The major structural elements of the Greater Caucasus province are reviewed, though with all too generalized maps for reference. These structures are reviewed in the light of their evolution in three stages: the first ending in the Medial-Late Jurassic, the second ending in the Middle Paleogene, and the third occupying the Oligocene-Neogene-Quaternary periods. A major synclinorium and anticlinorium of long duration are postulated. The granite layer is summarized in an isopachous map. This is correlated with a contour map of the Moho. Inheritances of earlier geosynclinal cycles (Hercynian). The primary geosyncline is related to planetary rifts. The thickest part of the crust is centered on the meganticlinorium in the Alpine structures of the Caucasus. Formation of folds, foredeeps, and folding after sedimentation is related to development of the granite layer during continental evolution. Deep-seated piercement of the granite into the cover in the axial portion is indicated. The observable seismicity is also correlated with evolution of the granite layer.--B. N. Cooper.     

Minor and trace elements in some meteoritic minerals

The mineral phases including olivine, orthopyroxene, clinopyroxene, troilite, nickel-iron, plagioclase, chromite and the phosphates were separated from several meteorites. These were a hypersthene chondrite (Modoc), a bronzite chondrite (Guareña), an enstatite chondrite (Khairpur), and two eucrites (Haraiya and Moore County); diopside was separated from the Nakhla achondrite. The purified minerals were analyzed for trace and minor elements by spark source mass spectrometry and instrumental neutron activation analysis. On the meteorites examined our results show that Co, Ni, Cu, Ge, As, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt and Au are entirely or almost entirely siderophile; Na, Rb, Sr, Y, Ba and the rare earth elements lithophile; Se chalcophile. The transition elements So, Ti, V, Cr and Mn are lithophile in most stony meteorites, but show chalcophile affinities in the enstatite chondrites (and enstatite achondrites), as do Zn, Zr and Nb. In the ordinary chondrites Ga shows both lithophile and siderophile affinities, but becomes entirely siderophile in the enstatite chondrites. Molybdenum and tellurium show strong siderophile and weaker chalcophile affinity. The lithophile elements are distributed among the minerals according to the crystallochemical factors, the most effective controlling factor being ionic size.     

Minor elements in quartz from hydrothermal-metamorphic veins in the Nether Polar Ural Province

Vein quartz from the Nether Polar Ural Province was examined by atomic emission spectrometry, gas chromatography, electron paramagnetic resonance, and electron microscopy. According to atomic emission spectrometric analysis, the total concentration of Al, Fe, Mg, Ti, Ca, Na, K, and other minor elements in the quartz varies from 8 to 47 ppm. The lowest concentrations of minor elements were detected in the granulated quartz. Giant-crystalline milk-white quartz is noted for higher concentrations of minor elements, including Na, K, and Ca, because it contains gas-liquid inclusions. The fine-grained quartz contains very small mineral inclusions and is thus noted for elevated concentrations of Ca, Fe, K, Mg, and Ti. Gas chromatographic data on the gas phase separated from the quartz at its heating indicate that this phase contains H₂O, CO₂, and other components. The H₂O concentration reaches 429 ??g/g, while the CO₂ content is commonly no higher than 20 ??g/g. Gas separation is at a maximum at temperatures of 100?C600°C, when gasliquid inclusions decrepitate, as is typical, first of all, of the giant-crystalline milk-white quartz. Gas separation continues at higher temperatures (below 1000°C) but is much less intense. The electron microscopic examination of quartz grains after their acid treatment indicates that the surface of these grains is covered by caverns of various morphology and size, which were produced by the partial dissolution of the quartz and the opening of its gas-liquid and mineral inclusions occurring near the surface; the inclusions were not, however, completely removed. The crystal structure of the quartz contains minor Al, Ge, Na, Li, Ti, and Fe. The lowest concentrations of Al and Ge paramagnetic centers are typical of the granulated (recrystallized) and fine-grained quartz. The giant-crystalline quartz, including its transparent varieties, and individual quartz crystals, first of all their smoky-citrine varieties, contain higher concentrations of minor elements. In the Nether Polar Ural Province, granulated quartz is potentially promising for producing especially pure quartz concentrates. The quality of the translucent coarse-to giant-crystalline quartz, which predominates in the resources and reserves, is deteriorated by gas-liquid inclusions in it and requires deep processing of the raw minerals.     

新疆火烧云超大型铅锌矿床闪锌矿微量(稀散)元素组成特征与指示意义北大核心CSCD

位于青藏高原西北部的新疆和田火烧云超大型铅锌矿床是近年来我国乃至全球最重要的铅锌找矿发现之一。该矿床矿石矿物以铅锌碳酸盐为主(菱锌矿和白铅矿),同时还发育有少量的铅锌硫化物矿体,目前对于火烧云矿床的成因仍存在较大分歧。本文以矿床硫化物矿体中的闪锌矿为研究对象,通过LAICP-MS微量元素测试和Mapping分析,揭示闪锌矿中微量元素(稀散元素)的富集规律和赋存状态,为矿床成因的厘定提供依据。结果表明,火烧云铅锌矿床闪锌矿中微量元素分布不均一,含量变化较大,以富集Cd、Tl、Ge等稀散元素为特征;Cd、Tl、Ge、Mn、As、Hg等微量元素以类质同象的形式赋存在闪锌矿中,其中,Cu与Ge的含量呈现较好的线性关系,推测在闪锌矿结晶过程中存在3Zn^(2+)Ge^(4+)+2Cu^(+)的替代机制,而Cd进入闪锌矿的方式可能为Zn^(2+)Cd^(2+),且Cd的异常富集可能与闪锌矿中低Fe含量有关;闪锌矿中微量元素Ga、Ge、Fe、Mn、In的组成特征指示了硫化物矿体形成于低温环境(65~140℃),与MVT型矿床的成矿温度一致。总体上,该矿床中的闪锌矿以富集Cd、Tl、Ge,贫Fe、Mn、In为特征,这与典型的MVT型矿床基本一致,明显区别于SEDEX、VMS与矽卡岩型铅锌矿床。结合矿床地质特征,笔者认为火烧云铅锌矿床中硫化物矿体成因与金顶铅锌矿床类似,属于MVT型矿床。     

内蒙古黄岗梁铁锡矿床闪锌矿LA-ICP-MS微量元素组成及其指示意义

黄岗梁铁锡矿床位于大兴安岭中南段晚古生代增生造山带。矿区内闪锌矿产于矽卡岩中,可分为浸染状和层纹状闪锌矿。本文对两种闪锌矿进行了高精度LA-ICP-MS元素含量测试,结果表明矿区两种闪锌矿具有相同成因特征,闪锌矿中Mn、Cu、As、In较富集,Ga、Ge、Cd含量较低,而As、Sn、Bi、Pb含量变化较大。Cu、Sn、Bi、Pb等元素在闪锌矿中以独立矿物赋存,Mn、Fe、Ga、Ge、Cd、In、Sb以类质同像形式赋存在闪锌矿晶格中。In/Ga、In/Ge比值较低,Zn/Cd比值为233~250,指示闪锌矿形成于中高温环境。Cd/Fe、Cd/Mn比值分别小于0.1和0.5,指示闪锌矿成因与岩浆活动有关,In Ge特征图解也指示其矽卡岩成因。通过与国内外典型矿床闪锌矿微量元素特征对比,结合矿床地质特征认为黄岗梁铁锡矿床中闪锌矿属于与燕山期岩浆作用有关的中高温矽卡型闪锌矿。     

Trace elements of Indium-bearing sphalerite from tin-polymetallic deposits in Bolivia,China and Japan: A femto-second LA-ICPMS study

Indium-bearing tin-polymetallic base metal deposits in Japan (Toyoha, Ashio and Akenobe), China (Dulong and Dachang), and Bolivia (Potosi, Huari Huari, Bolivar and Porco), were studied using femto-second Laser Ablation ICPMS (fsLA-ICPMS) and EPMA analyses for major and minor elements in sphalerite, paying special attention to In concentrations.Sphalerite is a principal mineral in these tin-polymetallic deposits and a broad range of In concentration is measured in the ores. There are distinct differences in mode of occurrence of the sphalerite and the distribution of In. The highest In concentration (up to 18 wt.%) occur as a Zn–In mineral within black sphalerite zones in an oscillatory-zoned sphalerite from the Huari Huari deposits. Additionally, jamesonite from the Huari Huari deposit also contains anomalous In values, ranging from several hundreds to thousands μg/g. Sphalerite from the Toyoha and the other Bolivian deposits are characterized by oscillatory and chemical zoning, whereas those from Akenobe and the Chinese deposits are represented by homogeneous distribution of In. The 1000In/Zn values of sphalerite are in good agreement with those of the ore grade for each of the selected tin polymetallic deposits indicating that sphalerite is the principal host of In.The In-bearing sphalerite principally involves the combined coupled substitutions (2Zn^2 +) ↔ (Cu⁺, In^3 +), (3Zn^2 +) ↔ (Cu⁺, Ag⁺, Sn^4 +) and (3Zn^2 +) ↔ (2Cu⁺, Sn^4 +). The first of these is apparent in sphalerite from Huari Huari and Bolivar, whereas the second is prominent in sphalerite from Toyoha, Ashio, Potosi, Porco and Dachang. Akenobe and Dulong sphalerite features the dominant coupled substitution of (2Zn^2 +) ↔ (Cu⁺ or Ag⁺, In^3 +), owing to their poor Sn content. Occasionally, sub-micron inclusions of minerals such as stannite and Pb–Sb-bearing sulfides can occur in sphalerite, contributing to high Cu–Sn and high-Ag contents, respectively. The observed correlations of each element in the In–Cu–Ag–Sn-bearing sphalerite can be proposed as a fundamental reason for the indium enrichment related to sulfur-rich oxidized magmatism. In addition, the Ag content in sphalerite is considered a possible indicator of formation depth, which ranges from plutonic to subvolcanic environments.     

闪锌矿LA-ICP-MS微量元素组成对西藏纳如松多铅锌矿床成矿作用的制约

西藏纳如松多铅锌矿床是冈底斯北侧Pb-Zn-Ag-Mo成矿带中规模最大且最为典型的与斑岩系统相关的铅锌矿床,发育有多种矿化样式。本次研究选取该矿床隐爆角砾岩型矿体中的闪锌矿开展LA-ICP-MS微量元素组成研究,发现其中Fe含量不高,不属于高温铁闪锌矿,以富集Cd、Mn、Co,而贫In、Ga、Ge、Se、Te为特征。闪锌矿In/Ga值、In/Ge值及Zn/Cd值指示纳如松多隐爆角砾岩型铅锌矿体形成于中低温环境,且属于热液型矿床的范畴。闪锌矿原位微量元素特征指示纳如松多铅锌矿床的形成主要受到来自于岩浆热液作用的影响和控制,成矿物质主要来自于深部斑岩岩浆系统。     

云南澜沧老厂铅锌多金属矿床闪锌矿微量元素组成

云南澜沧老厂是三江成矿带南段最重要铅锌多金属矿床之一,通过LA-ICPMS和ICP-MS微量元素组成分析结果表明,矿床中闪锌矿属于铁闪锌矿,形成于中温环境,以富Fe、Mn、Cd和In等元素为特征,其中Fe、Mn、Cd、In等元素以类质同象形式赋存于闪锌矿中,而Pb、Cu 、Sn和Bi等元素含量变化范围较大,以显微包裹体(方铅矿和黄铜矿等)赋存于闪锌矿中。本矿床闪锌矿中Fe和Mn等微量元素组成与VMS矿床类似,但In和Cd的异常富集可能暗示其独特的成矿机制。总体而言,其闪锌矿微量元素组成特征和与燕山-喜山期花岗岩叠加改造作用有关的喷流沉积铅锌矿床(如云南白牛厂和广东大宝山)相似,而明显不同与矽卡岩型矿床(如核桃坪与鲁子园),更不同于MVT型铅锌矿床(牛角塘、会泽和勐兴)和金顶铅锌矿床。结合矿床产出地质特征,笔者认为云南澜沧老厂铅锌多金属矿区经历了古、中、新特提斯期不同程度的拉张与闭合发展演化,使矿床多期同位叠加成矿特征明显,其闪锌矿微量元素组成具喷流沉积成因特征,深部喜山期花岗斑岩与铅锌成矿作用关系不大,但在其侵入过程中叠加改造作用使闪锌矿等硫化物组合及其微量元素组成发生一定程度变化(如局部富集Sn和Sb等元素)。此外,两种测试方法结果对比可以看出,在硫化物单矿物微量元素分析中,LA-ICPMS相对于ICP-MS分析具有更高精度,不仅可以进行硫化物原位分析,并能即时了解微量元素在硫化物中赋存状态,而且克服了ICP-MS分析中由于单矿物选样不纯致使测试误差大等弱点。     

Determination of major and trace elements in sphalerite using laser ablation double focusing sector field ICP-MS

The analytical performance of laser ablation (LA) for the determination of Co, Fe, Cd, Ag, Mn, Cu and S in sphalerite was evaluated using double focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS). Samples were collected from Zinkgruvan, situated in the south central Sweden. The use of Zn for internal standardisation, together with correction for FeS impurities in sphalerite, allows straightforward quantification without using external methods for the determination of the actual Zn content. LA–ICP-SFMS results were compared with data obtained by conventional pneumatic nebulisation introduction of sample solutions following acid digestion. Good agreement between the two methods was obtained for homogeneously distributed elements. For the majority of the elements under consideration, LA–ICP-SFMS precision was better than 10% RSD.